NMR Spectroscopy Explained: Simplified Theory, Applications and Examples for Organic Chemistry and Structural Biology by Neil E. JacobsenNMR Spectroscopy Explained: Simplified Theory, Applications and Examples for Organic Chemistry and Structural Biology by Neil E. Jacobsen

NMR Spectroscopy Explained: Simplified Theory, Applications and Examples for Organic Chemistry and…

byNeil E. Jacobsen

Hardcover | August 24, 2007

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NMR Spectroscopy Explained : Simplified Theory, Applications and Examples for Organic Chemistry and Structural Biology provides a fresh, practical guide to NMR for both students and practitioners, in a clearly written and non-mathematical format. It gives the reader an intermediate level theoretical basis for understanding laboratory applications, developing concepts gradually within the context of examples and useful experiments.
  • Introduces students to modern NMR as applied to analysis of organic compounds.
  • Presents material in a clear, conversational style that is appealing to students.
  • Contains comprehensive coverage of how NMR experiments actually work.
  • Combines basic ideas with practical implementation of the spectrometer.
  • Provides an intermediate level theoretical basis for understanding laboratory experiments.
  • Develops concepts gradually within the context of examples and useful experiments.
  • Introduces the product operator formalism after introducing the simpler (but limited) vector model.
Neil E. Jacobsen, PHD, is the NMR Facility Manager in the Department of Chemistry at the University of Arizona in Tucson, where he also teaches graduate-level NMR courses. He received his PhD in organic chemistry at the University of California-Berkeley and gained experience in protein NMR spectroscopy at the University of Washington a...
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Title:NMR Spectroscopy Explained: Simplified Theory, Applications and Examples for Organic Chemistry and…Format:HardcoverDimensions:688 pages, 10.3 × 7.15 × 1.55 inPublished:August 24, 2007Publisher:WileyLanguage:English

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ISBN - 10:0471730963

ISBN - 13:9780471730965

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-26.4252 -1.2 TD [(carbon)-216.3(is)-216.3(unique)-216.3(within)-216.3(the)-216.3(molecule)-216.3(because)-216.3(it)-216.3(has)-216.3(tw)10(o)-216.3(bonds)-216.3(to)-216.3(oxygen)-216.3(whereas)-216.3(all)-216.3(of)-216.3(the)]TJ T* [(other)-186.3(carbons)-186.3(ha)20(v)15(e)-186.3(only)-186.3(one)-186.3(bond)-186.3(to)-186.3(oxygen.)-186.3(Normally)-186.3(the)-186.3(open-chain)-186.3(monosaccharide)-186.3(will)]TJ T* [(form)-282.3(a)-282.3()0(v)15(e)0(-)-282.3(o)0(r)-282.3(six-membered)-282.3(ring)-282.3(as)-282.3(a)-282.3(result)-282.3(of)-282.3(the)-282.3(addition)-282.3(of)-282.3(one)-282.3(of)-282.3(the)-282.3(alcohol)-282.3(groups)]TJ T* -0.0001 Tc [(\(usually)-198.2(the)-198.2(second)-198.2(to)-198.2(last)-198.2(in)-198.2(the)-198.2(chain\))-198.2(to)-198.2(the)-198.2(k)9.9(etone)-198.2(or)-198.2(aldehyde,)-198.2(changing)-198.2(the)-198.2(C)]TJ ET 0 G 0 J 0 j 0.498 w 10 M []0 d 1 i 436.635 242.45 m 442.613 242.45 l 436.635 244.442 m 442.613 244.442 l S BT 9.9626 0 0 9.9626 442.613 240.208 Tm 0 Tc [(O)-198.1(double)]TJ -32.3583 -1.2 TD [(bond)-250(to)-250(an)-250(OH)-250(group.)]TJ 1.2 -1.2 TD [(The)-222.1(six-membered)-222.1(ring)-222.1(of)-222.1(glucose)-222.1(prefers)-222.1(the)-222.1(chair)-222.1(conformation)-222.1(sho)25(wn)-222.1(in)-222.1(Figure)-222.1(1.12,)]TJ -1.2 -1.2 TD [(with)-369.4(nearly)-369.4(all)-369.4(of)-369.4(the)-369.4(OH)-369.3(groups)-369.4(arranged)-369.4(in)-369.4(the)-369.4(equatorial)-369.4(positions)-369.4(\(sticking)-369.4(out)-369.4(and)]TJ T* [(roughly)-147.1(in)-147.1(the)-147.1(plane)-147.1(of)-147.1(the)-147.1(ring\))-147.1(with)-147.1(the)-147.1(less)-147.1(b)20(ulk)15(y)-147.1(H)-147(atoms)-147.1(in)-147.1(the)-147.1(axial)-147.1(positions)-147.1(\(pointing)-147.1(up)]TJ T* [(or)-154.7(do)25(wn,)-154.7(abo)15(v)15(e)-154.7(or)-154.7(belo)25(w)-154.7(the)-154.7(plane)-154.7(of)-154.7(the)-154.7(ring\).)-154.7(This)-154.7(limits)-154.7(the)-154.7(dihedral)-154.7(angles)-154.7(between)-154.7(neigh-)]TJ T* 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/F8 1 Tf 2.041 0 TD [(\):)-305.9(60)]TJ /F3 1 Tf 7.5716 0 0 7.5716 340.1063 148.1831 Tm ()Tj /F8 1 Tf 9.9626 0 0 9.9626 347.4374 144.5667 Tm [(dihedral)-305.9(angle,)-305.9(small)]TJ /F4 1 Tf 8.7777 0 TD (!)Tj /F8 1 Tf 0.7498 0 TD (\()Tj /F3 1 Tf 0.333 0 TD ()Tj /F8 1 Tf 0.78 0 TD [(4)-305.9(Hz\).)]TJ ET endstream endobj 27 0 obj > /ExtGState > >> endobj 28 0 obj > endobj 29 0 obj > endobj 30 0 obj > endobj 31 0 obj > endobj 32 0 obj > stream BT /F8 1 Tf 7.9701 0 0 7.9701 159.9242 730.6316 Tm 0 g /GS1 gs 0 Tc 0 Tw [(EXAMPLES:)-250(NMR)-250(SPECTR)40(OSCOPY)-250(OF)-250(OLIGOSA)40(CCHARIDES)-250(AND)-250(TERPENOIDS)]TJ /F1 1 Tf 8.9664 0 0 8.9664 468.5827 730.6316 Tm ('')Tj /F8 1 Tf 9.9626 0 0 9.9626 118.8941 706.4592 Tm (\()Tj /F4 1 Tf 0.333 0 TD (!)Tj /F8 1 Tf 0.444 0 TD [(,)-229.5(i)0(n)-229.5(frequenc)15(y)-229.5(units)-229.5(of)-229.5(Hz\))-229.5(between)-229.5(the)-229.5(tw)10(o)-229.5(component)-229.5(peaks)-229.5(of)-229.5(the)-229.5(doublet)-229.5(is)-229.5(a)-229.5(measure)]TJ 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[(conformation.)-307.1(F)14.9(o)-0.1(r)-307.1(man)14.9(y)-307.1(common)-307.1(sugars)-307.1(\(glucose,)-307.1(galactose,)-307.1(etc.\))-307.1(all)-307.1(or)-307.1(nearly)-307.1(all)-307.1(of)-307.1(the)]TJ T* 0 Tc [(b)20(ulk)15(y)-297.8(groups)-297.8(on)-297.8(the)-297.8(ring)-297.8(\(OH)-297.8(or)-297.8(CH)]TJ 7.5716 0 0 7.5716 267.1556 645.1891 Tm (2)Tj 9.9626 0 0 9.9626 271.4698 646.6835 Tm [(OH\))-297.8(can)-297.8(be)-297.8(oriented)-297.8(in)-297.8(the)-297.8(less)-297.8(cro)25(wded)-297.8(equatorial)]TJ -15.3148 -1.2 TD -0.0001 Tc [(position)-196.9(in)-196.9(one)-196.9(of)-196.9(the)-196.9(tw)9.9(o)-196.9(chair)-196.9(forms.)-196.9(Thus)-196.9(the)-196.9(sugar)-196.9(ring)-196.9(is)-196.9(ef)24.9(fecti)24.9(v)14.9(ely)-196.9(lock)9.9(ed)-196.9(in)-196.9(this)-196.9(one)]TJ T* 0 Tc 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/F8 1 Tf 0.6588 0 TD [(\(about)-214.8(10)-214.8(Hz)]TJ -30.8497 -1.2 TD [(separation)-158.6(of)-158.6(the)-158.6(tw)10(o)-158.6(peaks)-158.6(of)-158.6(the)-158.6(doublet\).)-158.6(This)-158.6(does)-158.6(not)-158.6(mak)10(e)-158.6(intuiti)25(v)15(e)-158.6(sense)-158.6(because)-158.6(in)-158.6(this)]TJ T* [(arrangement)-181.1(the)-181.1(tw)10(o)-181.1(protons)-181.1(are)-181.1(as)-181.1(f)10(a)0(r)-181.1(apart)-181.1(as)-181.1(possible;)-181.1(ho)25(we)25(v)15(e)0(r)40(,)-181.1(it)-181.1(is)-181.1(the)-181.1(parallel)-181.1(alignment)]TJ T* [(of)-286.6(the)-286.7(tw)10(o)-286.7(CH)-286.6(bonds)-286.6(that)-286.6(leads)-286.7(to)-286.6(the)-286.7(strong)-286.7(coupling)-286.7(because)-286.7(the)]TJ /F4 1 Tf 27.4917 0 TD (!)Tj /F8 1 Tf 0.444 0 TD [(-coupling)-286.7(\(splitting\))]TJ -27.9357 -1.2 TD [(interaction)-312.7(is)-312.7(transmitted)-312.7(through)-312.7(bonds)-312.7(and)-312.7(not)-312.7(through)-312.7(space.)-312.7(T)80(w)10(o)-312.7(vicinal)-312.7(protons)-312.7(in)-312.7(a)]TJ T* [(lock)10(ed)-302.7(chair)-302.7(with)-302.7(an)-302.7(axialequatorial)-302.7(or)-302.7(an)-302.7(equatorialequatorial)-302.7(relationship)-302.7(will)-302.7(ha)20(v)15(e)-302.7(a)]TJ T* [(much)-260.2(smaller)-260.2(coupling)-260.2(constant)-260.2(\(much)-260.2(narro)25(wer)-260.2(pair)-260.2(of)-260.2(peaks)-260.2(in)-260.2(the)-260.2(doublet\))-260.2(in)-260.2(the)-260.2(range)]TJ T* [(of)-335.7(4)-335.7(Hz.)-335.7(Thus)-335.7(we)-335.7(can)-335.7(use)-335.7(NMR)-335.6(coupling)-335.7(constants)-335.7(to)-335.7(determine)-335.7(the)-335.7(stereochemistry)-335.7(of)]TJ T* -0.0007 Tc (sugars.)Tj 1.2 -1.2 TD -0.0001 Tc [(Here)-360.5(is)-360.5(ho)24.9(w)-360.5(w)-0.1(e)-360.5(can)-360.5(use)-360.5(this)-360.5(in)-360.5(the)-360.5(analysis)-360.5(of)-360.5(carbohydrate)]TJ 7.5716 0 0 7.5716 382.2489 482.9277 Tm 0 Tc (1)Tj 9.9626 0 0 9.9626 386.5328 479.3112 Tm [(H)-360.3(NMR)-360.3(spectra:)-360.4(most)]TJ -26.8642 -1.2 TD -0.0001 Tc [(naturally)-277.1(occurring)-277.1(sugars)-277.1(ha)19.9(v)14.9(e)-277.1(an)-277.1(equatorial)-277.1(OH)-277.1(at)-277.1(the)-277.1(2)-277.1(position)-277.1(\(numbering)-277.1(starts)-277.1(with)]TJ T* 0 Tc [(the)-290.3(anomeric)-290.3(position)-290.3(as)-290.3(number)-290.3(1\),)-290.3(so)-290.3(the)-290.3(proton)-290.3(at)-290.3(carbon)-290.3(2)-290.3(i)0(s)-290.3(axial)-290.3(in)-290.3(a)-290.3(six-membered)]TJ T* -0.0002 Tc [(ring)-252.5(sugar)54.8(.)-252.5(I)-0.2(n)-252.5(addition,)-252.5(the)-252.5(CH)]TJ 7.5716 0 0 7.5716 240.4429 441.9514 Tm 0 Tc (2)Tj 9.9626 0 0 9.9626 244.7571 443.4458 Tm -0.0001 Tc [(OH)-252.4(group)-252.4(is)-252.4(also)-252.4(equatorial)-252.4(in)-252.4(most)-252.4(p)9.9(yranose)-252.4(sugars.)-252.4(So)-252.4(if)]TJ -12.6335 -1.2 TD 0 Tc [(the)-280.5(anomeric)-280.5(proton)-280.5(is)-280.5(axial,)-280.5(we)-280.5(should)-280.5(see)-280.5(it)-280.5(in)-280.5(the)]TJ 7.5716 0 0 7.5716 329.7677 435.1071 Tm (1)Tj 9.9626 0 0 9.9626 334.0516 431.4906 Tm [(H)-280.5(NMR)-280.4(spectrum)-280.5(as)-280.5(a)-280.5(doublet)-280.5(with)]TJ -21.5964 -1.2 TD [(a)-320.2(lar)18(ge)-320.2(coupling)-320.2(\(10)-320.2(Hz\),)-320.2(because)-320.2(the)-320.2(H)]TJ 7.5716 0 0 7.5716 281.8607 418.0411 Tm (1)Tj 9.9626 0 0 9.9626 286.1446 419.5355 Tm (H)Tj 7.5716 0 0 7.5716 298.319 418.0411 Tm (2)Tj 9.9626 0 0 9.9626 305.8235 419.5355 Tm [(relationship)-320.2(is)-320.2(axialaxial.)-320.2(If)-320.2(the)-320.2(anomeric)]TJ -18.7631 -1.2 TD -0.0001 Tc [(proton)-217.9(is)-217.9(axial,)-217.9(then)-217.9(the)-217.9(anomeric)-217.9(OH)-217.9(or)-217.9(OR)-217.9(substituent)-217.9(is)-217.9(equatorial)-217.9(and)-217.9(the)-217.9(sugar)-217.9(is)-217.9(in)-217.9(the)]TJ /F2 1 Tf T* 0 Tc ()Tj /F8 1 Tf 0.7848 0 TD [(conguration)-204.8(\(anomeric)-204.8(OH)-204.7(or)-204.8(OR)]TJ /F4 1 Tf 14.0769 0 TD ( )Tj /F8 1 Tf 1.3158 0 TD [(to)-204.8(the)-204.8(CH)]TJ 7.5716 0 0 7.5716 317.9085 394.1308 Tm (2)Tj 9.9626 0 0 9.9626 322.2227 395.6251 Tm [(OH)-204.7(group)-204.8(at)-204.8(C)]TJ 7.5716 0 0 7.5716 379.8101 394.0897 Tm (5)Tj 9.9626 0 0 9.9626 384.0941 395.6251 Tm [(\).)-204.8(If)-204.8(we)-204.8(see)-204.8(an)-204.8(anomeric)]TJ -26.6195 -1.2 TD [(proton)-239.9(with)-239.9(a)-239.9(small)-239.9(\(4)-239.9(Hz\))-239.9(coupling,)-239.9(then)-239.9(the)-239.9(anomeric)-239.9(proton)-239.9(is)-239.9(equatorial,)-239.9(the)-239.9(OH)-239.9(or)-239.9(OR)]TJ T* [(group)-254.7(is)-254.7(axial,)-254.7(and)-254.7(we)-254.7(ha)20(v)15(e)-254.7(an)]TJ /F2 1 Tf 12.3842 0 TD (\015)Tj /F8 1 Tf 0.8257 0 TD -0.0003 Tc [(sugar)-255(\(anomeric)-255(OH)-255(or)-255(OR)]TJ /F4 1 Tf 11.1547 0 TD 0 Tc [( \012)15( )]TJ /F8 1 Tf 2.2957 0 TD [(to)-254.7(the)-254.7(CH)]TJ 7.5716 0 0 7.5716 423.3411 370.2204 Tm (2)Tj 9.9626 0 0 9.9626 427.6553 371.7148 Tm [(OH)-254.7(group)-254.7(at)]TJ -30.9919 -1.2 TD (C)Tj 7.5716 0 0 7.5716 125.5392 358.2242 Tm (5)Tj 9.9626 0 0 9.9626 129.8232 359.7596 Tm [(\).)-219(This)-219(reasoning)-219(w)10(orks)]TJ /F4 1 Tf 9.5591 0 TD ( \015)Tj /F8 1 Tf 1.941 0 TD [(if)-219(we)-219(are)-219(dealing)-219(with)-219(an)-219(aldop)10(yranose)-219(\(six-membered)-219(ring)]TJ -12.5971 -1.2 TD -0.0002 Tc [(sugar)-300.2(based)-300.2(on)-300.2(an)-300.2(open-chain)-300.2(aldehyde\))-300.2(with)-300.2(an)-300.2(equatorial)-300.2(OH)-300.2(at)-300.2(C)]TJ 7.5716 0 0 7.5716 394.035 346.3101 Tm 0 Tc (2)Tj 9.9626 0 0 9.9626 398.3492 347.8045 Tm [(;)-300(fortunately)65(,)-300(nature)]TJ -28.0503 -1.2 TD [(seems)-250(to)-250(f)10(a)20(v)20(o)0(r)-250(this)-250(situation.)]TJ /F1 1 Tf 0 -3 TD [(&)-1000(\015!)-250(  )]TJ /F8 1 Tf 0 -1.8 TD -0.0001 Tc [(If)-281.9(the)-281.9(anomeric)-281.9(carbon)-281.9(of)-281.9(a)-281.9(sugar)-281.9(in)-281.9(the)-281.9(ring)-281.9(form)-281.9(bears)-281.9(an)-281.9(OH)-281.8(substituent)-281.9(instead)-281.9(of)-281.9(OC)]TJ 0 -1.2 TD [(\(glycosidic)-287.6(linkage\),)-287.6(it)-287.6(will)-287.6(ha)19.9(v)14.9(e)-287.6(the)-287.6(possibility)-287.6(of)-287.6(opening)-287.6(to)-287.6(the)-287.6(open-chain)-287.6(aldehyde)-287.6(or)]TJ T* 0 Tc [(k)10(etone)-250.3(form)-250.3(and)-250.3(reclosing)-250.3(in)-250.3(either)-250.3(the)]TJ /F2 1 Tf 15.7389 0 TD (\015)Tj /F8 1 Tf 0.8213 0 TD [(or)-250.3(the)]TJ /F2 1 Tf 2.5555 0 TD ()Tj /F8 1 Tf 0.8303 0 TD [(conguration.)-250.3(This)-250.3(is)-250.3(called)-250.3(a)-250.3(reducing)]TJ -19.946 -1.2 TD -0.0001 Tc [(sugar)-390.5(because)-390.5(the)-390.5(open-chain)-390.5(aldehyde)-390.5(form)-390.5(is)-390.5(accessible)-390.5(and)-390.5(can)-390.5(be)-390.5(oxidized)-390.5(to)-390.5(the)]TJ T* 0 Tc [(carboxylic)-271.1(acid.)-271.1(The)-271.1(tw)10(o)-271.1(isomers)-271.1(\()]TJ /F2 1 Tf 13.9818 0 TD (\015)Tj /F8 1 Tf 0.8421 0 TD (and)Tj /F2 1 Tf 1.7151 0 TD ()Tj /F8 1 Tf 0.58 0 TD [(\))-271.1(are)-271.1(in)-271.1(equilibrium)-271.1(and)-271.1(we)-271.1(usually)-271.1(see)-271.1(about)-271.1(a)]TJ -17.1191 -1.2 TD [(2:1)-289.9(ratio)-289.9(of)]TJ /F2 1 Tf 4.8137 0 TD ()Tj /F8 1 Tf 0.8699 0 TD (to)Tj /F2 1 Tf 1.0679 0 TD (\015)Tj /F8 1 Tf 0.8609 0 TD [(forms.)-289.9(The)-289.9(equilibration)-289.9(is)-289.9(slo)25(w)-289.9(o)0(n)-289.9(the)-289.9(NMR)-289.8(timescale)-289.9(\(milliseconds\))]TJ -7.6123 -1.2 TD [(and)-295(so)-295(we)-295(see)-295(tw)10(o)-295(distinct)-295(NMR)-295(peaks)-295(for)-295(the)-295(tw)10(o)-295(isomers.)-295(The)-295(anomeric)-295(proton)-295(for)-295(the)]TJ T* (major)Tj /F2 1 Tf 2.6336 0 TD ()Tj /F8 1 Tf 0.8806 0 TD [(form)-300.6(will)-300.6(be)-300.6(a)-300.6(doublet)-300.6(with)-300.6(a)-300.6(lar)18(ge)-300.6(coupling)-300.6(constant)-300.6(\(10)-300.6(Hz\))-300.6(and)-300.6(for)-300.6(the)-300.6(minor)]TJ -3.5142 -1.2 TD [(form)-352.1(a)-352.1(doublet)-352.1(at)-352.1(a)-352.1(dif)25(ferent)-352.1(chemical)-352.1(shift)-352.1(with)-352.1(a)-352.1(small)-352.1(coupling)-352.1(constant)-352.1(\(4)-352.1(Hz\).)-352.1(The)]TJ T* [(ratio)-223.5(of)-223.5(inte)15(grals)-223.5(for)-223.5(these)-223.5(tw)10(o)-223.5(peaks)-223.5(will)-223.5(be)-223.5(about)-223.5(2:1)-223.5(\(0.67:0.33)-223.5(for)-223.5(normalized)-223.5(inte)15(grals\).)]TJ T* -0.0001 Tc [(This)-300.6(pattern)-300.6(is)-300.6(a)-300.6(dead)-300.6(gi)24.9(v)14.9(e)-0.1(a)14.9(w)9.9(ay)-300.6(that)-300.6(you)-300.6(ha)19.9(v)14.9(e)-300.6(a)-300.6(free)-300.6(\(reducing\))-300.6(aldop)9.9(yranose)-300.6(sugar)54.9(.)-300.6(This)]TJ T* [(monosaccharide)-283.6(could)-283.6(still)-283.6(be)-283.6(link)9.9(ed)-283.6(to)-283.6(other)-283.6(sugars)-283.6(by)-283.6(formation)-283.6(of)-283.6(a)-283.6(glycosidic)-283.6(linkage)]TJ T* 0 Tc [(with)-250(one)-250(of)-250(the)-250(nonanomeric)-250(OH)-250(groups.)]TJ ET endstream endobj 33 0 obj > endobj 34 0 obj > endobj 35 0 obj > endobj 36 0 obj > endobj 37 0 obj > endobj 38 0 obj > endobj 39 0 obj > endobj 40 0 obj > endobj 41 0 obj > endobj 42 0 obj > endobj 43 0 obj > endobj 44 0 obj > endobj 45 0 obj > endobj 46 0 obj > endobj 47 0 obj > stream BT /F8 1 Tf 7.9701 0 0 7.9701 190.5693 730.6316 Tm 0 g /GS1 gs 0 Tc 0 Tw [(TYPICAL)-250(V)135(ALUES)-250(OF)-250(CHEMICAL)-250(SHIFTS)-250(AND)-250(COUPLING)-250(CONST)93(ANTS)]TJ /F1 1 Tf 8.9664 0 0 8.9664 468.5827 730.6316 Tm (+)Tj /F8 1 Tf 9.9626 0 0 9.9626 118.8941 706.4592 Tm [(the)-181.5(relaxation)-181.5(delay)-181.5(is)-181.5(short)-181.5(\(in)-181.5(this)-181.5(case)-181.5(the)-181.5(rec)15(ycle)-181.5(delay)-181.5(w)10(a)0(s)-181.5(only)-181.5(1.74)-181.5(s)-181.5(\(1.04)-181.5(s)-181.5(acquisition)]TJ 0 -1.2 TD [(time)-250.5(and)-250.5(0.7)-250.5(s)-250.5(relaxation)-250.5(delay\).)-250.5(So)-250.5(we)-250.5(can)-250.5(assign)-250.5(peak)-250.5(aa)-250.5(\(140.75\))-250.5(to)-250.5(C-5)-250.5(and)-250.5(peak)-250.5(z)]TJ T* [(\(121.69\))-246.6(to)-246.6(C-6.)-246.6(Note)-246.6(also)-246.6(that)-246.6(the)-246.6(more)-246.6(substituted)-246.6(carbon,)-246.6(C-5)-246.6(\(three)-246.6(bonds)-246.6(to)-246.6(carbon\))-246.6(is)]TJ T* [(shifted)-250(do)25(wneld)-250(relati)25(v)15(e)-250(to)-250(C-6)-250(\(tw)10(o)-250(bonds)-250(to)-250(carbon\))-250(due)-250(to)-250(the)-250(steric)-250(cro)25(wding)-250(ef)25(fect.)]TJ 1.2 -1.2 TD [(Peak)-202.1(y)-202.1(\(71.78)-202.1(ppm\))-202.1(is)-202.1(in)-202.1(the)-202.1(alcohol)-202.1(re)15(gion)-202.1(\(CO\))-202.1(in)-202.1(the)-202.1(range)-202.1(e)15(xpected)-202.1(for)-202.1(methine)]TJ -1.2 -1.2 TD [(carbon)-381.9(\(CHO\),)-381.9(so)-381.9(it)-381.9(can)-381.9(be)-381.9(assigned)-381.9(to)-381.9(C-3.)-381.9(The)-381.9(ne)15(xt)-381.9(three)-381.9(carbons)-381.9(\(peaks)-381.9(x,)70()-381.9()0(w)65(,)70()]TJ T* [(and)-315.5(v)65(,)70()-315.5(5057)-315.5(ppm\))-315.5(could)-315.5(be)-315.5(methoxy)-315.5(\(CH)]TJ 7.5716 0 0 7.5716 299.7605 633.2339 Tm (3)Tj 9.9626 0 0 9.9626 304.0444 634.7283 Tm [(O\))-315.4(groups,)-315.5(b)20(u)0(t)-315.5(because)-315.5(we)-315.5(ha)20(v)15(e)-315.5(accounted)]TJ -18.5845 -1.2 TD [(for)-342.7(all)-342.7(the)-342.7(functional)-342.7(groups)-342.7(of)-342.7(cholesterol)-342.7(the)15(y)-342.7(must)-342.7(be)-342.7(either)-342.7(close)-342.7(to)-342.7(these)-342.7(functional)]TJ T* [(groups)-272.6(\(inducti)25(v)15(e)-272.6(ef)25(fect\))-272.6(or)-272.6(shifted)-272.6(do)25(wneld)-272.6(due)-272.6(to)-272.6(steric)-272.6(cro)25(wding.)-272.6(The)-272.6(inducti)25(v)15(e)-272.6(ef)25(fect)]TJ T* [(\(electron)-306(withdra)15(wing)-306(and)-306(donating)-306(groups\))-306(is)-306(most)-306(important)-306(for)]TJ 7.5716 0 0 7.5716 388.0284 602.4792 Tm (1)Tj 9.9626 0 0 9.9626 392.3123 598.8629 Tm [(H)-306(chemical)-306(shifts,)-306(so)]TJ -27.4444 -1.2 TD [(let)-335.6(us)-335.6(consider)-335.6(the)-335.6(steric)-335.6(ef)25(fects.)-335.6(The)-335.6(most)-335.6(sterically)-335.6(cro)25(wded)-335.6(carbons)-335.6(in)-335.6(the)-335.6(cholesterol)]TJ T* [(structure)-306.8(are)-306.8(the)-306.8(methine)-306.8(\(CH\))-306.7(groups)-306.8(ne)15(xt)-306.8(to)-306.8(an)-306.8(sp)]TJ 7.5716 0 0 7.5716 328.3085 578.569 Tm (3)Tj 9.9626 0 0 9.9626 332.5925 574.9525 Tm -0.0002 Tc [(-hybridized)-307(quaternary)-307(carbon:)-307(C-9,)]TJ -21.45 -1.2 TD 0 Tc [(C-14,)-342.9(and)-342.9(C-17.)-342.9(These)-342.9(three)-342.9(carbons)-342.9(account)-342.9(for)-342.9(this)-342.9(group)-342.9(of)-342.9(do)25(wneld-shifted)-342.9(peaks.)]TJ T* [(The)-243.7(rest)-243.7(of)-243.7(the)]TJ 7.5716 0 0 7.5716 178.957 554.6586 Tm (13)Tj 9.9626 0 0 9.9626 187.0267 551.0422 Tm -0.0001 Tc [(C)-243.8(peaks)-243.8(\(au\))-243.8(lie)-243.8(in)-243.8(the)-243.8(re)14.9(gion)-243.8(of)-243.8(saturated)-243.8(hydrocarbon)-243.8(\(sp)]TJ 7.5716 0 0 7.5716 423.591 554.6587 Tm 0 Tc (3)Tj 9.9626 0 0 9.9626 430.3027 551.0422 Tm [(carbon)-243.7(with)]TJ -31.2576 -1.2 TD [(no)-249.3(functional)-249.3(groups\))-249.3(and)-249.3(cannot)-249.3(be)-249.3(assigned)-249.3(without)-249.3(more)-249.3(adv)25(anced)-249.3(e)15(xperiments)-249.3(such)-249.3(as)]TJ T* [(DEPT)-250(and)-250(2D)-250(HSQC/HMBC.)]TJ /F1 1 Tf 0 -3.4433 TD [($)-1000( \012)-250( > endobj 49 0 obj > stream BT /F1 1 Tf 8.9664 0 0 8.9664 120.239 730.6316 Tm 0 g /GS1 gs 0 Tc 0 Tw (.)Tj /F8 1 Tf 7.9701 0 0 7.9701 147.1382 730.6316 Tm [(FUND)40(AMENT)93(ALS)-250(OF)-250(NMR)-250(SPECTR)40(OSCOPY)-250(IN)-250(LIQ)10(UIDS)]TJ 9.9626 0 0 9.9626 131.6363 704.5911 Tm (\(d\))Tj /F4 1 Tf 1.586 0 TD [()20( )-318.8( )-318.8()-318.8( \015)10()]TJ /F8 1 Tf 7.3693 0 TD [(:)-318.8(HCO)-318.7(\(attached)-318.8(to)-318.8(an)-318.8(sp)]TJ 7.5716 0 0 7.5716 333.0228 708.2075 Tm (3)Tj 9.9626 0 0 9.9626 337.3068 704.5911 Tm -0.0002 Tc [(-hybridized)-319(carbon)-319(with)-319(one)-319(single)]TJ -19.0582 -1.2 TD 0 Tc [(bond)-250(to)-250(oxygen\):)]TJ 0.43 -1.2015 TD [(1.)-520(alcohol)-250(or)-250(ether)-250(\(HCOH)-250(or)-250(HCOC\):)-250(3.3)]TJ 0 -1.2 TD [(2.)-520(ester)-250(\(HCOCOR\):)-250(3.8.)]TJ -1.96 -1.2015 TD [(\(e\))-420()]TJ /F4 1 Tf 1.974 0 TD ()Tj /F8 1 Tf 3.166 0 TD [(:)-324.1(HC)]TJ ET 0 G 0 J 0 j 0.498 w 10 M []0 d 1 i 212.644 658.983 m 218.622 658.983 l 212.644 660.975 m 218.622 660.975 l S BT 9.9626 0 0 9.9626 218.6217 656.7412 Tm [(C:)-324.1(56)-324.1(ppm)-324.1(\(where)-324.1(C)]TJ ET 307.911 658.983 m 313.889 658.983 l 307.911 660.975 m 313.889 660.975 l S BT 9.9626 0 0 9.9626 313.8887 656.7412 Tm [(C)-324(i)0(s)-324.1(not)-324.1(part)-324.1(of)-324.1(an)-324.1(aromatic)-324.1(ring\).)-324.1(Reso-)]TJ -16.7076 -1.2 TD [(nance)-287.4(ef)25(fects)-287.4(can)-287.4(shift)-287.4(out)-287.4(of)-287.4(this)-287.4(range:)-287.4(up)-287.4(to)-287.4(1)-287.4(ppm)-287.4(upeld)-287.4(for)-287.4(electron-donating)]TJ T* [(groups)-347.9(\(e.g.,)-347.9(HC)]TJ ET 220.502 635.072 m 226.479 635.072 l 220.502 637.065 m 226.479 637.065 l S BT 9.9626 0 0 9.9626 226.4792 632.8309 Tm [(CO\))-347.9(and)-347.9(1)-347.9(ppm)-347.9(do)25(wneld)-347.9(for)-347.9(electron-withdra)15(wing)-347.9(groups)]TJ -7.9339 -1.2 TD [(\(e.g.,)-189.7(HC)]TJ ET 188.341 623.117 m 194.319 623.117 l 188.341 625.11 m 194.319 625.11 l S BT 9.9626 0 0 9.9626 194.3186 620.8757 Tm (CC)Tj ET 212.59 623.117 m 218.568 623.117 l 212.59 625.11 m 218.568 625.11 l S BT 9.9626 0 0 9.9626 218.5678 620.8757 Tm [(O\).)-189.7(This)-189.7(is)-189.7(a)-189.7(result)-189.7(of)-189.7(increased)-189.7(or)-189.7(decreased)-189.7(electron)-189.7(density)-189.7(at)-189.7(the)]TJ -7.1398 -1.2 TD [(carbon)-266.9(bearing)-266.9(the)-266.9(proton)-266.9(in)-266.9(resonance)-266.9(structures)-266.9(such)-266.9(as)-266.9(HC)]TJ /F3 1 Tf 7.5716 0 0 7.5716 398.2441 612.537 Tm ()Tj /F8 1 Tf 9.9626 0 0 9.9626 404.648 608.9206 Tm (C)Tj ET 416.275 611.162 m 422.252 611.162 l 416.275 613.155 m 422.252 613.155 l S BT 9.9626 0 0 9.9626 422.2521 608.9206 Tm (O)Tj /F3 1 Tf 7.5716 0 0 7.5716 429.4452 612.537 Tm ()Tj /F8 1 Tf 9.9626 0 0 9.9626 435.8492 608.9207 Tm [()-266.9(\(electron)]TJ -28.9494 -1.2 TD [(donation:)-313.5(vin)15(yl)-313.5(ether\))-313.5(and)-313.5(HC)]TJ /F3 1 Tf 7.5716 0 0 7.5716 274.342 600.5818 Tm ()Tj /F8 1 Tf 9.9626 0 0 9.9626 280.746 596.9654 Tm (C)Tj ET 292.372 599.207 m 298.35 599.207 l 292.372 601.2 m 298.35 601.2 l S BT 9.9626 0 0 9.9626 298.35 596.9654 Tm (CO)Tj /F3 1 Tf 7.5716 0 0 7.5716 317.1696 600.5818 Tm ()Tj /F8 1 Tf 9.9626 0 0 9.9626 326.6968 596.9654 Tm [(\(electron)-313.5(withdra)15(w)10(al:)]TJ /F2 1 Tf 8.9331 0 TD (\015)Tj /F8 1 Tf 0.571 0 TD (,)Tj /F2 1 Tf 0.25 0 TD ()Tj /F8 1 Tf 0.58 0 TD (-unsaturated)Tj -28.3273 -1.2 TD [(k)10(etone\).)]TJ -1.419 -1.4 TD [(\(f\))-420()]TJ /F4 1 Tf 1.863 0 TD ( \012)Tj /F8 1 Tf 3.8881 0 TD [(:)-247.3(HC\(O\)O)-247.3(\(attached)-247.3(to)-247.3(an)-247.3(sp)]TJ 7.5716 0 0 7.5716 322.4377 574.679 Tm (3)Tj 9.9626 0 0 9.9626 326.7216 571.0626 Tm -0.0002 Tc [(-hybridized)-247.5(carbon)-247.5(that)-247.5(has)-247.5(tw)9.8(o)-247.5(single)]TJ -17.9957 -1.2 TD 0 Tc [(bonds)-250(to)-250(oxygen\):)-250(56)-250(ppm.)]TJ -1.586 -1.4 TD [(\(g\))-420()]TJ /F4 1 Tf 2.03 0 TD [(\012)45(  )]TJ /F8 1 Tf 3.677 0 TD [(:)-245.9(attached)-245.9(to)-245.9(carbon)-245.9(of)-245.9(a)-245.9(benzene,)-245.9(furan,)-245.9(p)10(yrrole,)-245.9(p)10(yridine,)-245.9(indole,)-245.9(naph-)]TJ -4.1211 -1.2 TD [(thalene,)-186.2(and)-186.2(so)-186.2(on,)-186.2(ring:)-186.2(generic)-186.2(78)-186.2(ppm.)-186.2(The)-186.2(ef)25(fect)-186.2(of)-186.2(substituents)-186.2(due)-186.2(to)-186.2(resonance)]TJ T* [(ef)25(fects)-250(\(strongest)-250(at)]TJ /F4 1 Tf 8.0561 0 TD ( \012  )Tj /F8 1 Tf 2.417 0 TD (position\):)Tj -10.5431 -1.4015 TD [(1.)-520(electron-rich)-312.6(carbon)-312.6(\(e.g.,)]TJ /F4 1 Tf 12.0648 0 TD ( \012  )Tj /F8 1 Tf 2.4796 0 TD (or)Tj /F4 1 Tf 1.1456 0 TD [(\012)15()]TJ /F8 1 Tf 2.1866 0 TD [(to)-312.6(O)-312.5(o)0(r)-312.6(N)-312.5(of)-312.5(phenol,)-312.5(aniline,)-312.5(phenolic)]TJ -16.6065 -1.2 TD [(ether)40(,)-250(o)0(r)-250(i)0(n)-250(a)0(n)-250(electron-rich)-250(heteroaromatic:)-250(p)10(yrrole,)-250(furan\):)-250(67)-250(ppm;)]TJ -1.27 -1.2 TD [(2.)-520(electron-poor)-300.8(carbon)-300.8(\(e.g.,)]TJ /F4 1 Tf 12.3075 0 TD ( \012  )Tj /F8 1 Tf 2.4678 0 TD (or)Tj /F4 1 Tf 1.1338 0 TD [(\012)15()]TJ /F8 1 Tf 2.1748 0 TD [(to)-300.8(C)]TJ ET 344.297 485.618 m 350.275 485.618 l 344.297 487.611 m 350.275 487.611 l S BT 9.9626 0 0 9.9626 350.2746 483.3767 Tm 0.3008 Tc [(Oo)300.8(rN)300.8(O)]TJ 7.5716 0 0 7.5716 386.146 481.8824 Tm 0 Tc (2)Tj 9.9626 0 0 9.9626 390.4602 483.3767 Tm [(,)-300.8(o)0(r)-300.8(i)0(n)-300.8(the)-300.8(tw)10(o)-300.8(o)0(r)-300.8(four)]TJ -23.1935 -1.2 TD [(position)-250(of)-250(p)10(yridine\):)-250(89)-250(ppm.)]TJ -2.786 -1.4015 TD (\(h\))Tj /F4 1 Tf 1.586 0 TD (\015)Tj /F8 1 Tf 3.721 0 TD [(:)-250(HC)]TJ ET 208.588 459.701 m 214.566 459.701 l 208.588 461.693 m 214.566 461.693 l S BT 9.9626 0 0 9.9626 214.566 457.4593 Tm [(O:)-250(10)-250(ppm.)]TJ -8.1021 -1.4 TD [(\(i\))-420(Carboxylic)-250(acid:)-250(HOC\()]TJ ET 245.391 445.753 m 251.368 445.753 l 245.391 447.746 m 251.368 447.746 l S BT 9.9626 0 0 9.9626 251.3685 443.5116 Tm [(O\))-250(or)]TJ /F4 1 Tf 2.388 0 TD ( )Tj /F8 1 Tf 3.444 0 TD [(:)-250(HOC\(aromatic\):)-250(1214)-250(ppm.)]TJ -18.9942 -2.3015 TD 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()Tj /F9 1 Tf 9.9626 0 0 9.9626 250.2485 319.5404 Tm [(angle)-257.9(to)-257.9(the)-257.9(e)15(xternal)-257.9(magnetic)]TJ /F8 1 Tf 12.3278 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-257.9(and)-257.9(one)-257.9(with)-257.9(the)-257.9(spin)]TJ -23.5635 -1.2 TD [(axis)-282.3(at)-282.3(a)-282.3(135)]TJ /F3 1 Tf 7.5716 0 0 7.5716 194.8972 311.2017 Tm ()Tj /F9 1 Tf 9.9626 0 0 9.9626 201.9931 307.5852 Tm [(angle)-282.3(to)-282.3(the)-282.3(e)15(xternal)]TJ /F8 1 Tf 8.5011 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld.)-282.3(A)-282.2(spin-1)-282.3(nucleus)-282.3(can)-282.3(be)-282.3(vie)25(wed)-282.3(as)-282.3(ha)20(ving)]TJ -14.8932 -1.2 TD [(three)-221(possible)-221(states:)-221(45)]TJ /F3 1 Tf 7.5716 0 0 7.5716 237.8989 299.2465 Tm ()Tj /F9 1 Tf 9.9626 0 0 9.9626 242.1829 295.6301 Tm 0.221 Tc [(,9)221(0)]TJ /F3 1 Tf 7.5716 0 0 7.5716 256.8381 299.2465 Tm 0 Tc ()Tj /F9 1 Tf 9.9626 0 0 9.9626 261.122 295.6301 Tm [(,)-221(and)-221(135)]TJ /F3 1 Tf 7.5716 0 0 7.5716 297.3466 299.2466 Tm ()Tj /F9 1 Tf 9.9626 0 0 9.9626 301.6305 295.6302 Tm [(.)-221(I)0(n)-221(this)-221(book)-221(we)-221(will)-221(be)-221(concerned)-221(primarily)]TJ -15.8372 -1.2 TD [(with)-250(spin-)]TJ /F8 1 Tf 4.028 0 TD ()Tj /F9 1 Tf 1 0 TD (nuclei.)Tj -7.3981 -2.762 TD [(Here)-441.4(are)-441.4(some)-441.4(e)15(xamples)-441.4(sho)25(wing)-441.4(the)-441.4(composition)-441.4(of)-441.4(the)-441.4(nucleus)-441.4(\()]TJ /F4 1 Tf 28.4249 0 TD ()Tj /F3 1 Tf 0.9414 0 TD ()Tj /F9 1 Tf 1.2214 0 TD (protons,)Tj /F4 1 Tf 3.6914 0 TD ()Tj /F3 1 Tf 0.9414 0 TD ()Tj /F9 1 Tf -35.2204 -1.2 TD (neutrons\):)Tj ET 0 G 0 J 0 j 0.398 w 10 M []0 d 1 i 204.697 241.204 m 394.436 241.204 l S BT 8.9664 0 0 8.9664 204.6974 229.3487 Tm [(Spin-0)-6766(spin-)]TJ /F8 1 Tf 9.9626 0 0 9.9626 307.2096 229.3487 Tm ()Tj /F9 1 Tf 8.9664 0 0 8.9664 351.6747 229.3487 Tm (spin)Tj /F2 1 Tf 1.917 0 TD ( )Tj /F9 1 Tf 1.03 0 TD (1/2)Tj ET 204.697 225.862 m 394.436 225.862 l S BT 5.9776 0 0 5.9776 204.6974 217.2611 Tm (12)Tj 8.9664 0 0 8.9664 211.197 214.0062 Tm 0.25 Tc [(C\()250(6)]TJ /F4 1 Tf 1.75 0 TD 0 Tc ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (6)Tj /F4 1 Tf 0.5 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 278.1878 217.261 Tm (1)Tj 8.9664 0 0 8.9664 281.6747 214.0062 Tm 0.25 Tc [(H\()250(1)]TJ /F4 1 Tf 1.805 0 TD 0 Tc ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (0)Tj /F4 1 Tf 0.5 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 345.6916 217.261 Tm (2)Tj 8.9664 0 0 8.9664 349.2025 214.0062 Tm 0.25 Tc [(H\()250(1)]TJ /F4 1 Tf 1.805 0 TD 0 Tc ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (1)Tj /F4 1 Tf 0.5 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 204.6974 206.3021 Tm (16)Tj 8.9664 0 0 8.9664 211.1731 203.0473 Tm 0.25 Tc [(O\()250(8)]TJ /F4 1 Tf 1.805 0 TD 0 Tc ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (8)Tj /F4 1 Tf 0.5 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 278.1878 206.3021 Tm (3)Tj 8.9664 0 0 8.9664 281.6747 203.0473 Tm 0.25 Tc [(H\()250(1)]TJ /F4 1 Tf 1.805 0 TD 0 Tc ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (2)Tj /F4 1 Tf 0.5 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 344.2062 206.3021 Tm (14)Tj 8.9664 0 0 8.9664 350.6879 203.0473 Tm 0.25 Tc [(N\()250(7)]TJ /F4 1 Tf 1.805 0 TD 0 Tc ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (7)Tj /F4 1 Tf 0.5 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 204.6974 195.3432 Tm (18)Tj 8.9664 0 0 8.9664 211.1731 192.0884 Tm 0.25 Tc [(O\()250(8)]TJ /F4 1 Tf 1.805 0 TD 0 Tc ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (10)Tj /F4 1 Tf 1 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 276.94 195.3432 Tm (13)Tj 8.9664 0 0 8.9664 283.4157 192.0884 Tm 0.25 Tc [(C\()250(6)]TJ /F4 1 Tf 1.75 0 TD 0 Tc ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (7)Tj /F4 1 Tf 0.5 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 344.2092 195.3432 Tm (17)Tj 8.9664 0 0 8.9664 350.6849 192.0884 Tm 0.25 Tc [(O\()250(8)]TJ /F4 1 Tf 1.805 0 TD 0 Tc ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (9)Tj /F4 1 Tf 0.5 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 276.6934 184.3843 Tm (15)Tj 8.9664 0 0 8.9664 283.1691 181.1295 Tm 0.25 Tc [(N\()250(7)]TJ /F4 1 Tf 1.805 0 TD 0 Tc ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (8)Tj /F4 1 Tf 0.5 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 275.196 173.4254 Tm (19)Tj 8.9664 0 0 8.9664 281.6717 170.1706 Tm 0.25 Tc [(F\()250(9)]TJ /F4 1 Tf 1.639 0 TD 0 Tc ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (10)Tj /F4 1 Tf 1 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 271.7081 162.4665 Tm (29)Tj 8.9664 0 0 8.9664 278.1838 159.2117 Tm [(Si)-250(\(14)]TJ /F4 1 Tf 2.417 0 TD ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (15)Tj /F4 1 Tf 1 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj 5.9776 0 0 5.9776 272.9544 151.5076 Tm (31)Tj 8.9664 0 0 8.9664 279.4301 148.2528 Tm [(P)-250(\(15)]TJ /F4 1 Tf 2.139 0 TD ()Tj /F3 1 Tf 0.75 0 TD ()Tj /F9 1 Tf 1.03 0 TD (16)Tj /F4 1 Tf 1 0 TD ()Tj /F9 1 Tf 0.5 0 TD (\))Tj ET 204.697 144.766 m 394.436 144.766 l S endstream 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[(ef)25(fects)-250(of)-250(a)-250(spin-1)-250(\(three)-250(quantum)-250(states\))-250(nucleus.)]TJ /F1 1 Tf 0 -2.96 TD -0.018 Tw [(&)-1000( !)]TJ /F9 1 Tf 0 -1.8 TD 0 Tw [(When)-347.5(we)-347.5(place)-347.5(a)-347.5(spin-)]TJ /F8 1 Tf 9.4981 0 TD ()Tj /F9 1 Tf 1.0975 0 TD [(nucleus)-347.5(in)-347.5(a)-347.5(strong)-347.5(e)15(xternal)-347.5(magnetic)]TJ /F8 1 Tf 15.7342 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld,)-347.5(the)-347.5(nucleus)-347.5(w)10(ants)]TJ -26.8858 -1.2 TD [(to)-296(align)-296(itself)-296(with)-296(the)-296(magnetic)]TJ /F8 1 Tf 13.2202 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld,)-296(just)-296(lik)10(e)-296(a)-296(compass)-296(needle)-296(mo)15(v)15(e)0(s)-296(t)0(o)-296(align)-296(with)-296(the)]TJ -13.7762 -1.2 TD (earth)Tj /F8 1 Tf 1.999 0 TD ()Tj /F9 1 Tf 0.278 0 TD [(s)-238.4(magnetic)]TJ /F8 1 Tf 4.5318 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld.)-238.4(But)-238.4(because)-238.4(the)-238.4(nucleus)-238.4(is)-238.4(spinning)-238.4(\(i.e.,)-238.4(it)-238.4(has)-238.4(an)-238.4(intrinsic)-238.4(property)]TJ -7.3648 -1.2 TD [(of)-237.4(angular)-237.4(momentum\),)-237.4(it)-237.4(cannot)-237.4(simply)-237.4(change)-237.4(its)-237.4(angle)-237.4(with)-237.4(the)-237.4(magnetic)]TJ /F8 1 Tf 30.3736 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-237.4(from)-237.4(45)]TJ /F3 1 Tf 7.5716 0 0 7.5716 473.2693 543.1019 Tm ()Tj /F9 1 Tf 9.9626 0 0 9.9626 118.8941 527.5304 Tm [(to)-194.1(0)]TJ /F3 1 Tf 7.5716 0 0 7.5716 133.5606 531.1468 Tm ()Tj /F9 1 Tf 9.9626 0 0 9.9626 137.8445 527.5304 Tm [(.)-194.1(The)-194.1(torque)-194.1(it)-194.1(e)15(xperiences)-194.1(from)-194.1(the)-194.1(e)15(xternal)-194.1(magnetic)]TJ /F8 1 Tf 21.4065 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-194.1(instead)-194.1(causes)-194.1(the)-194.1(spin)-194.1(axis)]TJ -23.8646 -1.2 TD (to)Tj /F8 1 Tf 1.0072 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(w)10(obble)]TJ /F8 1 Tf 2.934 0 TD ()Tj /F9 1 Tf 0.6732 0 TD [(or)-229.2(precess)-229.2(around)-229.2(the)-229.2(magnetic)]TJ /F8 1 Tf 12.5872 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-229.2(direction.)-229.2(This)-229.2(is)-229.2(analogous)-229.2(to)-229.2(a)-229.2(spinning)]TJ -18.2017 -1.2 TD [(top)-182.4(or)-182.4(gyroscope,)-182.4(which)-182.4(responds)-182.4(to)-182.4(the)-182.4(torque)-182.4(produced)-182.4(by)-182.4(the)-182.4(earth)]TJ /F8 1 Tf 26.9732 0 TD ()Tj /F9 1 Tf 0.278 0 TD [(s)-182.4(gra)20(vitational)]TJ /F8 1 Tf 5.7888 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-182.4(by)]TJ -33.596 -1.2 TD [(describing)-188.2(a)-188.2(circle)-188.2(with)-188.2(its)-188.2(spin)-188.2(axis.)-188.2(The)-188.2(precession)-188.2(rate)-188.2(of)-188.2(the)-188.2(nucleus)-188.2(in)-188.2(a)-188.2(magnetic)]TJ /F8 1 Tf 33.3672 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-188.2(is)]TJ -33.9232 -1.2 TD (the)Tj /F4 1 Tf 1.3762 0 TD [(\012)37(  )-154.2(\012)37(\) \015)]TJ /F9 1 Tf 7.6774 0 TD [(referred)-154.2(to)-154.2(in)-154.2(the)-154.2(name)]TJ 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1 Tf 13.1316 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-276.9(strength,)]TJ /F4 1 Tf 5.2479 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 400.503 370.4861 Tm (o)Tj 9.9626 0 0 9.9626 404.7869 371.9805 Tm [(.)-276.9(This)-276.9(relationship)]TJ -28.6965 -1.2 TD [(forms)-357.1(the)-357.1(basis)-357.1(of)-357.1(nearly)-357.1(e)25(v)15(ery)-357.1(phenomenon)-357.1(observ)15(ed)-357.1(in)-357.1(NMR.)-357.1(There)-357.1(are)-357.1(tw)10(o)-357.1(w)10(ays)-357.1(to)]TJ T* [(measure)-221.2(the)-221.2(precession)-221.2(rate:)-221.2(the)-221.2(angular)-221.2(v)15(elocity)65(,)]TJ /F2 1 Tf 19.7136 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 321.9989 346.5757 Tm (o)Tj 9.9626 0 0 9.9626 326.2828 348.0702 Tm [(,)-221.2(i)0(n)-221.2(units)-221.2(of)-221.2(radians)-221.2(per)-221.2(second)-221.2(and)-221.2(the)]TJ -20.8167 -1.2 TD [(frequenc)15(y)65(,)]TJ /F2 1 Tf 4.3898 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 167.4702 334.6206 Tm (o)Tj 9.9626 0 0 9.9626 171.7541 336.115 Tm 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()Tj /F9 1 Tf 7.5716 0 0 7.5716 208.7802 214.8697 Tm (o)Tj /F3 1 Tf 9.9626 0 0 9.9626 215.8315 216.3641 Tm ()Tj /F2 1 Tf 1.0578 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 238.1458 214.8697 Tm (o)Tj /F2 1 Tf 9.9626 0 0 9.9626 242.4297 216.3641 Tm ()Tj /F9 1 Tf 0.47 0 TD (2)Tj /F2 1 Tf 0.504 0 TD ()Tj /F3 1 Tf 0.9038 0 TD ()Tj /F9 1 Tf 1.0578 0 TD (3)Tj /F2 1 Tf 0.5 0 TD (\012)Tj /F9 1 Tf 0.275 0 TD (001)Tj /F3 1 Tf 1.7222 0 TD ()Tj /F9 1 Tf 1.0062 0 TD (10)Tj 7.5716 0 0 7.5716 316.5921 220.4787 Tm (8)Tj 9.9626 0 0 9.9626 322.5365 216.3641 Tm (Hz)Tj /F3 1 Tf 1.4468 0 TD ()Tj /F9 1 Tf 1.0578 0 TD (300)Tj /F2 1 Tf 1.505 0 TD (\012)Tj /F9 1 Tf 0.275 0 TD [(1)-166.7(MHz)]TJ -24.7252 -2.4067 TD [(Such)-213.9(a)-213.9(magnet)-213.9(w)10(ould)-213.9(be)-213.9(called)-213.9(a)]TJ /F8 1 Tf 13.1517 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(300)-213.9(MHz)]TJ /F8 1 Tf 3.769 0 TD ()Tj /F9 1 Tf 0.6579 0 TD [(magnet)-213.9(because)-213.9(the)]TJ 7.5716 0 0 7.5716 377.8786 196.0038 Tm (1)Tj 9.9626 0 0 9.9626 382.1625 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[(e)25(v)15(ery)-226.2(100)-226.2(carbon)-226.2(atoms)-226.1(is)-226.2(participating)-226.2(in)-226.2(the)-226.1(NMR)-226.1(e)15(xperiment.)-226.2(Ho)25(we)25(v)15(e)0(r)40(,)-226.2(we)-226.2(will)-226.2(see)-226.2(that)]TJ T* [(there)-262.7(are)-262.7(adv)25(antages)-262.7(to)-262.7(ha)20(ving)-262.7(a)]TJ /F8 1 Tf 13.1383 0 TD ()Tj /F9 1 Tf 0.444 0 TD (dilute)Tj /F8 1 Tf 2.278 0 TD ()Tj /F9 1 Tf 0.7067 0 TD (nucleus)Tj /F8 1 Tf 3.055 0 TD ()Tj /F9 1 Tf 1 0 TD [(one)-262.7(that)-262.7(is)]TJ /F8 1 Tf 4.3991 0 TD ()Tj /F9 1 Tf 0.444 0 TD (sprinkled)Tj /F8 1 Tf 3.722 0 TD ()Tj /F9 1 Tf 0.7067 0 TD [(lightly)-262.7(o)15(v)15(e)0(r)-262.7(the)]TJ -29.894 -1.2 TD [(collection)-204.6(of)-204.6(molecules)-204.6(in)-204.6(the)-204.7(sample.)-204.6(W)80(e)-204.6(can)-204.6(impro)15(v)15(e)-204.6(on)-204.6(nature)-204.7(by)-204.6(isotopically)-204.6(labeling)-204.7(or)]TJ T* [(enriching)-245.7(the)-245.7(sample)-245.7(either)-245.7(by)-245.7(synthesis)-245.7(from)-245.7(labeled)-245.7(starting)-245.7(materials)-245.7(or)-245.7(by)-245.7(biosynthesis)]TJ T* [(on)-202.4(labeled)-202.4(gro)25(wth)-202.4(media.)-202.4(Man)15(y)-202.4(compounds)-202.4(can)-202.4(be)-202.4(purchased)-202.4(with)-202.4(nearly)-202.4(100%)-202.4(ab)20(undance)]TJ T* (of)Tj 7.5716 0 0 7.5716 131.5544 413.0445 Tm (13)Tj 9.9626 0 0 9.9626 139.6241 409.4281 Tm (C,)Tj 7.5716 0 0 7.5716 151.7763 413.0445 Tm (2)Tj 9.9626 0 0 9.9626 156.0905 409.4281 Tm [(H,)-302.8(or)]TJ 7.5716 0 0 7.5716 180.106 413.0445 Tm (15)Tj 9.9626 0 0 9.9626 188.1757 409.4281 Tm [(N)-302.7(either)-302.8(at)-302.8(one)-302.8(site)-302.8(in)-302.8(the)-302.8(molecule)-302.8(or)-302.8(at)-302.8(all)-302.8(sites)-302.8(\()]TJ /F8 1 Tf 20.5194 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(uniformly)-302.8(labeled)]TJ /F8 1 Tf 7.1909 0 TD ()Tj /F9 1 Tf 0.444 0 TD (\).)Tj -35.4174 -1.2 TD [(This)-284.8(can)-284.8(be)-284.8(v)15(ery)-284.8(costly)65(,)-284.8(b)20(ut)-284.8(the)-284.8(bene)]TJ /F8 1 Tf 14.8078 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(ts)-284.8(often)-284.8(justify)-284.8(the)-284.8(cost.)-284.8(F)15(o)0(r)-284.8(e)15(xample,)-284.8(with)-284.8(uniform)]TJ 7.5716 0 0 7.5716 120.239 389.1342 Tm (13)Tj 9.9626 0 0 9.9626 128.3088 385.5177 Tm [(C)-268.2(labelling,)-268.2(the)]TJ 7.5716 0 0 7.5716 192.5047 389.1342 Tm (13)Tj 9.9626 0 0 9.9626 200.5744 385.5177 Tm [(C)-268.2(signal)-268.2(can)-268.2(be)-268.2(increased)-268.2(by)-268.2(a)-268.2(f)10(actor)-268.2(of)-268.2(100,)-268.2(reducing)-268.2(the)-268.2(e)15(xperiment)]TJ -8.0637 -1.2 TD [(time)-233.9(by)-233.9(a)-233.9(f)10(actor)-233.9(of)-233.9(10,000.)-233.9(It)-233.9(should)-233.9(be)-233.9(noted)-233.9(that)-233.9(all)-233.9(three)-233.9(of)-233.9(these)-233.9(isotopes)-233.9(are)-233.9(stable,)-233.9(that)]TJ T* [(is,)-250(the)15(y)-250(are)-250(not)-250(radioacti)25(v)15(e)0(.)]TJ /F1 1 Tf 0 -3.1652 TD [(&$)-1000(#)-250( %")]TJ /F9 1 Tf 0 -1.8 TD [(Because)-315.3(at)-315.3(an)15(y)-315.3(g)0(i)25(v)15(en)]TJ /F8 1 Tf 8.9264 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-315.3(strength)-315.3(each)-315.3(nucleus)-315.3(has)-315.3(a)-315.3(characteristic)-315.3(resonant)-315.3(frequenc)15(y)65(,)]TJ -9.4824 -1.2 TD [(we)-299.9(can)]TJ /F8 1 Tf 3.1538 0 TD ()Tj /F9 1 Tf 0.444 0 TD (tune)Tj /F8 1 Tf 1.722 0 TD ()Tj /F9 1 Tf 0.7439 0 TD [(the)-299.9(radio)-299.9(dial)-299.9(to)-299.9(an)15(y)-299.9(nucleus)-299.9(we)-299.9(are)-299.9(interested)-299.9(in)-299.9(observing.)-299.9(W)80(e)-299.9(can)-299.9(think)]TJ -6.0637 -1.2 TD [(of)-308.4(the)-308.4(v)25(arious)-308.4(NMR-acti)25(v)15(e)-308.4(nuclei)-308.4(in)-308.4(the)-308.4(sample)-308.4(as)]TJ /F8 1 Tf 20.8188 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(radio)-308.4(stations)]TJ /F8 1 Tf 5.4195 0 TD ()Tj /F9 1 Tf 0.7524 0 TD [(that)-308.4(we)-308.4(can)-308.4(tune)-308.4(into)]TJ -27.4347 -1.2 TD [(v)15(ery)-314.1(accurately)65(,)-314.1(just)-314.1(as)-314.1(stations)-314.1(come)-314.1(into)-314.1(tune)-314.1(in)-314.1(a)-314.1(v)15(ery)-314.1(narro)25(w)-314.1(range)-314.1(of)-314.1(frequencies)-314.1(on)]TJ T* [(an)-359.3(FM)-359.2(radio.)-359.3(Ha)20(ving)-359.3(chosen)-359.3(a)]TJ /F8 1 Tf 12.9946 0 TD ()Tj /F9 1 Tf 0.444 0 TD (station)Tj /F8 1 Tf 2.667 0 TD ()Tj /F9 1 Tf 0.8033 0 TD [(to)-359.3(listen)-359.3(to,)-359.3(what)-359.3(can)-359.3(we)-359.3(learn)-359.3(by)-359.3(observing)-359.3(a)]TJ -16.9089 -1.2 TD [(particular)-255.1(type)-255.1(of)-255.1(nucleus?)-255.1(The)-255.1(resonant)-255.1(frequenc)15(y)-255.1(i)0(s)-255.1(a)0(l)10(w)10(ays,)-255.1(al)10(w)10(ays,)-255.1(al)10(w)10(ays)-255.1(proportional)]TJ T* [(to)-250(the)-250(magnetic)]TJ /F8 1 Tf 6.4161 0 TD ()Tj /F9 1 Tf 0.556 0 TD (eld:)Tj /F2 1 Tf 8.3032 -2.4101 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 277.1231 214.9042 Tm (o)Tj /F3 1 Tf 9.9626 0 0 9.9626 284.1744 216.3986 Tm ()Tj /F2 1 Tf 1.0578 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 306.4886 214.9043 Tm (o)Tj /F2 1 Tf 9.9626 0 0 9.9626 310.7726 216.3986 Tm ()Tj /F9 1 Tf 0.47 0 TD (2)Tj /F2 1 Tf 0.504 0 TD ()Tj /F9 1 Tf -20.0988 -2.4101 TD [(b)20(u)0(t)-280(the)-280(e)15(xact)-280(magnetic)]TJ /F8 1 Tf 9.3611 0 TD ()Tj /F9 1 Tf 0.556 0 TD (eld)Tj /F4 1 Tf 1.502 0 TD [()20(\012)-280(\(\015)-280( )-280(  )]TJ /F9 1 Tf 11.1521 0 TD [(may)-280(be)-280(slightly)-280(dif)25(ferent)-280(than)-280(the)]TJ -22.5713 -1.2 TD [(e)15(xternal)-234.1(magnetic)]TJ /F8 1 Tf 7.3403 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld.)-234.1(The)-234.1(nucleus)-234.1(is)-234.1(located)-234.1(at)-234.1(the)-234.1(center)-234.1(of)-234.1(a)-234.1(cloud)-234.1(of)-234.1(electrons,)-234.1(and)-234.1(we)]TJ -7.8963 -1.2 TD [(kno)25(w)-203.1(that)-203.1(electrons)-203.1(are)-203.1(easily)-203.1(pulled)-203.1(a)15(w)10(ay)-203.1(or)-203.1(pushed)-203.1(to)25(w)10(ard)-203.1(an)-203.1(atom,)-203.1(changing)-203.1(the)-203.1(electron)]TJ T* [(density)-261.1(around)-261.1(that)-261.1(nucleus.)-261.1(Furthermore,)-261.1(electron)-261.1(clouds)-261.1(can)-261.1(be)15(gin)-261.1(to)-261.1(circulate)-261.1(under)-261.1(the)]TJ T* (in)Tj /F8 1 Tf 0.778 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(uence)-224.6(of)-224.6(the)-224.6(laboratory)]TJ /F8 1 Tf 9.3956 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld,)-224.6(creating)-224.6(their)-224.6(o)25(w)0(n)-224.6(magnetic)]TJ /F8 1 Tf 13.0122 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(elds,)-224.6(which)-224.6(subtract)-224.6(from)-224.6(or)]TJ ET endstream endobj 64 0 obj > endobj 65 0 obj > stream BT /F9 1 Tf 7.9701 0 0 7.9701 253.6448 730.6316 Tm 0 g /GS1 gs 0 Tc 0 Tw [(FUND)40(AMENT)93(AL)-250(CONCEPTS)-250(OF)-250(NMR)-250(SPECTR)40(OSCOPY)]TJ /F1 1 Tf 8.9664 0 0 8.9664 468.5827 730.6316 Tm ($$)Tj /F9 1 Tf 9.9626 0 0 9.9626 118.8941 706.4592 Tm [(add)-280.7(to)-280.7(the)-280.7(e)15(xternal)]TJ /F8 1 Tf 7.773 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld.)-280.7(So)-280.7(the)-280.7(nucleus)]TJ /F8 1 Tf 7.928 0 TD ()Tj /F9 1 Tf 0.444 0 TD (feels)Tj /F8 1 Tf 1.888 0 TD ()Tj /F9 1 Tf 0.7247 0 TD [(a)-280.7(slightly)-280.7(dif)25(ferent)]TJ /F8 1 Tf 7.7053 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld,)-280.7(depending)-280.7(on)-280.7(its)]TJ -27.5751 -1.2 TD [(position)-250(within)-250(a)-250(molecule)-250(\(its)]TJ /F8 1 Tf 12.4171 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(chemical)-250(en)40(vironment)]TJ /F8 1 Tf 8.8751 0 TD ()Tj /F9 1 Tf 0.444 0 TD (\):)Tj /F2 1 Tf -13.5113 -2.3571 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 212.0345 669.4853 Tm [(ef)25(f)]TJ /F3 1 Tf 9.9626 0 0 9.9626 224.1133 671.0208 Tm ()Tj /F2 1 Tf 1.0578 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 241.4262 669.5264 Tm (o)Tj 9.9626 0 0 9.9626 247.3706 671.0208 Tm (\(1)Tj /F3 1 Tf 1.0552 0 TD ()Tj /F2 1 Tf 1.0022 0 TD ()Tj /F9 1 Tf 0.593 0 TD (\))Tj /F2 1 Tf 1.333 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 291.7588 669.5264 Tm (o)Tj /F3 1 Tf 9.9626 0 0 9.9626 298.8101 671.0208 Tm ()Tj /F2 1 Tf 1.0578 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 321.1244 669.4853 Tm [(ef)25(f)]TJ /F3 1 Tf 9.9626 0 0 9.9626 333.2031 671.0208 Tm ()Tj /F2 1 Tf 1.0578 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 355.5174 669.5264 Tm (o)Tj 9.9626 0 0 9.9626 361.4617 671.0208 Tm (\(1)Tj /F3 1 Tf 1.0552 0 TD ()Tj /F2 1 Tf 1.0022 0 TD ()Tj /F9 1 Tf 0.593 0 TD (\))Tj -26.9982 -2.3571 TD (Where)Tj /F2 1 Tf 2.9191 0 TD ()Tj /F9 1 Tf 0.8471 0 TD [(is)-254.1(a)]TJ /F8 1 Tf 1.6191 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(shielding)-254.1(constant)]TJ /F8 1 Tf 7.2542 0 TD ()Tj /F9 1 Tf 0.6981 0 TD [(in)-254.1(units)-254.1(of)-254.1(parts)-254.1(per)-254.1(million,)-254.1(which)-254.1(re)]TJ /F8 1 Tf 14.9166 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(ects)-254.1(the)-254.1(e)15(xtent)-254.1(to)]TJ -29.2541 -1.2 TD [(which)-273(the)-273(electron)-273(cloud)-273(around)-273(the)-273(nucleus)]TJ /F8 1 Tf 18.0742 0 TD ()Tj /F9 1 Tf 0.444 0 TD (shields)Tj /F8 1 Tf 2.778 0 TD ()Tj /F9 1 Tf 0.717 0 TD [(it)-273(from)-273(the)-273(e)15(xternal)-273(magnetic)]TJ /F8 1 Tf 11.9591 0 TD ()Tj /F9 1 Tf 0.556 0 TD (eld.)Tj -34.5284 -1.2 TD [(These)-347.9(dif)25(ferences,)-347.9(which)-347.9(we)-347.9(call)]TJ /F8 1 Tf 13.8485 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(chemical)-347.9(shifts)]TJ /F8 1 Tf 6.1249 0 TD ()Tj /F9 1 Tf 0.7919 0 TD [(are)-347.9(really)-347.9(tin)15(y:)-347.9(for)-347.9(a)]TJ 7.5716 0 0 7.5716 416.5349 627.2435 Tm (1)Tj 9.9626 0 0 9.9626 420.8189 623.6271 Tm [(H)-347.8(nucleus)-347.9(the)]TJ /F8 1 Tf -30.3057 -1.2 TD ()Tj /F9 1 Tf 0.444 0 TD (spread)Tj /F8 1 Tf 2.61 0 TD ()Tj /F9 1 Tf 0.6937 0 TD [(of)-249.7(resonant)-249.7(frequencies)-249.7(around)-249.7(the)-249.7(fundamental)-249.7(frequenc)15(y)-249.7(i)0(s)-249.7(only)-249.7(about)-249.7(10)-249.7(ppm.)]TJ -3.7477 -1.2 TD [(That)-334(means)-334(that)-334(on)-334(a)-334(500)-334(MHz)-334(NMR)-333.9(instrument,)-334(the)-334(protons)-334(in)-334(a)-334(molecule)-334(might)-334(ha)20(v)15(e)]TJ T* [(a)-364.1(range)-364.1(of)-364.1(resonant)-364.1(frequencies)-364.1(between)-364.1(499.9975)-364.1(and)-364.1(500.0025)-364.1(MHz)-364.1(\(0.0025)-364.1(MHz)-364.1(is)]TJ T* [(5)-274.5(ppm)-274.5(of)-274.5(500)-274.5(MHz\),)-274.5(depending)-274.5(on)-274.5(their)-274.5(location)-274.5(within)-274.5(the)-274.5(molecule.)-274.5(Thus)-274.5(we)-274.5(tune)-274.5(in)-274.5(to)]TJ T* (a)Tj /F8 1 Tf 0.7864 0 TD ()Tj /F9 1 Tf 0.444 0 TD (station)Tj /F8 1 Tf 2.667 0 TD ()Tj /F9 1 Tf 0.7864 0 TD (\(499.9975)Tj /F8 1 Tf 4.0831 0 TD ()Tj /F9 1 Tf 0.5 0 TD [(500.0025)-342.4(MHz\))-342.4(and)-342.4(study)-342.4(the)-342.4(tin)15(y)-342.4(v)25(ariations)-342.4(\(chemical)-342.4(shifts\))-342.4(in)]TJ -9.2668 -1.2 TD [(resonant)-221.8(frequenc)15(y)-221.8(t)0(o)-221.8(learn)-221.8(something)-221.8(about)-221.8(the)-221.8(chemical)-221.8(structure)-221.8(of)-221.8(the)-221.8(molecule.)-221.8(In)-221.8(this)]TJ T* -0.0001 Tc [(w)9.9(a)-0.1(y)64.9(,)-246.3(physics)-246.3(\(and)-246.3(radio)-246.3(electronics\))-246.3(comes)-246.3(to)-246.3(the)-246.3(aid)-246.3(of)-246.3(chemistry)-246.3(in)-246.3(helping)-246.3(us)-246.3(determine)]TJ T* 0 Tc [(a)-250.6(molecule)]TJ /F8 1 Tf 4.3606 0 TD ()Tj /F9 1 Tf 0.278 0 TD [(s)-250.6(structure.)-250.6(An)-250.6(NMR)-250.6(spectrum)-250.6(is)-250.6(just)-250.6(a)-250.6(graph)-250.6(of)-250.6(intensity)-250.6(v)15(ersus)-250.6(frequenc)15(y)-250.6(for)]TJ -4.6386 -1.2 TD [(the)-285.4(narro)25(w)-285.4(range)-285.4(of)-285.4(frequencies)-285.4(corresponding)-285.4(to)-285.4(the)-285.4(particular)-285.4(nucleus)-285.4(we)-285.4(are)-285.4(interested)]TJ T* [(in.)-238.6(Each)]TJ /F8 1 Tf 3.5043 0 TD ()Tj /F9 1 Tf 0.444 0 TD (peak)Tj /F8 1 Tf 1.888 0 TD ()Tj /F9 1 Tf 0.6826 0 TD [(in)-238.6(this)-238.6(graph)-238.6(corresponds)-238.6(to)-238.6(a)-238.6(particular)-238.6(en)40(vironment)-238.6(within)-238.6(the)-238.6(molecule,)]TJ -6.5189 -1.2 TD -0.0001 Tc [(such)-242.6(as)-242.6(a)-242.6(particular)-242.6(hydrogen)-242.6(atom)-242.6(position)-242.6(in)-242.6(an)-242.6(or)17.9(ganic)-242.6(structure.)-242.6(When)-242.6(each)-242.6(position)-242.6(in)]TJ T* 0 Tc [(a)-201.9(molecule)-201.9(has)-201.9(a)-201.9(dif)25(ferent)-201.9(chemical)-201.9(shift,)-201.9(we)-201.9(can)]TJ /F8 1 Tf 19.314 0 TD ()Tj /F9 1 Tf 0.444 0 TD (talk)Tj /F8 1 Tf 1.5 0 TD ()Tj /F9 1 Tf 0.6459 0 TD [(to)-201.9(these)-201.9(atoms)-201.9(indi)25(vidually)-201.9(in)-201.9(NMR)]TJ -21.9039 -1.2 TD [(e)15(xperiments,)-277.9(looking)-277.9(around)-277.9(at)-277.9(the)-277.9(local)-277.9(en)40(vironment)-277.9(from)-277.9(the)-277.9(point)-277.9(of)-277.9(vie)25(w)-277.9(o)0(f)-277.9(one)-277.9(atom)]TJ T* [(in)-250(the)-250(structure)-250(at)-250(a)-250(time.)]TJ /F1 1 Tf 0 -2.4857 TD -0.01 Tw [(&&)-1000( )-250(! :)-250( )-10(#)]TJ /F9 1 Tf 0 -1.8 TD 0 Tw [(If)-200.2(we)-200.2(consider)-200.2(the)-200.2(ener)18(gy)-200.2(of)-200.2(a)-200.2(nucleus)-200.2(as)-200.2(it)-200.2(interacts)-200.2(with)-200.2(the)-200.2(e)15(xternal)-200.2(magnetic)]TJ /F8 1 Tf 31.129 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld,)-200.2(we)-200.2(see)]TJ -31.685 -1.2 TD [(that)-292.1(there)-292.1(are)-292.1(tw)10(o)-292.1(ener)18(gy)-292.1(le)25(v)15(els)-292.1(for)-292.1(a)-292.1(spin-)]TJ /F8 1 Tf 17.1527 0 TD ()Tj /F9 1 Tf 1.0421 0 TD [(nucleus.)-292.1(The)]TJ /F8 1 Tf 5.4442 0 TD ()Tj /F9 1 Tf 0.444 0 TD (aligned)Tj /F8 1 Tf 2.944 0 TD ()Tj /F9 1 Tf 0.7361 0 TD [(state)-292.1(\(or)]TJ /F2 1 Tf 3.5832 0 TD (\015)Tj /F9 1 Tf 0.8631 0 TD [(state\))-292.1(has)]TJ -32.2093 -1.2 TD [(the)-233.5(nuclear)-233.5(magnet)-233.5(aligned)-233.5(with)-233.5(the)-233.5(laboratory)]TJ /F8 1 Tf 18.7977 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld,)-233.5(gi)25(ving)-233.5(it)-233.5(a)-233.5(l)0(o)25(wer)-233.5(ener)18(gy)-233.5(\(more)-233.5(stable\))]TJ -19.3537 -1.2 TD [(state)-258.9(\(Fig.)-258.9(1.2\).)-258.9(The)]TJ /F8 1 Tf 8.1738 0 TD ()Tj /F9 1 Tf 0.444 0 TD (disaligned)Tj /F8 1 Tf 4.1111 0 TD ()Tj /F9 1 Tf 0.7029 0 TD [(state)-258.9(\(or)]TJ /F2 1 Tf 3.5169 0 TD ()Tj /F9 1 Tf 0.8389 0 TD [(state\))-258.9(is)-258.9(aligned)-258.9(opposite)-258.9(to)-258.9(the)-258.9(e)15(xternal)]TJ /F8 1 Tf 16.1847 0 TD ()Tj /F9 1 Tf 0.556 0 TD (eld,)Tj -34.5284 -1.2 TD [(resulting)-250(in)-250(a)-250(higher)-250(ener)18(gy)65(.)-250(The)-250(ener)18(gy)]TJ /F8 1 Tf 16.1732 0 TD ()Tj /F9 1 Tf 0.444 0 TD -0.0025 Tc (gap)Tj /F8 1 Tf 1.439 0 TD 0 Tc ()Tj /F9 1 Tf 0.694 0 TD [(between)-250(these)-250(tw)10(o)-250(l)0(e)25(v)15(els)-250(is:)]TJ /F2 1 Tf -5.4678 -2.3571 TD ()Tj /F3 1 Tf 1.8138 0 TD ()Tj /F2 1 Tf 1.0578 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 290.0826 340.7595 Tm (o)Tj /F3 1 Tf 9.9626 0 0 9.9626 297.1339 342.2539 Tm ()Tj /F2 1 Tf 1.0578 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 324.9974 340.7596 Tm (o)Tj /F2 1 Tf 9.9626 0 0 9.9626 329.2813 342.2539 Tm ()Tj /F9 1 Tf 0.47 0 TD (2)Tj /F2 1 Tf 0.504 0 TD ()Tj /F9 1 Tf -22.0916 -2.3571 TD (where)Tj /F4 1 Tf 2.6592 0 TD ()Tj /F9 1 Tf 0.7162 0 TD [(is)-216.2(Planck)]TJ /F8 1 Tf 3.6052 0 TD ()Tj /F9 1 Tf 0.278 0 TD [(s)-216.2(constant)-216.2(and)]TJ /F2 1 Tf 5.8145 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 253.9783 317.2762 Tm (o)Tj 9.9626 0 0 9.9626 260.4156 318.7706 Tm [(is)-216.2(the)-216.2(Larmor)-216.2(\()]TJ /F8 1 Tf 5.8695 0 TD ()Tj /F9 1 Tf 0.444 0 TD (resonant)Tj /F8 1 Tf 3.388 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(\))-216.2(frequenc)15(y)65(.)-216.2(This)-216.2(relationship)]TJ -24.3508 -1.2 TD -0.0001 Tc [(between)-241(the)-241(ener)17.9(gy)-241(gap)-241(between)-241(tw)9.9(o)-241(quantum)-241(states)-241(and)-241(the)-241(frequenc)14.9(y)-241(o)-0.1(f)-241(electromagnetic)]TJ T* 0 Tc [(radiation)-231.9(\()]TJ /F8 1 Tf 4.1199 0 TD ()Tj /F9 1 Tf 0.444 0 TD (photons)Tj /F8 1 Tf 3.167 0 TD ()Tj /F9 1 Tf 0.444 0 TD 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[(we)-288.8(ha)20(v)15(e)-288.8(to)-288.8(w)10(ork)-288.8(with)-288.8(and)-288.8(to)-288.8(detect)-288.8(in)-288.8(the)-288.8(NMR)-288.7(e)15(xperiment.)-288.8(Because)-288.8(the)-288.8(dif)25(ference)-288.8(is)-288.8(so)]TJ T* [(small,)-202.7(the)-202.7(sensiti)25(vity)-202.7(of)-202.7(NMR)-202.6(is)-202.7(in)-202.7(man)15(y)-202.7(orders)-202.7(of)-202.7(magnitude)-202.7(lo)25(wer)-202.7(than)-202.7(all)-202.7(other)-202.7(analytical)]TJ T* [(techniques;)-257.6(so)-257.6(lo)25(w)65(,)-257.6(in)-257.6(f)10(act,)-257.6(that)-257.6(NMR)-257.6(is)-257.6(not)-257.6(considered)-257.6(a)-257.6(branch)-257.6(of)]TJ /F8 1 Tf 27.0227 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(analytical)-257.6(chemistry)]TJ /F8 1 Tf 8.0897 0 TD ()Tj /F9 1 Tf -35.5564 -1.2 TD -0.0001 Tc [(b)19.9(u)-0.1(t)-250.1(rather)-250.1(a)-250.1(tool)-250.1(used)-250.1(by)-250.1(or)17.9(ganic)-250.1(chemists)-250.1(and)-250.1(biologists.)]TJ /F1 1 Tf 0 -3.5 TD 0 Tc [(&*)-1000(")-250(!"="!)-250(")-250(46 #)]TJ /F9 1 Tf 0 -1.8 TD 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[(is)-194.3(the)-194.3(microscopic)-194.3(gas)-194.3(constant,)]TJ /F4 1 Tf 12.6588 0 TD 0 Tc ()Tj /F9 1 Tf 0.7501 0 TD [(is)-194.1(the)-194.1(absolute)-194.1(temperature)-194.1(in)-194.1(k)10(elvin)-194.1(\(K\),)-194.1(and)]TJ /F2 1 Tf 17.9012 0 TD ()Tj /F4 1 Tf 0.804 0 TD ()Tj /F9 1 Tf -35.3894 -1.2 TD [(is)-217.9(the)-217.9(dif)25(ference)-217.9(in)-217.9(ener)18(gy)-217.9(between)-217.9(the)-217.9(tw)10(o)-217.9(states)]TJ /F8 1 Tf 19.4072 0 TD ()Tj /F9 1 Tf 1 0 TD (the)Tj /F8 1 Tf 1.4399 0 TD ()Tj /F9 1 Tf 0.444 0 TD -0.0005 Tc [(ener)17.5(gy)-218.4(gap.)]TJ /F8 1 Tf 4.5399 0 TD 0 Tc ()Tj /F9 1 Tf 0.6619 0 TD [(W)80(e)-217.9(can)-217.9(think)-217.9(of)]TJ /F4 1 Tf 6.4566 0 TD (-)Tj /F9 1 Tf 1.2179 0 TD (as)Tj -35.1674 -1.2 TD [(the)-203.7(a)20(v)15(erage)-203.7(amount)-203.7(of)-203.7(total)-203.7(ener)18(gy)-203.7(that)-203.7(a)-203.7(molecule)-203.7(has)]TJ /F8 1 Tf 21.3867 0 TD ()Tj /F9 1 Tf 1 0 TD [(analogous)-203.7(to)-203.7(the)-203.7(amount)-203.7(of)-203.7(mone)15(y)]TJ -22.3867 -1.2 TD [(the)-244.6(a)20(v)15(erage)-244.6(person)-244.6(is)-244.6(carrying)-244.6(in)-244.6(his)-244.6(or)-244.6(her)-244.6(pock)10(et.)]TJ /F2 1 Tf 20.3685 0 TD ()Tj /F4 1 Tf 0.804 0 TD ()Tj /F9 1 Tf 0.8556 0 TD [(is)-244.6(analogous)-244.6(to)-244.6(the)-244.6(price)-244.6(dif)25(ference)]TJ -22.0281 -1.2 TD [(between)-277.6(a)-277.6(hamb)20(ur)18(ger)-277.6(and)-277.6(a)-277.6(cheeseb)20(ur)18(ger)55(.)-277.6(I)0(f)-277.6(the)-277.7(amount)-277.6(of)-277.6(mone)15(y)-277.6(the)-277.6(a)20(v)15(erage)-277.7(person)-277.6(has)]TJ T* (\()Tj /F4 1 Tf 0.333 0 TD (-)Tj /F9 1 Tf 1 0 TD [(\))-333.8(i)0(s)-333.9(v)15(ery)-333.9(small)-333.9(and)-333.9(the)-333.9(price)-333.9(dif)25(ference)-333.9(\()]TJ /F2 1 Tf 16.6261 0 TD ()Tj /F4 1 Tf 0.804 0 TD ()Tj /F9 1 Tf 0.611 0 TD [(\))-333.8(i)0(s)-333.9(lar)18(ge,)-333.9(then)-333.9(nearly)-333.9(e)25(v)15(eryone)-333.9(will)-333.9(tak)10(e)]TJ -19.3742 -1.2 TD [(the)-299.4(hamb)20(ur)18(ger)55(.)-299.4(But)-299.4(if)-299.4(the)-299.4(a)20(v)15(erage)-299.4(person)-299.4(is)-299.4(carrying)-299.4(around)-299.4(a)-299.4(lot)-299.4(of)-299.4(mone)15(y)-299.4(and)-299.4(the)-299.4(price)]TJ T* [(dif)25(ference)-251.2(is)-251.2(v)15(ery)-251.2(small,)-251.2(there)-251.2(will)-251.2(be)-251.2(only)-251.2(a)-251.2(v)15(ery)-251.2(slight)-251.2(preference)-251.2(for)-251.2(the)-251.2(hamb)20(ur)18(ger)55(.)-251.2(Just)]TJ T* [(ho)25(w)-289.2(big)-289.2(is)]TJ /F4 1 Tf 4.5095 0 TD (-)Tj /F9 1 Tf 1.2891 0 TD [(compared)-289.2(to)-289.2(the)-289.2(ener)18(gy)-289.2(dif)25(ference)-289.2(in)-289.2(NMR?)-289.2(At)-289.2(25)]TJ /F3 1 Tf 7.5716 0 0 7.5716 384.1152 198.3285 Tm ()Tj /F9 1 Tf 9.9626 0 0 9.9626 388.3991 194.712 Tm [(C)-289.1(\(298)-289.2(K\),)]TJ /F4 1 Tf 4.6725 0 TD (-)Tj /F9 1 Tf 1.2891 0 TD [(is)-289.2(equal)]TJ -32.8782 -1.2 TD [(to)-299.1(2478)-299.1(J/mol.)-299.1(F)15(o)0(r)-299.1(a)-299.1(proton)-299.1(\()]TJ 7.5716 0 0 7.5716 237.8729 186.3733 Tm (1)Tj 9.9626 0 0 9.9626 242.1568 182.7569 Tm [(H\))-299(in)-299.1(a)-299.1(7.05)-299.1(T)-299(magnetic)]TJ /F8 1 Tf 10.0984 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-299.1(\()]TJ /F2 1 Tf 1.8541 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 371.6161 181.2625 Tm (o)Tj /F3 1 Tf 9.9626 0 0 9.9626 378.8795 182.7569 Tm ()Tj /F9 1 Tf 1.0791 0 TD [(300)-299.1(MHz\),)-299.1(the)-299.1(ener)18(gy)]TJ -27.0401 -1.2 TD -0.001 Tc [(gap)-251(is:)]TJ /F2 1 Tf 10.4002 -2.6333 TD 0 Tc ()Tj /F3 1 Tf 1.8138 0 TD ()Tj /F2 1 Tf 1.0578 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 262.7128 143.0724 Tm (o)Tj /F3 1 Tf 9.9626 0 0 9.9626 269.7641 144.5667 Tm ()Tj /F7 1 Tf 1.0578 0 TD ()Tj /F9 1 Tf 0.5403 0 TD (\()Tj /F2 1 Tf 0.333 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 300.7787 143.0723 Tm (o)Tj 9.9626 0 0 9.9626 305.0626 144.5667 Tm (\))Tj /F3 1 Tf 0.6108 0 TD ()Tj /F9 1 Tf 1.0578 0 TD (0)Tj /F2 1 Tf 0.505 0 TD (\012)Tj /F9 1 Tf 0.275 0 TD [(0315)-166.7(J)]TJ /F2 1 Tf 2.5657 0 TD ()Tj /F9 1 Tf 0.47 0 TD (mol)Tj ET endstream endobj 68 0 obj > /ExtGState > >> endobj 69 0 obj > endobj 70 0 obj > endobj 71 0 obj > stream BT /F9 1 Tf 7.9701 0 0 7.9701 253.6448 730.6316 Tm 0 g /GS1 gs 0 Tc 0 Tw [(FUND)40(AMENT)93(AL)-250(CONCEPTS)-250(OF)-250(NMR)-250(SPECTR)40(OSCOPY)]TJ /F1 1 Tf 8.9664 0 0 8.9664 468.5827 730.6316 Tm ($'')Tj /F9 1 Tf 9.9626 0 0 9.9626 118.8941 706.4592 Tm -0.0001 Tc [(So)-214.9(the)-214.9(ener)17.9(gy)-214.9(gap)-214.9(i)-0.1(s)-214.9(v)14.9(ery)64.9(,)-214.9(v)14.9(ery)-214.9(small)-214.9(compared)-214.9(to)-214.9(the)-214.9(a)19.9(v)14.9(erage)-214.9(ener)17.9(gy)-214.9(that)-214.9(a)-214.9(molecule)-214.9(has)-214.9(at)]TJ 0 -1.2 TD 0 Tc [(room)-254.7(temperature.)-254.7(Another)-254.7(w)10(a)0(y)-254.7(o)0(f)-254.7(saying)-254.7(this)-254.7(is)-254.7(that)]TJ /F2 1 Tf 21.4188 0 TD ()Tj /F4 1 Tf 0.804 0 TD ()Tj /F9 1 Tf 0.611 0 TD (/)Tj /F4 1 Tf 0.278 0 TD (-)Tj /F9 1 Tf 1.2547 0 TD [(is)-254.7(a)-254.7(number)-254.7(much,)-254.7(much)-254.7(less)]TJ -24.3666 -1.2 TD [(than)-294.3(1.)-294.3(The)-294.3(e)15(xponential)-294.3(function)-294.3(can)-294.3(be)-294.3(simpli)]TJ /F8 1 Tf 18.9042 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(ed)-294.3(by)-294.3(approximation)-294.3(if)-294.3(the)-294.3(ar)18(gument)-294.3(is)-294.3(a)]TJ -19.4602 -1.2 TD [(v)15(ery)-250(small)-250(number)-250(compared)-250(to)-250(1:)]TJ 13.2548 -2.388 TD (e)Tj /F3 1 Tf 7.5716 0 0 7.5716 255.4596 650.9175 Tm ()Tj /F2 1 Tf 0.78 0 TD ()Tj /F3 1 Tf 9.9626 0 0 9.9626 267.3325 646.803 Tm ()Tj /F9 1 Tf 0.9467 0 TD (1)Tj /F3 1 Tf 0.7222 0 TD ()Tj /F2 1 Tf 1.0022 0 TD ( )Tj /F9 1 Tf 1.9977 0 TD (if)Tj /F2 1 Tf 0.8567 0 TD ()Tj /F3 1 Tf 0.6697 0 TD ()Tj /F9 1 Tf 1.1507 0 TD (1)Tj -22.2453 -2.388 TD [(W)80(e)-250(can)-250(no)25(w)-250(simplify)-250(the)-250(Boltzmann)-250(equation:)]TJ /F2 1 Tf 11.167 -2.388 TD ()Tj 7.5716 0 0 7.5716 236.4338 597.7271 Tm ()Tj 9.9626 0 0 9.9626 241.3234 599.2214 Tm ()Tj 7.5716 0 0 7.5716 252.2924 597.7271 Tm (\015)Tj /F3 1 Tf 9.9626 0 0 9.9626 259.8813 599.2214 Tm 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468.1928 Tm (and)Tj /F4 1 Tf 1.7429 0 TD (#)Tj /F2 1 Tf 7.5716 0 0 7.5716 436.9888 466.6984 Tm ()Tj /F9 1 Tf 9.9626 0 0 9.9626 444.8562 468.1928 Tm [(are)-298.9(v)15(ery)]TJ -32.7185 -1.2 TD [(close)-249.1(to)-249.1(half)-249.1(the)-249.1(total)-249.1(number)-249.1(of)-249.1(spins)-249.1(in)-249.1(the)-249.1(sample.)-249.1(Finally)65(,)-249.1(substituting)]TJ /F7 1 Tf 29.3407 0 TD ()Tj /F2 1 Tf 0.5403 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 428.4932 454.7432 Tm (o)Tj 9.9626 0 0 9.9626 435.2589 456.2376 Tm (for)Tj /F2 1 Tf 1.4151 0 TD ()Tj /F4 1 Tf 0.804 0 TD ()Tj /F9 1 Tf 0.8601 0 TD (we)Tj -34.8344 -1.2 TD (obtain:)Tj /F2 1 Tf 13.052 -2.388 TD ()Tj 7.5716 0 0 7.5716 255.213 418.9973 Tm (\015)Tj /F3 1 Tf 9.9626 0 0 9.9626 262.2484 420.4917 Tm ()Tj /F2 1 Tf 1.0022 0 TD ()Tj 7.5716 0 0 7.5716 278.5197 418.9973 Tm ()Tj /F3 1 Tf 9.9626 0 0 9.9626 286.1767 420.4917 Tm ()Tj /F2 1 Tf 1.0578 0 TD ()Tj /F7 1 Tf 0.824 0 TD ()Tj /F2 1 Tf 0.5403 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 322.0829 418.9973 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1 Tf 9.9626 0 0 9.9626 338.2338 301.1792 Tm ()Tj /F9 1 Tf 7.5716 0 0 7.5716 345.0085 299.6848 Tm (o)Tj /F2 1 Tf 9.9626 0 0 9.9626 349.2924 301.1792 Tm ()Tj /F9 1 Tf 0.47 0 TD (2)Tj /F2 1 Tf 0.504 0 TD ()Tj /F9 1 Tf -24.1003 -2.388 TD [(The)-214.5(net)-214.5(magnetization)-214.5(of)-214.5(the)-214.5(sample)-214.5(at)-214.5(equilibrium)-214.5(is)-214.5(proportional)-214.5(to)-214.5(the)-214.5(amount)-214.5(of)-214.5(sample)]TJ 0 -1.2 TD (\()Tj /F4 1 Tf 0.333 0 TD ()Tj /F9 1 Tf 0.667 0 TD [(\),)-187.3(the)-187.3(square)-187.3(of)-187.3(the)-187.3(nuclear)-187.3(magnet)-187.3(strength)-187.3(\()]TJ /F2 1 Tf 17.4109 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 308.1331 269.0497 Tm (2)Tj 9.9626 0 0 9.9626 312.4474 265.4333 Tm [(\),)-187.3(and)-187.3(the)]TJ /F8 1 Tf 3.811 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-187.3(strength)-187.3(\()]TJ /F4 1 Tf 5.1517 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 413.3666 263.9389 Tm (o)Tj 9.9626 0 0 9.9626 417.6505 265.4333 Tm [(\),)-187.3(and)-187.3(in)40(v)15(ersely)]TJ 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()Tj /F9 1 Tf 0.58 0 TD (\))Tj /F3 1 Tf -5.8907 -1.2 TD ()Tj /F2 1 Tf -4.5331 -1.2 TD -0.013 Tc ()Tj /F9 1 Tf 1.208 0 TD 0 Tc (2)Tj /F3 1 Tf 0.7262 0 TD ()Tj /F2 1 Tf 1.0022 0 TD 3.4323 Tc [( )3445.3()]TJ /F9 1 Tf 5.0703 0 TD 1.004 Tc (2\()Tj /F2 1 Tf 1.837 0 TD 0 Tc (\015)Tj /F9 1 Tf 0.571 0 TD (\))Tj -23.0364 -2.2503 TD (where)Tj /F4 1 Tf 2.6612 0 TD ()Tj /F9 1 Tf 0.8851 0 TD [(is)-218.2(the)-218.2(total)-218.2(number)-218.2(of)-218.2(identical)-218.2(spins)-218.2(in)-218.2(the)-218.2(sample)-218.2(and)]TJ /F2 1 Tf 21.732 0 TD ( )Tj /F9 1 Tf 0.6482 0 TD [(is)-218.2(a)-218.2(v)15(ery)-218.2(small)-218.2(fraction)-218.2(of)]TJ -25.9265 -1.2 TD [(this)-257.1(number)55(.)-257.1(W)40(ith)-257.1(the)-257.1(equal)-257.1(populations,)-257.1(the)-257.1(rate)-257.1(of)-257.1(absorption)-257.1(equals)-257.1(the)-257.1(rate)-257.1(of)-257.1(emission)]TJ T* 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TD [(strength)-153.2(\()]TJ /F4 1 Tf 3.7082 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 163.2699 238.7137 Tm (o)Tj 9.9626 0 0 9.9626 167.5538 240.208 Tm [(\))-153.2(remaining)-153.2(constant.)-153.2(A)-153.1(detector)-153.2(in)-153.2(the)-153.2(transmitter)-153.2(circuit)-153.2(monitors)-153.2(the)-153.2(amount)-153.2(of)]TJ -4.7492 -1.2 TD [(RF)-205.5(ener)18(gy)-205.5(absorbed,)-205.5(and)-205.5(this)-205.5(signal)-205.5(is)-205.5(applied)-205.5(to)-205.5(a)-205.5(pen,)-205.5(which)-205.5(mo)15(v)15(e)0(s)-205.5(u)0(p)-205.5(and)-205.5(do)25(wn.)-205.5(The)-205.5(pen)]TJ T* [(mo)15(v)15(e)0(s)-216.6(from)-216.6(left)-216.6(to)-216.6(right)-216.6(across)-216.6(the)-216.6(paper)-216.6(as)-216.6(the)-216.6(frequenc)15(y)-216.6(i)0(s)-216.6(gradually)-216.6(decreased,)-216.6(and)-216.6(when)]TJ T* [(we)-240.8(reach)-240.8(the)-240.8(Larmor)-240.8(frequenc)15(y)-240.8(\()]TJ /F2 1 Tf 13.0719 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 255.3116 202.8481 Tm (o)Tj 9.9626 0 0 9.9626 259.5956 204.3425 Tm [(\),)-240.8(there)-240.8(is)-240.8(a)-240.8(net)-240.8(absorption)-240.8(of)-240.8(ener)18(gy)-240.8(and)-240.8(the)-240.8(pen)-240.8(mo)15(v)15(e)0(s)]TJ -13.9879 -1.2 TD [(up.)-205.8(As)-205.8(we)-205.8(pass)-205.8(through)-205.8(the)-205.8(Larmor)-205.8(frequenc)15(y)65(,)-205.8(the)-205.8(resonance)-205.8(condition)-205.8(is)-205.8(no)-205.8(longer)-205.8(met)-205.8(and)]TJ T* [(absorption)-312.8(stops,)-312.8(so)-312.8(the)-312.8(pen)-312.8(mo)15(v)15(e)0(s)-312.8(back)-312.8(do)25(wn.)-312.8(The)-312.8(spins)-312.8(ne)25(v)15(e)0(r)-312.8(reach)-312.8(the)-312.8(saturated)-312.8(state)]TJ T* [(because)-236.4(the)-236.4(RF)-236.4(ener)18(gy)-236.4(le)25(v)15(e)0(l)-236.4(i)0(s)-236.4(v)15(ery)-236.4(lo)25(w)65(,)-236.4(and)-236.4(after)-236.4(passing)-236.4(through)-236.4(the)-236.4(resonance)-236.4(condition)]TJ T* 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[(narro)25(w)]TJ /F8 1 Tf 2.807 0 TD ()Tj /F9 1 Tf 1 0 TD [(for)-206.2(e)15(xample,)-206.2(from)-206.2(500.0025)-206.2(MHz)-206.2(do)25(wn)-206.2(to)-206.2(499.9975)-206.2(MHz,)-206.2(and)-206.2(the)-206.2(position)-206.2(of)-206.2(the)]TJ -3.8071 -1.2 TD [(absorption)-179.9(peak)-179.9(on)-179.9(the)-179.9(spectrum)-179.9(\(its)]TJ /F8 1 Tf 14.3553 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(chemical)-179.8(shift)]TJ /F8 1 Tf 5.5679 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(\))-179.9(tells)-179.9(us)-179.9(something)-179.9(about)-179.9(the)-179.9(chemical)]TJ -20.8112 -1.2 TD [(en)40(vironment)-292.2(of)-292.2(the)-292.2(spin)-292.2(within)-292.2(the)-292.2(molecule.)-292.2(This)-292.2(technique)-292.2(is)-292.2(called)]TJ /F8 1 Tf 28.3662 0 TD ()Tj /F9 1 Tf 0.444 0 TD [(continuous)-292.2(w)10(a)20(v)15(e)]TJ /F8 1 Tf 6.7462 0 TD ()Tj /F9 1 Tf -35.5564 -1.2 TD [(\(CW\))-218(NMR)-218(because)-218(the)-218(radio)-218(frequenc)15(y)-218(ener)18(gy)-218(is)-218(applied)-218(continuously)-218(as)-218(the)-218(frequenc)15(y)-218(i)0(s)]TJ T* [(gradually)-213.4(v)25(aried.)-213.4(The)]TJ /F8 1 Tf 8.6962 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(rst)-213.4(commercial)-213.4(NMR)-213.3(spectrometers)-213.4(\(e.g.,)-213.4(the)-213.4(V)111(arian)-213.4(T)92(-60)-213.4(operating)]TJ -9.2522 -1.2 TD [(at)-250.9(60)-250.9(MHz\))-250.9(were)-250.9(all)-250.9(continuous)-250.9(w)10(a)20(v)15(e)0(.)-250.9(I)0(n)-250.9(the)-250.9(earliest)-250.9(CW)-250.9(instruments,)-250.9(the)-250.9(radio)-250.9(frequenc)15(y)]TJ T* [(w)10(a)0(s)-253.9(held)-253.9(constant)-253.9(and)-253.9(the)]TJ /F8 1 Tf 10.5358 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-253.9(\()]TJ /F4 1 Tf 1.809 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 253.5066 621.2787 Tm (o)Tj 9.9626 0 0 9.9626 257.7905 622.7731 Tm [(\))-253.9(w)10(as)-253.9(gradually)-253.9(changed)-253.9(\()]TJ /F8 1 Tf 10.3358 0 TD ()Tj /F9 1 Tf 0.444 0 TD (swept)Tj /F8 1 Tf 2.333 0 TD ()Tj /F9 1 Tf 0.444 0 TD -0.0007 Tc [(\).)-254.6(This)-254.6(ga)19.3(v)14.3(e)-254.6(the)-254.6(same)]TJ -27.4986 -1.2 TD 0 Tc [(result)-218.7(because)-218.7(the)-218.7(absorption)-218.7(of)-218.7(RF)-218.7(ener)18(gy)-218.7(led)-218.7(to)-218.7(a)-218.7(peak)-218.7(when)-218.7(the)]TJ /F8 1 Tf 26.1535 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(eld)-218.7(reached)-218.7(a)-218.7(v)25(alue)-218.7(that)]TJ -26.7095 -1.2 TD (satis)Tj /F8 1 Tf 1.778 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(ed)-297.3(the)-297.3(resonance)-297.3(condition)-297.3(\()]TJ /F2 1 Tf 11.4642 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 261.2029 597.3685 Tm (o)Tj /F3 1 Tf 9.9626 0 0 9.9626 268.2541 598.8629 Tm ()Tj /F2 1 Tf 1.0773 0 TD ()Tj /F4 1 Tf 0.584 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 290.8922 597.3685 Tm (o)Tj /F2 1 Tf 9.9626 0 0 9.9626 295.1761 598.8629 Tm ()Tj /F9 1 Tf 0.47 0 TD (2)Tj /F2 1 Tf 0.504 0 TD ()Tj /F9 1 Tf 0.626 0 TD 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[(f)10(aster)-278.9(and)-278.9(allo)25(ws)-278.9(repeating)-278.9(the)-278.9(e)15(xperiment)-278.9(man)15(y)-278.9(times)-278.9(and)-278.9(summing)-278.9(the)-278.9(resulting)-278.8(data)-278.9(to)]TJ T* [(increase)-348.6(sensiti)25(vity)65(.)-348.6(A)-348.5(v)15(ery)-348.6(brief)-348.6(pulse)-348.6(of)-348.6(high-po)25(wer)-348.6(radio)-348.6(frequenc)15(y)-348.6(ener)18(gy)-348.6(is)-348.6(used)-348.6(to)]TJ T* [(e)15(xcite)-243.1(all)-243.1(of)-243.1(the)-243.1(nuclei)-243.1(in)-243.1(the)-243.1(sample)-243.1(of)-243.1(a)-243.1(g)0(i)25(v)15(en)-243.1(type)-243.1(\(e.g.,)]TJ 7.5716 0 0 7.5716 348.7623 447.0622 Tm (1)Tj 9.9626 0 0 9.9626 353.0462 443.4458 Tm [(H\).)-243.1(Immediately)-243.1(after)-243.1(the)-243.1(pulse)]TJ -23.503 -1.2 TD -0.0001 Tc [(is)-203.2(o)14.9(v)14.9(e)-0.1(r)39.9(,)-203.2(the)-203.2(nuclei)-203.2(are)-203.2(or)17.9(ganized)-203.2(in)-203.2(such)-203.2(a)-203.2(w)9.9(ay)-203.2(that)-203.2(their)-203.2(precessing)-203.2(magnets)-203.2(sum)-203.2(together)-203.2(to)]TJ T* 0 Tc [(form)-187.3(a)-187.3(net)-187.3(magnetization)-187.3(of)-187.3(the)-187.3(sample,)-187.3(which)-187.3(rotates)-187.3(at)-187.3(the)-187.3(Larmor)-187.3(frequenc)15(y)65(.)-187.3(The)-187.3(coil)-187.3(that)]TJ T* [(w)10(a)0(s)-286.9(used)-286.9(to)-286.9(transmit)-286.9(RF)-286.9(is)-286.9(no)25(w)-286.9(used)-286.9(as)-286.9(a)-286.9(recei)25(v)15(e)0(r)40(,)-286.9(and)-286.9(a)-286.9(signal)-286.9(is)-286.9(observ)15(ed)-286.9(at)-286.9(the)-286.9(precise)]TJ T* [(Larmor)-365.4(frequenc)15(y)65(,)]TJ /F2 1 Tf 7.8979 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 202.4195 394.1308 Tm (o)Tj 9.9626 0 0 9.9626 206.7035 395.6251 Tm [(.)-365.4(This)-365.4(signal,)-365.4(which)-365.4(oscillates)-365.4(in)-365.4(time)-365.4(at)-365.4(the)-365.4(Larmor)-365.4(frequenc)15(y)65(,)-365.4(is)]TJ -8.8139 -1.2 TD [(recorded)-154.8(by)-154.8(a)-154.8(computer)-154.8(and)-154.8(a)-154.8(mathematical)-154.8(calculation)-154.8(called)-154.8(the)-154.8(F)15(ourier)-154.8(transform)-154.8(con)40(v)15(erts)]TJ T* [(it)-320.9(to)-320.9(a)-320.9(spectrum,)-320.9(a)-320.9(graph)-320.9(of)-320.8(intensity)-320.9(v)15(ersus)-320.9(frequenc)15(y)65(.)-320.9(Essentially)-320.9(the)-320.9(F)15(ourier)-320.9(transform)]TJ T* [(measures)-182.9(the)-182.9(frequenc)15(y)-182.9(o)0(f)-182.9(oscillation)-182.9(of)-182.9(the)-182.9(signal.)-182.9(If)-182.9(there)-182.9(are)-182.9(a)-182.9(number)-182.9(of)-182.9(slightly)-182.9(dif)25(ferent)]TJ T* [(Larmor)-308.6(frequencies,)-308.6(corresponding)-308.6(to)-308.6(dif)25(ferent)-308.6(positions)-308.6(within)-308.6(a)-308.6(molecule,)-308.6(their)-308.6(signals)]TJ T* [(add)-372.6(together)-372.6(to)-372.6(gi)25(v)15(e)-372.6(the)-372.6(recorded)-372.6(signal,)-372.6(and)-372.6(the)-372.6(F)15(ourier)-372.6(transform)-372.6(can)-372.6(sort)-372.6(out)-372.6(all)-372.6(the)]TJ T* [(signals)-317.7(into)-317.7(a)-317.7(spectrum)-317.7(with)-317.7(man)15(y)-317.7(peaks)-317.7(at)-317.7(dif)25(ferent)-317.7(frequencies.)-317.7(The)-317.7(whole)-317.7(e)15(xperiment)]TJ T* [(\(pulse)-160.3(follo)25(wed)-160.3(by)-160.3(recording)-160.3(the)]TJ /F8 1 Tf 12.8295 0 TD ()Tj /F9 1 Tf 0.444 0 TD (echo)Tj /F8 1 Tf 1.888 0 TD ()Tj /F9 1 Tf 0.6043 0 TD [(signal\))-160.3(tak)10(es)-160.3(only)-160.3(a)-160.3(f)0(e)25(w)-160.3(seconds)-160.3(and)-160.3(can)-160.3(be)-160.3(repeated)]TJ -15.7658 -1.2 TD [(as)-250(man)15(y)-250(times)-250(as)-250(desired,)-250(summing)-250(the)-250(data)-250(to)-250(get)-250(a)-250(stronger)-250(signal.)]TJ /F1 1 Tf 0 -3 TD [(&3)-1000( !")10(2":)-250(%)-250(")-250(\015)-250(5\( #!")]TJ /F9 1 Tf 0 -1.8 TD [(Although)-246.8(techniques)-246.8(lik)10(e)-246.8(mass)-246.8(spectrometry)-246.8(require)-246.8(only)-246.8(nanograms)-246.8(\(10)]TJ /F3 1 Tf 7.5716 0 0 7.5716 408.5284 255.7796 Tm ()Tj /F9 1 Tf 0.78 0 TD (9)Tj 9.9626 0 0 9.9626 421.1773 252.1632 Tm [(gram\))-246.8(of)-246.8(sam-)]TJ -30.3417 -1.2 TD [(ple,)-201.4(NMR)-201.4(requires)-201.4(milligrams)-201.4(\(10)]TJ /F3 1 Tf 7.5716 0 0 7.5716 252.8305 243.8245 Tm ()Tj /F9 1 Tf 0.78 0 TD (3)Tj 9.9626 0 0 9.9626 265.0271 240.208 Tm -0.0001 Tc [(gram\))-201.5(of)-201.5(a)-201.5(typical)-201.5(or)17.9(ganic)-201.5(molecule.)-201.5(This)-201.5(insensiti)24.9(vity)]TJ -14.6681 -1.2 TD 0 Tc [(stems)-261.6(primarily)-261.6(from)-261.6(the)-261.6(f)10(act)-261.6(that)-261.6(only)-261.6(the)]TJ /F4 1 Tf 17.2481 0 TD [()18(\012)37()]TJ /F9 1 Tf 4.2057 0 TD [(in)-261.6(population)-261.6(at)-261.6(thermal)-261.6(equilibrium)]TJ -21.4538 -1.2 TD [(is)-243.7(acti)25(v)15(e)-243.7(in)-243.7(the)-243.7(e)15(xperiment.)-243.7(That)-243.7(means)-243.7(that)-243.7(only)-243.7(approximately)-243.7(one)-243.7(spin)-243.7(in)-243.7(10)]TJ 7.5716 0 0 7.5716 430.2256 219.9141 Tm (6)Tj 9.9626 0 0 9.9626 436.9377 216.2977 Tm [(is)-243.7(actually)]TJ -31.9236 -1.2 TD [(detected.)-358.7(W)80(e)-358.7(sa)15(w)-358.7(this)-358.7(in)-358.7(the)-358.7(CW)-358.6(e)15(xperiment,)-358.7(where)-358.7(absorption)-358.7(of)-358.7(RF)-358.6(ener)18(gy)-358.7(is)-358.7(almost)]TJ T* [(completely)-238.9(cancelled)-238.9(by)-238.9(stimulated)-238.9(emission.)-238.9(Another)-238.9(important)-238.9(aspect)-238.9(is)-238.9(the)-238.9(relati)25(v)15(e)-238.9(sen-)]TJ T* [(siti)25(vity)-282.3(of)-282.3(dif)25(ferent)-282.3(nuclei:)-282.3(because)-282.3(of)-282.3(the)-282.3(inherent)-282.3(dif)25(ferences)-282.3(between)-282.3(dif)25(ferent)-282.3(nuclei)-282.3(in)]TJ T* [(the)-182.7(strength)-182.7(of)-182.7(the)-182.7(nuclear)-182.7(magnet)-182.7(\()]TJ /F2 1 Tf 13.8156 0 TD ()Tj /F9 1 Tf 0.584 0 TD [(\),)-182.7(the)-182.7(signal)-182.7(strength)-182.7(recei)25(v)15(e)0(d)-182.7(can)-182.7(be)-182.7(v)15(ery)-182.7(much)-182.7(weak)10(er)]TJ -14.3996 -1.2 TD [(than)-168.3(a)-168.3(proton)-168.3(signal.)-168.3(There)-168.3(are)-168.3(three)-168.3(w)10(ays)-168.3(in)-168.3(which)]TJ /F2 1 Tf 19.9184 0 TD ()Tj /F9 1 Tf 0.7523 0 TD [(af)25(fects)-168.3(the)-168.3(sensiti)25(vity)-168.3(of)-168.3(the)-168.3(e)15(xperiment)]TJ -20.6707 -1.2 TD (\()Tj /F8 1 Tf 0.333 0 TD ()Tj /F9 1 Tf 0.444 0 TD -0.0004 Tc [(the)-250.4(three)-250.4(gammas)]TJ /F8 1 Tf 7.0491 0 TD 0 Tc ()Tj /F9 1 Tf 0.444 0 TD (\):)Tj ET endstream endobj 76 0 obj > endobj 77 0 obj > stream BT /F1 1 Tf 8.9664 0 0 8.9664 120.239 730.6316 Tm 0 g /GS1 gs 0 Tc 0 Tw ($.)Tj /F9 1 Tf 7.9701 0 0 7.9701 147.1382 730.6316 Tm [(FUND)40(AMENT)93(ALS)-250(OF)-250(NMR)-250(SPECTR)40(OSCOPY)-250(IN)-250(LIQ)10(UIDS)]TJ 9.9626 0 0 9.9626 132.1942 706.4592 Tm [(1.)-420(The)]TJ /F4 1 Tf 3.2289 0 TD [(    )-503.9()18(\012)37()]TJ /F9 1 Tf 9.2859 0 TD [(at)-503.9(thermal)-503.9(equilibrium)-503.9(is)-503.9(proportional)-503.9(to)-503.9(the)-503.9(ener)18(gy)]TJ -11.3448 -1.2 TD -0.0002 Tc [(gap,)-394.7(which)-394.7(is)-394.7(in)-394.7(turn)-394.7(proportional)-394.7(to)]TJ /F2 1 Tf 15.6727 0 TD 0 Tc ()Tj /F4 1 Tf 0.584 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 311.8972 693.0097 Tm (o)Tj 9.9626 0 0 9.9626 316.1811 694.5041 Tm [(,)-394.5(and)-394.5(in)40(v)15(ersely)-394.5(proportional)-394.5(to)-394.5(absolute)]TJ -17.2977 -1.2 TD [(temperature.)-558.9(This)-558.9(population)-558.9(dif)25(ference)-558.9(is)-558.9(the)-558.9(only)-558.9(thing)-558.9(we)-558.9(can)-558.9(observ)15(e)-558.9(b)0(y)]TJ T* (NMR.)Tj -1.17 -1.4 TD [(2.)-420(As)-175.4(the)-175.4(nuclear)-175.4(magnet)-175.4(precesses,)-175.4(it)-175.4(induces)-175.4(a)-175.4(signal)-175.4(in)-175.4(the)-175.4(recei)25(v)15(e)0(r)-175.4(coil.)-175.4(The)-175.4(amplitude)]TJ 1.17 -1.2 TD [(of)-386.9(this)-386.9(signal)-386.9(is)-386.9(proportional)-386.9(to)-386.9(the)]TJ /F4 1 Tf 14.9862 0 TD [( \012)37( )-386.9( )-386.9( )-386.9(\012)45(  )-386.9()10( )]TJ /F9 1 Tf 12.9006 0 TD [(,)-386.9(which)-386.9(is)-386.9(the)]TJ -27.8867 -1.2 TD [(magnetogyric)-250(ratio)]TJ /F2 1 Tf 7.8321 0 TD ()Tj /F9 1 Tf 0.584 0 TD (.)Tj -9.5861 -1.4 TD [(3.)-420(The)]TJ /F4 1 Tf 2.9931 0 TD [(\012)15( )-268.1( )-268.1('')15()-268.1( )-268.1( \012)-268.1()10( )-268.1(\012)37(  )]TJ /F9 1 Tf 17.6307 0 TD (\()Tj /F2 1 Tf 0.333 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 345.8211 617.2937 Tm (o)Tj 9.9626 0 0 9.9626 350.1051 618.7881 Tm [(\))-268.1(i)0(s)-268.1(also)-268.1(proportional)-268.1(to)]TJ /F2 1 Tf 9.6735 0 TD ()Tj /F4 1 Tf 0.584 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 458.3838 617.2937 Tm (o)Tj 9.9626 0 0 9.9626 462.6677 618.7881 Tm 0.2681 Tc [(.A)268.1(s)]TJ -32.0013 -1.2 TD 0 Tc [(with)-231.5(an)15(y)-231.5(electrical)-231.5(generator)40(,)-231.5(i)0(f)-231.5(you)-231.5(turn)-231.5(the)-231.5(crank)-231.5(f)10(aster)-231.5(you)-231.5(get)-231.5(a)-231.5(higher)-231.5(v)20(oltage)-231.5(out)]TJ T* [(of)-250(the)-250(generator)55(.)]TJ -2.37 -2.365 TD [(F)15(actors)-320.5(1)-320.5(and)-320.5(2)-320.5(tak)10(en)-320.5(together)-320.5(gi)25(v)15(e)-320.5(the)-320.5(net)-320.5(magnetization)-320.5(at)-320.5(equilibrium,)]TJ /F4 1 Tf 30.0829 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 428.2435 569.8221 Tm (o)Tj 9.9626 0 0 9.9626 432.5275 571.3165 Tm 0.3205 Tc [(,s)320.5(ow)320.5(ec)320.5(a)320.5(n)]TJ -31.346 -1.2 TD 0 Tc [(also)-257.2(think)-257.2(of)-257.2(a)-257.2(lar)18(ge)-257.2(magnet)-257.2(of)-257.2(strength)]TJ /F4 1 Tf 15.9821 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 287.7616 557.867 Tm (o)Tj 9.9626 0 0 9.9626 294.6083 559.3614 Tm [(rotating)-257.2(in)-257.2(the)]TJ /F4 1 Tf 5.8828 0 TD ()Tj /F9 1 Tf 0.444 0 TD (-)Tj /F4 1 Tf 0.333 0 TD (\015)Tj /F9 1 Tf 0.7012 0 TD [(plane)-257.2(when)-257.2(we)-257.2(consider)-257.2(the)]TJ /F8 1 Tf -24.8633 -1.2 TD ()Tj /F9 1 Tf 0.556 0 TD [(nal)-268.7(f)10(actor)40(,)-268.6(the)-268.7(rate)-268.7(of)-268.7(rotation)-268.7(\(3\).)-268.6(Either)-268.6(w)10(a)0(y)-268.7(w)0(e)-268.7(can)-268.7(say)-268.7(that)-268.7(the)-268.7(amplitude)-268.7(of)-268.7(the)-268.7(NMR)]TJ -0.556 -1.2 TD [(signal)-250(\(sensiti)25(vity\))-250(for)-250(a)-250(spin-)]TJ /F8 1 Tf 11.7521 0 TD ()Tj /F9 1 Tf 1 0 TD [(nucleus)-250(is)-250(proportional)-250(to:)]TJ -3.2481 -2.365 TD ([)Tj /F2 1 Tf 0.333 0 TD ()Tj /F3 1 Tf 1.0462 0 TD ()Tj /F2 1 Tf 1.0062 0 TD ()Tj 7.5716 0 0 7.5716 250.4661 510.3955 Tm ()Tj 9.9626 0 0 9.9626 254.75 511.8899 Tm 0.07 Tc ()Tj /F9 1 Tf 1.225 0 TD 0 Tc (])Tj /F3 1 Tf 0.5552 0 TD ()Tj /F9 1 Tf 1.0062 0 TD ([)Tj /F2 1 Tf 0.333 0 TD ()Tj /F9 1 Tf 0.584 0 TD (])Tj /F3 1 Tf 0.5552 0 TD ()Tj /F9 1 Tf 1.0062 0 TD ([)Tj /F2 1 Tf 0.333 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 322.2961 510.3955 Tm (o)Tj 9.9626 0 0 9.9626 326.58 511.8899 Tm (])Tj /F3 1 Tf 0.6108 0 TD ()Tj /F2 1 Tf 1.0578 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 356.5035 516.0045 Tm (3)Tj /F2 1 Tf 9.9626 0 0 9.9626 360.7874 511.89 Tm ()Tj /F9 1 Tf 7.5716 0 0 7.5716 367.6916 516.0045 Tm (2)Tj -0.0171 -0.8974 TD (o)Tj /F2 1 Tf 9.9626 0 0 9.9626 372.0058 511.89 Tm 0.07 Tc ()Tj /F9 1 Tf -25.2711 -2.365 TD 0 Tc (where)Tj /F4 1 Tf 2.6513 0 TD ()Tj /F9 1 Tf 0.8752 0 TD [(is)-208.3(the)-208.3(number)-208.3(of)-208.3(identical)-208.3(spins)-208.3(in)-208.3(the)-208.3(sample.)-208.3(This)-208.3(tells)-208.3(us)-208.3(that)-208.3(sensiti)25(vity)-208.3(depends)]TJ -3.5265 -1.2 TD [(on)-281.7(the)-281.7(third)-281.7(po)25(wer)-281.7(of)]TJ /F2 1 Tf 8.8267 0 TD ()Tj /F9 1 Tf 0.8657 0 TD [(as)-281.7(well)-281.7(as)-281.7(the)-281.7(square)-281.7(of)]TJ /F4 1 Tf 9.7435 0 TD ()Tj /F9 1 Tf 7.5716 0 0 7.5716 319.9595 474.8791 Tm (o)Tj 9.9626 0 0 9.9626 324.2435 476.3734 Tm [(.)-281.7(S)0(o)-281.7(i)0(t)-281.7(i)0(s)-281.7(w)10(orth)-281.7(a)-281.7(lot)-281.7(of)-281.7(mone)15(y)-281.7(t)0(o)-281.7(b)20(uild)]TJ -20.4769 -1.2 TD [(lar)18(ger)-214.6(and)-214.6(more)-214.6(po)25(werful)-214.6(magnets,)-214.6(and)-214.6(we)-214.6(will)-214.6(pay)-214.6(a)-214.6(big)-214.6(price)-214.6(in)-214.6(sensiti)25(vity)-214.6(to)-214.6(study)-214.6(nuclei)]TJ T* [(with)-238.9(relati)25(v)15(ely)-238.9(small)]TJ /F2 1 Tf 8.3987 0 TD ()Tj /F9 1 Tf 0.584 0 TD -0.0001 Tc [(.)-239(Consider)-239(some)-239(of)-239(the)-239(most)-239(useful)-239(nuclei)-239(for)-239(or)17.9(ganic)-239(chemistry)-239(and)]TJ -8.9827 -1.2 TD 0 Tc [(biological)-250(research:)]TJ ET 0 G 0 J 0 j 0.398 w 10 M []0 d 1 i 158.808 427.357 m 440.325 427.357 l S BT /F4 1 Tf 8.9664 0 0 8.9664 183.7131 415.5018 Tm ()Tj /F9 1 Tf 5.9776 0 0 5.9776 189.1914 414.1568 Tm (o)Tj /F3 1 Tf 8.9664 0 0 8.9664 194.92 415.5018 Tm ()Tj /F9 1 Tf 1.03 0 TD [(7.05)-250(T)]TJ /F4 1 Tf 3.9444 0 TD ()Tj /F9 1 Tf 5.9776 0 0 5.9776 245.0002 414.1569 Tm (o)Tj /F3 1 Tf 8.9664 0 0 8.9664 250.7287 415.5018 Tm ()Tj /F9 1 Tf 1.03 0 TD [(11.74)-250(T)]TJ /F2 1 Tf 4.4444 0 TD ()Tj /F9 1 Tf 0.584 0 TD (/)Tj /F2 1 Tf 0.278 0 TD ()Tj /F9 1 Tf 5.9776 0 0 5.9776 312.7788 414.1569 Tm (H)Tj 8.9664 0 0 8.9664 317.6466 415.5018 Tm (\(%\))Tj /F2 1 Tf 2.8324 0 TD ()Tj /F9 1 Tf 5.9776 0 0 5.9776 348.2788 418.7566 Tm (3)Tj 8.9664 0 0 8.9664 351.7657 415.5018 Tm (/)Tj /F2 1 Tf 0.278 0 TD ()Tj /F9 1 Tf 5.9776 0 0 5.9776 359.4946 414.1569 Tm (H)Tj 0.8143 0.7695 TD (3)Tj 8.9664 0 0 8.9664 384.1384 415.5018 Tm [(Ab)20(undance)-250(\(%\))]TJ ET 158.808 409.026 m 440.325 409.026 l S BT 5.9776 0 0 5.9776 158.8085 398.4328 Tm (1)Tj 8.9664 0 0 8.9664 162.2954 395.178 Tm [(H)-1666.7(300.0)-250(MHz)-1669.3(500.0)-250(MHz)-2169.3(1.000)-2571.2(1.000)-4349.9(99.98)]TJ 5.9776 0 0 5.9776 158.8085 387.4739 Tm (13)Tj 8.9664 0 0 8.9664 165.2842 384.2191 Tm [(C)-1888.3(75.43)-3474.3(125.72)-3974.3(0.2514)-2071.3(0.0159)-4349.9(1.11)]TJ 5.9776 0 0 5.9776 158.8085 376.515 Tm (15)Tj 8.9664 0 0 8.9664 165.2842 373.2602 Tm [(N)-1833.3(30.40)-3974.3(50.66)-3974.3(0.1013)-2071.3(0.00104)-3849.9(0.37)]TJ ET 158.808 369.773 m 440.325 369.773 l S BT 9.9626 0 0 9.9626 120.239 347.8045 Tm [(Using)-231.3(our)-231.3(rule)-231.3(of)-231.3(thumb)-231.3(that)]TJ 7.5716 0 0 7.5716 235.3478 351.4209 Tm (13)Tj 9.9626 0 0 9.9626 243.4176 347.8045 Tm [(C)-231.3(has)-231.3(a)]TJ /F2 1 Tf 3.138 0 TD ()Tj /F9 1 Tf 0.8153 0 TD [(v)25(alue)-231.3(four)-231.3(times)-231.3(smaller)-231.3(than)]TJ 7.5716 0 0 7.5716 400.3294 351.4209 Tm (1)Tj 9.9626 0 0 9.9626 404.6134 347.8045 Tm [(H)-231.3(and)-231.3(that)]TJ 7.5716 0 0 7.5716 448.0504 351.421 Tm (15)Tj 9.9626 0 0 9.9626 456.1201 347.8046 Tm [(N)-231.3(has)]TJ -33.7141 -1.2 TD (a)Tj /F2 1 Tf 0.6424 0 TD ()Tj /F9 1 Tf 0.7824 0 TD [(v)25(alue)-198.4(10)-198.4(times)-198.4(smaller)-198.4(than)]TJ 7.5716 0 0 7.5716 243.6844 339.4658 Tm (1)Tj 9.9626 0 0 9.9626 247.9683 335.8493 Tm [(H,)-198.4(we)-198.4(can)-198.4(see)-198.4(that)-198.4(the)-198.4(FID)-198.3(signal)-198.4(will)-198.4(be)-198.4(4)]TJ 7.5716 0 0 7.5716 412.4413 339.4658 Tm (3)Tj /F3 1 Tf 9.9626 0 0 9.9626 418.7017 335.8493 Tm ()Tj /F9 1 Tf 0.9784 0 TD [(64)-198.4(times)-198.4(less)]TJ -30.9366 -1.2 TD (with)Tj 7.5716 0 0 7.5716 140.2765 327.5106 Tm (13)Tj 9.9626 0 0 9.9626 148.3463 323.8941 Tm [(C)-233.2(and)-233.2(10)]TJ 7.5716 0 0 7.5716 183.9876 327.5106 Tm (3)Tj /F3 1 Tf 9.9626 0 0 9.9626 190.5952 323.8941 Tm ()Tj /F9 1 Tf 1.0133 0 TD [(1000)-233.2(times)-233.2(less)-233.2(with)]TJ 7.5716 0 0 7.5716 284.1573 327.5106 Tm (15)Tj 9.9626 0 0 9.9626 292.2271 323.8941 Tm [(N)-233.2(when)-233.2(compared)-233.2(to)]TJ 7.5716 0 0 7.5716 377.3282 327.5106 Tm (1)Tj 9.9626 0 0 9.9626 381.6122 323.8941 Tm [(H)-233.2(with)-233.2(the)-233.2(same)-233.2(number)]TJ -26.2353 -1.2 TD [(of)-240.7(identical)-240.7(nuclei)-240.7(\()]TJ /F4 1 Tf 7.7762 0 TD ()Tj /F9 1 Tf 0.667 0 TD [(\))-240.7(i)0(n)-240.7(the)-240.7(sample.)-240.7(But)-240.7(e)25(v)15(en)-240.7(at)-240.7(the)-240.7(same)-240.7(sample)-240.7(concentration)-240.7(we)-240.7(do)-240.7(not)]TJ -8.4432 -1.2 TD [(ha)20(v)15(e)-220.8(the)-220.8(same)-220.8(number)-220.8(of)-220.8(nuclei)-220.8(because)-220.8(for)]TJ 7.5716 0 0 7.5716 295.1811 303.6003 Tm (13)Tj 9.9626 0 0 9.9626 303.2509 299.9838 Tm [(C)-220.8(only)-220.8(about)-220.8(one)-220.8(in)-220.8(100)-220.8(carbon)-220.8(atoms)-220.8(is)]TJ 7.5716 0 0 7.5716 464.1832 303.6003 Tm (13)Tj 9.9626 0 0 9.9626 472.2529 299.9839 Tm (C)Tj -35.3334 -1.2 TD [(and)-225.2(for)]TJ 7.5716 0 0 7.5716 150.7288 291.6451 Tm (15)Tj 9.9626 0 0 9.9626 158.7986 288.0287 Tm [(N)-225.2(only)-225.2(about)-225.2(one)-225.2(in)-225.2(300)-225.2(nitrogen)-225.2(atoms)-225.2(is)]TJ 7.5716 0 0 7.5716 326.7674 291.6451 Tm (15)Tj 9.9626 0 0 9.9626 334.8371 288.0287 Tm [(N.)-225.2(Accounting)-225.2(for)-225.2(this)-225.2(smaller)-225.2(v)25(alue)]TJ -21.5403 -1.2 TD [(of)-243.6(N,)-243.6(the)-243.6(signal)-243.6(strength)-243.6(\(sensiti)25(vity\))-243.6(is)-243.6(5670)-243.6(times)-243.6(less)-243.6(than)]TJ 7.5716 0 0 7.5716 360.6025 279.6899 Tm (1)Tj 9.9626 0 0 9.9626 364.8864 276.0735 Tm [(H)-243.6(for)]TJ 7.5716 0 0 7.5716 388.5491 279.69 Tm (13)Tj 9.9626 0 0 9.9626 396.6189 276.0735 Tm [(C)-243.6(and)-243.6(260,000)-243.6(times)]TJ -27.7416 -1.2 TD [(less)-313(than)]TJ 7.5716 0 0 7.5716 158.5759 267.7348 Tm (1)Tj 9.9626 0 0 9.9626 162.8598 264.1184 Tm [(H)-313(for)]TJ 7.5716 0 0 7.5716 187.9057 267.7348 Tm (15)Tj 9.9626 0 0 9.9626 195.9755 264.1184 Tm [(N)-313(a)0(t)-313(natural)-313(ab)20(undance.)-313(F)15(o)0(r)-313(this)-313(reason,)-313(commercial)-313(continuous)-313(w)10(a)20(v)15(e)]TJ -7.602 -1.2 TD [(NMR)-258.5(spectrometers)-258.5(could)-258.5(only)-258.5(detect)]TJ 7.5716 0 0 7.5716 274.7863 255.7796 Tm (1)Tj 9.9626 0 0 9.9626 279.0702 252.1632 Tm [(H.)-258.5(W)40(ith)-258.5(pulsed)-258.5(F)15(ourier)-258.5(transform)-258.5(NMR)-258.5(it)-258.5(became)]TJ -15.9427 -1.2 TD [(possible)-180.7(to)-180.7(detect)]TJ 7.5716 0 0 7.5716 189.8391 243.8245 Tm (13)Tj 9.9626 0 0 9.9626 197.9088 240.208 Tm [(C)-180.6(with)-180.7(long)-180.7(e)15(xperiments)-180.7(\(1)-180.7(h)-180.7(o)0(r)-180.7(more\))-180.7(and)-180.7(concentrated)-180.7(samples)-180.7(\(30)-180.7(mg)]TJ -7.7961 -1.2 TD -0.0001 Tc [(or)-156.1(more)-156.1(of)-156.1(a)-156.1(typical)-156.1(or)17.9(ganic)-156.1(molecule\).)-156.1(Detection)-156.1(of)]TJ 7.5716 0 0 7.5716 321.8559 231.8693 Tm 0 Tc (15)Tj 9.9626 0 0 9.9626 329.9257 228.2528 Tm [(N)-155.9(i)0(s)-156(still)-156(v)15(ery)-156(dif)]TJ /F8 1 Tf 6.362 0 TD ()Tj /F9 1 Tf 0.556 0 TD [(cult)-156(without)-156(isotopic)]TJ -27.9653 -1.2 TD [(labeling)-272.1(of)]TJ 7.5716 0 0 7.5716 166.0595 219.9141 Tm (15)Tj 9.9626 0 0 9.9626 174.1292 216.2977 Tm 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Table of Contents

Preface.

Acknowledgments.

1 Fundamentalsof NMR Spectroscopy in Liquids.

1.1 Introduction to NMR Spectroscopy.

1.2 Examples: NMR Spectroscopy of Oligosaccharides and Terpenoids.

1.3 Typical Values of Chemical Shifts and Coupling Constants.

1.4 Fundamental Concepts of NMR Spectroscopy.

2 Interpretation of Proton (1H) NMR Spectra.

2.1 Assignment.

2.2 Effect of Bo Field Strength on the Spectrum.

2.3 First-Order Splitting Patterns.

2.4 The Use of 1H–1H Coupling Constants to Determine Stereochemistry and Conformation.

2.5 Symmetry and Chirality in NMR.

2.6 The Origin of the Chemical Shift.

2.7 J Coupling to Other NMR-Active Nuclei.

2.8 Non-First-Order Splitting Patterns: Strong Coupling.

2.9 Magnetic Equivalence.

3 NMR Hardware and Software.

3.1 Sample Preparation.

3.2 Sample Insertion.

3.3 The Deuterium Lock Feedback Loop.

3.4 The Shim System.

3.5 Tuning and Matching the Probe.

3.6 NMR Data Acquisition and Acquisition Parameters.

3.7 Noise and Dynamic Range.

3.8 Special Topic: Oversampling and Digital Filtering.

3.9 NMR Data Processing—Overview.

3.10 The Fourier Transform.

3.11 Data Manipulation Before the Fourier Transform.

3.12 Data Manipulation After the Fourier Transform.

4 Carbon-13 (13C) NMR Spectroscopy.

4.1 Sensitivity of 13C.

4.2 Splitting of 13C Signals.

4.3 Decoupling.

4.4 Heteronuclear Decoupling: 1H Decoupled 13C Spectra.

4.5 Decoupling Hardware.

4.6 Decoupling Software: Parameters.

4.7 The Nuclear Overhauser Effect (NOE).

4.8 Heteronuclear Decoupler Modes.

5 NMR Relaxation—Inversion-Recovery and the Nuclear Overhauser Effect (NOE).

5.1 The Vector Model.

5.2 One Spin in a Magnetic Field.

5.3 A Large Population of Identical Spins: Net Magnetization.

5.4 Coherence: Net Magnetization in the xy Plane.

5.5 Relaxation.

5.6 Summary of the Vector Model.

5.7 Molecular Tumbling and NMR Relaxation.

5.8 Inversion-Recovery: Measurement of T1 Values.

5.9 Continuous-Wave Low-Power Irradiation of One Resonance.

5.10 Homonuclear Decoupling.

5.11 Presaturation of Solvent Resonance.

5.12 The Homonuclear Nuclear Overhauser Effect (NOE).

5.13 Summary of the Nuclear Overhauser Effect.

6 The Spin Echo and the Attached Proton Test (APT).

6.1 The Rotating Frame of Reference.

6.2 The Radio Frequency (RF) Pulse.

6.3 The Effect of RF Pulses.

6.4 Quadrature Detection, Phase Cycling, and the Receiver Phase.

6.5 Chemical Shift Evolution.

6.6 Scalar (J) Coupling Evolution.

6.7 Examples of J-coupling and Chemical Shift Evolution.

6.8 The Attached Proton Test (APT).

6.9 The Spin Echo.

6.10 The Heteronuclear Spin Echo: Controlling J-Coupling Evolution and Chemical Shift Evolution.

7 Coherence Transfer: INEPT and DEPT.

7.1 Net Magnetization.

7.2 Magnetization Transfer.

7.3 The Product Operator Formalism: Introduction.

7.4 Single Spin Product Operators: Chemical Shift Evolution.

7.5 Two-Spin Operators: J-coupling Evolution and Antiphase Coherence.

7.6 The Effect of RF Pulses on Product Operators.

7.7 INEPT and the Transfer of Magnetization from 1H to 13C.

7.8 Selective Population Transfer (SPT) as a Way of Understanding INEPT Coherence Transfer.

7.9 Phase Cycling in INEPT.

7.10 Intermediate States in Coherence Transfer.

7.11 Zero- and Double-Quantum Operators.

7.12 Summary of Two-Spin Operators.

7.13 Refocused INEPT: Adding Spectral Editing.

7.14 DEPT: Distortionless Enhancement by Polarization Transfer.

7.15 Product Operator Analysis of the DEPT Experiment.

8 Shaped Pulses, Pulsed Field Gradients, and Spin Locks: Selective 1D NOE and 1D TOCSY.

8.1 Introducing Three New Pulse Sequence Tools.

8.2 The Effect of Off-Resonance Pulses on Net Magnetization.

8.3 The Excitation Profile for Rectangular Pulses.

8.4 Selective Pulses and Shaped Pulses.

8.5 Pulsed Field Gradients.

8.6 Combining Shaped Pulses and Pulsed Field Gradients: "Excitation Sculpting."

8.7 Coherence Order: Using Gradients to Select a Coherence Pathway.

8.8 Practical Aspects of Pulsed Field Gradients and Shaped Pulses.

8.9 1D Transient NOE using DPFGSE.

8.10 The Spin Lock.

8.11 Selective 1D ROESY and 1D TOCSY.

8.12 Selective 1D TOCSY using DPFGSE.

8.13 RF Power Levels for Shaped Pulses and Spin Locks.

9 Two-Dimensional NMR Spectroscopy: HETCOR, COSY, and TOCSY.

9.1 Introduction to Two-Dimensional NMR.

9.2 HETCOR: A 2D Experiment Created from the 1D INEPT Experiment.

9.3 A General Overview of 2D NMR Experiments.

9.4 2D Correlation Spectroscopy (COSY).

9.5 Understanding COSY with Product Operators.

9.6 2D TOCSY (Total Correlation Spectroscopy).

9.7 Data Sampling in t1 and the 2D Spectral Window.

10 Advanced NMR Theory: NOESY and DQF-COSY.

10.1 Spin Kinetics: Derivation of the Rate Equation for Cross-Relaxation.

10.2 Dynamic Processes and Chemical Exchange in NMR.

10.3 2D NOESY and 2D ROESY.

10.4 Expanding Our View of Coherence: Quantum Mechanics and Spherical Operators.

10.5 Double-Quantum Filtered COSY (DQF-COSY).

10.6 Coherence Pathway Selection in NMR Experiments.

10.7 The Density Matrix Representation of Spin States.

10.8 The Hamiltonian Matrix: Strong Coupling and Ideal Isotropic (TOCSY) Mixing.

11 Inverse Heteronuclear 2D Experiments: HSQC, HMQC, and HMBC.

11.1 Inverse Experiments: 1H Observe with 13C Decoupling.

11.2 General Appearance of Inverse 2D Spectra.

11.3 Examples of One-Bond Inverse Correlation (HMQC and HSQC) Without 13C Decoupling.

11.4 Examples of Edited, 13C-Decoupled HSQC Spectra.

11.5 Examples of HMBC Spectra.

11.6 Structure Determination Using HSQC and HMBC.

11.7 Understanding the HSQC Pulse Sequence.

11.8 Understanding the HMQC Pulse Sequence.

11.9 Understanding the Heteronuclear Multiple-Bond Correlation (HMBC) Pulse Sequence.

11.10 Structure Determination by NMR—An Example.

12 Biological NMR Spectroscopy.

12.1 Applications of NMR in Biology.

12.2 Size Limitations in Solution-State NMR.

12.3 Hardware Requirements for Biological NMR.

12.4 Sample Preparation and Water Suppression.

12.5 1H Chemical Shifts of Peptides and Proteins.

12.6 NOE Interactions Between One Residue and the Next Residue in the Sequence.

12.7 Sequence-Specific Assignment Using Homonuclear 2D Spectra.

12.8 Medium and Long-Range NOE Correlations.

12.9 Calculation of 3D Structure Using NMR Restraints.

12.10 15N-Labeling and 3D NMR.

12.11 Three-Dimensional NMR Pulse Sequences: 3D HSQC–TOCSY and 3D TOCSY–HSQC.

12.12 Triple-Resonance NMR on Doubly-Labeled (15N, 13C) Proteins.

12.13 New Techniques for Protein NMR: Residual Dipolar Couplings and Transverse Relaxation Optimized Spectroscopy (TROSY).

Appendix A: A Pictorial Key to NMR SpinStates.

Appendix B: A Survey of Two-Dimensional NMR Experiments.

Index.