Exposure to air boosts CuAAC reactions catalyzed by PEG-stabilized Cu nanoparticles

Article abstract of DOI:10.1039/c7cc02504a

New PEG-stabilized CuNP catalysts are designed upon Cu(ii) reduction with sodium naphthalenide in MeCN followed by simple purification using the salting-out effect. Their catalytic activity in CuAAC is boosted upon 30 min exposure to air, producing Cu₂O NPs. These NPs are also supported on SBA-15, providing excellent recyclable heterogeneous catalysts that are applied in low amounts for efficient "click" functionalization.

Full text of DOI:10.1039/c7cc02504a

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Astruc, Chem. Commun., 2017, DOI: 10.1039/C7CC02504A.
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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
first methanofullerene derivatives of Sc
3
N@C2n (2n
=
68 and 80). Synthesis of the
3
N@D5h-C80
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Pleaseꢀd oC ꢀhn e omt ꢀ Ca od mj u ms tꢀmarginsꢀ
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DOI: 10.1039/C7CC02504A
JournalꢀNameꢀ
COMMUNICATIONꢀ
ꢀ
ExposureꢀtoꢀAirꢀBoostsꢀCuAACꢀReactionsꢀCatalyzedꢀbyꢀPEG-
stabilizedꢀCuꢀNanoparticlesꢀ
Receivedꢀ00thꢀJanuaryꢀ20xx,ꢀ
Acceptedꢀ00thꢀJanuaryꢀ20xxꢀ
a
bꢀ
a,ꢀc
a,ꢀd
b
b
FangyuꢀFu, ꢀAngelꢀMartinez, ChanglongꢀWang, ꢀRobertoꢀCiganda, ꢀLuisꢀYate, ꢀAneꢀEscobar, ꢀ
bꢀ
a
a
*aꢀ
SergioꢀMoya, EricꢀFouquet, ꢀJaimeꢀRuizꢀ ꢀandꢀDidierꢀAstruc
DOI:ꢀ10.1039/x0xx00000xꢀ
www.rsc.org/ꢀ
1
0,11
Newꢀ PEG-stabilizedꢀ CuNPꢀ catalystsꢀ areꢀ designedꢀ uponꢀ Cu(II)ꢀ zero-valentꢀ Cu,
ꢀ althoughꢀ Cuꢀ nanomaterialsꢀ underꢀ bothꢀ
12
13
reductionꢀwithꢀsodiumꢀnaphthalenideꢀinꢀMeCNꢀfollowedꢀbyꢀsimpleꢀ Cu(I) ꢀ andꢀ Cu(II) ꢀ oxidationꢀ statesꢀ haveꢀ alsoꢀ beenꢀ reportedꢀ
10-13
purificationꢀusingꢀtheꢀsalting-outꢀeffect.ꢀTheirꢀcatalyticꢀactivityꢀinꢀ withꢀ catalyticꢀ activityꢀ forꢀ thisꢀ reaction.
CuAACꢀ isꢀ boostedꢀ uponꢀ exposureꢀ 30ꢀ minꢀ inꢀ airꢀ producingꢀ Cu Oꢀ catalystsꢀ haveꢀ clearlyꢀ beenꢀ shownꢀ toꢀ beꢀ activeꢀ asꢀ Cu(I)ꢀ
NPs.ꢀTheseꢀNPsꢀareꢀalsoꢀsupportedꢀonꢀSBA-15ꢀprovidingꢀexcellentꢀ derivatives,
recyclableꢀ heterogeneousꢀ catalystsꢀ thatꢀ areꢀ appliedꢀ inꢀ lowꢀ activeꢀ inꢀ nanomaterialsꢀ isꢀ oftenꢀ notꢀ soꢀ wellꢀ defined.ꢀ Cu(0)ꢀ
ꢀ Molecularꢀ CuAACꢀ
2
2
,10,12
ꢀbutꢀtheꢀoxidationꢀstateꢀthatꢀisꢀactuallyꢀmostꢀ
10,11
amountsꢀforꢀefficientꢀ“click”ꢀfunctionalization.ꢀ
nanomaterialsꢀmightꢀbeꢀactiveꢀinꢀtheꢀCu(0)ꢀstate
areꢀeasilyꢀoxidizedꢀinꢀparticularꢀinꢀair,ꢀtheirꢀcatalyticꢀactivityꢀcanꢀ
ꢀor,ꢀasꢀtheyꢀ
1
Amongꢀtheꢀvariousꢀ“click”ꢀreactions ꢀCu-catalyzedꢀazideꢀalkyneꢀ
1
0,12
10,13
beꢀ dueꢀ toꢀ Cu(I)
ꢀ orꢀ Cu(II).
ꢀ Cu(II)ꢀ catalystsꢀ haveꢀ beenꢀ
2
cycloadditionꢀ (CuAAC) ꢀ (eqꢀ 1) undisputedlyꢀ dominatesꢀ withꢀ
ꢀ
proposedꢀforꢀclickꢀreactions,ꢀbutꢀtheꢀpossibilityꢀofꢀtheirꢀinꢀsituꢀ
reductionꢀ toꢀ Cu(I),ꢀ inꢀ particularꢀ byꢀ azidoꢀ derivativesꢀ orꢀ otherꢀ
substrates,ꢀcannotꢀbeꢀunderestimated.ꢀ
3
applicationsꢀspanningꢀoverꢀorganic, ꢀpolymer, ꢀbiomedical ꢀandꢀ
4
5
6
materials ꢀchemistry.ꢀ
HereꢀweꢀreportꢀnewꢀPEG-stabilized,ꢀrecyclable,ꢀhomogeneousꢀandꢀ
heterogeneousꢀ CuNPꢀ catalystsꢀ ofꢀ theꢀ CuAACꢀ reactionsꢀ includingꢀ
applicationsꢀ toꢀ variousꢀ biomoleculeꢀ functionalizationꢀ withꢀ lowꢀ Cuꢀ
amounts.ꢀ Inꢀ theꢀ sameꢀ timeꢀ weꢀ alsoꢀ wishꢀ toꢀ shedꢀ lightꢀ onꢀ theꢀ
problemꢀonꢀtheꢀoptimizedꢀCuꢀoxidationꢀstateꢀinꢀCuNPsꢀforꢀ“click”ꢀ
catalysisꢀbyꢀcomparingꢀtheꢀcatalyticꢀactivityꢀinꢀCuAACꢀreactionsꢀofꢀ
theseꢀnewꢀCu(0)NPsꢀwithꢀthoseꢀobtainedꢀuponꢀexposureꢀtoꢀair.ꢀInꢀ
particular,ꢀweꢀhaveꢀnowꢀexaminedꢀtheꢀcatalyticꢀactivityꢀofꢀCu(0)NPsꢀ
7
ꢀ+ꢀNaꢀascorbate, ꢀaꢀ
SinceꢀtheꢀearlyꢀreportꢀofꢀtheꢀuseꢀofꢀCuSO
4
largeꢀvarietyꢀofꢀmetalꢀcatalystsꢀhaveꢀbeenꢀpublishedꢀwithꢀtheꢀ
aimꢀtoꢀdecreaseꢀtheꢀamountꢀofꢀtoxicꢀCuꢀsourcesꢀandꢀimproveꢀ
2
-8
ꢀ
theꢀ greennessꢀ ofꢀ theꢀ reactionꢀ mediumꢀ andꢀ conditions.
Transitionꢀ metalꢀ nanoparticlesꢀ (NPs),ꢀ inꢀ particularꢀ thoseꢀ ofꢀ
nobleꢀ metals,ꢀ areꢀ excellentꢀ ligand-freeꢀ catalystsꢀ inꢀ greenꢀ
9
solventsꢀ forꢀ manyꢀ reactions. ꢀ Amongꢀ theseꢀ nanocatalysts,ꢀ
synthesizedꢀ byꢀ reductionꢀ ofꢀ CuSO
4 2
·5H Oꢀ byꢀ theꢀ strongꢀ reductantꢀ
sodiumꢀ naphthalenideꢀ andꢀ stabilizedꢀ byꢀ polyethyleneꢀ glycolꢀ (PEG-
biometalꢀ NPsꢀ ofꢀ theꢀ first-rawꢀ lateꢀ transitionꢀ metalsꢀ areꢀ
attractingꢀincreasingꢀattention,ꢀalthoughꢀtheyꢀareꢀtraditionallyꢀ
believeꢀ toꢀ beꢀ inferiorꢀ catalystsꢀ comparedꢀ toꢀ nobleꢀ transitionꢀ
metalꢀNPꢀcatalysts.ꢀAlongꢀthisꢀline,ꢀtheꢀfindingꢀbyꢀaꢀnumberꢀofꢀ
researchꢀgroupsꢀthatꢀCuNPsꢀandꢀCuꢀnanomaterialsꢀareꢀactiveꢀ
2
ꢀ
000,ꢀeqꢀ2).ꢀ
CuSO
4
ꢀ +ꢀ 2ꢀ Naꢀ naphthalenideꢀ +ꢀ PEGꢀ àCu(0)NP-PEGꢀ +ꢀ Na
2 4
SO ꢀ +ꢀ 2ꢀ
naphthaleneꢀꢀꢀ ꢀ
ꢀ
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ(eqꢀ2)ꢀ
catalystsꢀ forꢀ theꢀ CuAACꢀ reactionꢀ isꢀ ofꢀ particularꢀ interest,ꢀ Sodiumꢀ naphthalenide,ꢀ withꢀ aꢀ redoxꢀ potentialꢀ E°NaNaph/NaNaph-ꢀ ofꢀ -
14
becauseꢀtheseꢀcatalystsꢀavoidꢀtheꢀuseꢀofꢀcostlyꢀandꢀeventuallyꢀ 3.1Vꢀvs.ꢀNHEꢀinꢀTHF ꢀhasꢀrecentlyꢀbeenꢀusedꢀsuccessfullyꢀforꢀtheꢀ
9
toxicꢀligands. ꢀCuNPsꢀareꢀusuallyꢀformedꢀbyꢀreductionꢀofꢀaꢀCuꢀ reductionꢀofꢀearlyꢀtransitionꢀmetalꢀsaltsꢀtoꢀtheꢀcorrespondingꢀzero-
15
4
saltꢀ byꢀ aꢀ reductantꢀ suchꢀ asꢀ NaBH ꢀ inꢀ theꢀ presenceꢀ ofꢀ aꢀ valentꢀ NPs. ꢀ Weꢀ showꢀ hereinꢀ thatꢀ theꢀ catalyticꢀ activityꢀ ofꢀ CuNPsꢀ
stabilizer,ꢀ andꢀ theꢀ resultingꢀ CuNPsꢀ areꢀ supposedꢀ toꢀ containꢀ synthesizedꢀusingꢀthisꢀmethodꢀisꢀboostedꢀuponꢀexposureꢀtoꢀair.ꢀ
Whereasꢀ variousꢀ stabilizersꢀ suchꢀ asꢀ N,N-dimethylformamide,ꢀ
cetyltrimethylammoniumꢀ bromide,ꢀ alkylthiolates,ꢀ phosphinesꢀ areꢀ
a
º
ISM, UMR CNRS N 5255, Univ. Bordeaux, 33405 Talence Cedex, France.
b
toxic,ꢀpoly(ethyleneꢀglycol)ꢀ(PEG)ꢀhasꢀemergedꢀasꢀoneꢀofꢀtheꢀmostꢀ
Soft Matter Nanotechnology Lab, CIC biomaGUNE, Paseo Miramón 182. 20014.
1
6
Donostia-San Sebastián, Gipuzkoa, Spain.
promisingꢀnanocomponentsꢀinꢀbio-materialsꢀandꢀgreenꢀchemistry. ꢀ
Indeed,ꢀPEGsꢀareꢀcurrentlyꢀusedꢀasꢀcarriersꢀofꢀanticancerꢀdrugs,ꢀwithꢀ
efficiencyꢀ relatedꢀ toꢀ theꢀ enhancedꢀ permeabilityꢀ andꢀ retentionꢀ
c
LCC, UPR CNRS No. 8241, 31077 Toulouse Cedex, France
Facultad de Quimica , Universidad del Pais Vasco, Apdo 1072, 20080 San Sebastian,
d
Spain
1
7
effect. ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ1ꢀꢀ
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JournalꢀNameꢀ
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ꢀ
Figureꢀ2.ꢀ(a)ꢀTEMꢀofꢀtheꢀCu(I)NP-PEGꢀcatalyst.ꢀ(b)ꢀDetailꢀofꢀaꢀ4.8ꢀ
nmꢀNPꢀobservedꢀinꢀFigꢀS6ꢀandꢀ(c)ꢀcorrespondingꢀFastꢀFourierꢀ
TransformationꢀofꢀtheꢀHRTEMꢀimageꢀshownꢀinꢀFigꢀS6.ꢀ
ꢀ
ꢀ
smallꢀones,ꢀtwoꢀNPsꢀofꢀ4ꢀnmꢀ(SIꢀFigureꢀS8)ꢀandꢀ4.8ꢀnmꢀ(Figureꢀ
Figureꢀ1.ꢀSynthesisꢀandꢀpurificationꢀofꢀCu(0)NP-PEGꢀNPsꢀbyꢀsalting- 2b)ꢀrespectivelyꢀwereꢀselectedꢀinꢀtheꢀHRTEMꢀboth
ꢀ
showingꢀtheꢀ
clearꢀ latticeꢀ fringes.ꢀ Theꢀ latticeꢀ spacingꢀ isꢀ aboutꢀ 2.4ꢀ Å,ꢀ
assumingꢀ thatꢀ theꢀ crystallographicꢀ planeꢀ ofꢀ theꢀ Cu Oꢀ
outꢀunderꢀN
ꢀ
2
.ꢀ
2
Thusꢀ weꢀ haveꢀ usedꢀ PEG-2000ꢀ toꢀ stabilizeꢀ Cu(0)NPꢀ preparedꢀ byꢀ nanocrystalꢀ isꢀ {111}.ꢀ Thisꢀ indicatesꢀ thatꢀ theꢀ Cu(0)NP-PEGꢀ
reductionꢀ ofꢀ CuSO ·5H Oꢀ sodium-naphthalenideꢀ inꢀ CH CN.ꢀ Theseꢀ surfaceꢀwasꢀoxidizedꢀbyꢀO ꢀtoꢀformꢀCu OꢀNPs.ꢀTheꢀFastꢀFourierꢀ
Cu(0)NPsꢀ (notedꢀ Cu(0)NP-PEG-1ꢀ beforeꢀ purification)ꢀ haveꢀ beenꢀ TransformationꢀofꢀtheꢀHRTEMꢀimageꢀ(FigureꢀS6)ꢀfurtherꢀshowsꢀ
purifiedꢀbyꢀsimpleꢀextractionꢀwithꢀaꢀmixtureꢀofꢀCH Cl ꢀandꢀdegassedꢀ thatꢀaꢀgoodꢀcrystallinityꢀwasꢀachievedꢀinꢀthisꢀcase.ꢀꢀ
OꢀunderꢀN .ꢀInꢀthisꢀfirstꢀextraction,ꢀtheꢀCu(0)NPsꢀareꢀsolubleꢀinꢀtheꢀ Theꢀ CuNPsꢀ wereꢀ examinedꢀ forꢀ theirꢀ catalyticꢀ activityꢀ inꢀ theꢀ
organicꢀ phase,ꢀ dueꢀ toꢀ theꢀ salting-outꢀ effectꢀ ofꢀ Na
aqueousꢀ phase.ꢀ Thisꢀ allowedꢀ removingꢀ theꢀ colorlessꢀ aqueousꢀ differencesꢀ betweenꢀ theꢀ catalyticꢀ activitiesꢀ ofꢀ rawꢀ Cu(0)NP-
4
2
3
2
2
2
2
H
2
2
+
2-
2
4
SO ꢀ inꢀ theꢀ CuAACꢀ reactionꢀ inꢀ neatꢀ water.ꢀ Thereꢀ wereꢀ dramaticꢀ
+
2-
2 4
solutionꢀ containingꢀ Na SO ꢀ formedꢀ duringꢀ theꢀ synthesisꢀ ofꢀ theꢀ PEG-1,ꢀpurifiedꢀCu(0)NP-PEGꢀandꢀairꢀoxidizedꢀCu(I)NP-PEG.ꢀForꢀ
CuNPs.ꢀ Inꢀ aꢀ secondꢀ extractionꢀ ofꢀ theꢀ organicꢀ phaseꢀ byꢀ degassedꢀ instanceꢀ withꢀ 50ꢀ ppmꢀ Cu,ꢀ theꢀ isolatedꢀ yieldsꢀ ofꢀ theꢀ clickꢀ
water,ꢀtheꢀCuNPsꢀwereꢀtransferredꢀtoꢀtheꢀaqueousꢀphase,ꢀleavingꢀ reactionsꢀ betweenꢀ PhCCHꢀ andꢀ PhCH N ꢀ forꢀ theseꢀ 3ꢀ typesꢀ ofꢀ
2
3
naphthaleneꢀinꢀtheꢀorganicꢀphaseꢀthatꢀwasꢀalsoꢀwellꢀseparatedꢀinꢀ CuNP-PEGsꢀ wereꢀ respectivelyꢀ tracesꢀ (<1%),ꢀ 21%ꢀ andꢀ 72%ꢀ
thisꢀwayꢀ(Figureꢀ1).ꢀ
(Tableꢀ1).ꢀTheꢀfirstꢀconclusionꢀisꢀthatꢀpureꢀaqueousꢀCu(0)NP-
TheꢀabsenceꢀofꢀabsorptionꢀbandꢀinꢀtheꢀUV-vis.ꢀspectraꢀ(FigureꢀS1)ꢀ PEGꢀ performsꢀ betterꢀ inꢀ thisꢀ catalyticꢀ applicationꢀ thanꢀ theꢀ
showedꢀ thatꢀ theseꢀ purifiedꢀ CuNPsꢀ wereꢀ zero-valentꢀ Cuꢀ speciesꢀ Cu(0)NP-PEG-1ꢀ dissolvedꢀ inꢀ waterꢀ beforeꢀ theseꢀ purificationꢀ
(
notedꢀCu(0)NP-PEG).ꢀOnꢀtheꢀotherꢀhandꢀuponꢀexposureꢀtoꢀairꢀforꢀ steps,ꢀbecauseꢀtheseꢀsideꢀproductsꢀinhibitꢀtheꢀsurfaceꢀofꢀnon-
severalꢀminutesꢀtheseꢀCuNPsꢀwereꢀcharacterizedꢀbyꢀtheꢀapparitionꢀ purifiedꢀ Cu(0)NP-PEG-1.ꢀ Theꢀ secondꢀ conclusionꢀ isꢀ thatꢀ
1
8
2
ofꢀ aꢀ UV-vis.ꢀ bandꢀ atꢀ 360ꢀ nmꢀ forꢀ Cu Oꢀ andꢀ notedꢀ Cu(I)NP-PEG. ꢀ aerobicallyꢀoxidizedꢀCu(I)NP-PEGꢀisꢀaꢀmuchꢀbetterꢀcatalystꢀthanꢀ
Indeedꢀ UV-vis.ꢀ spectroscopyꢀ wasꢀ veryꢀ usefulꢀ toꢀ monitorꢀ thisꢀ beforeꢀoxidationꢀinꢀair,ꢀandꢀcon-ꢀversionꢀraisedꢀfromꢀ80%ꢀwithꢀ
oxidationꢀinꢀairꢀ(FigureꢀS2).ꢀTheseꢀchangesꢀappearedꢀtoꢀbeꢀcompleteꢀ 50ꢀppmꢀtoꢀ100%ꢀ(95%ꢀyield)ꢀwithꢀ100ꢀppmꢀCuꢀ(TONꢀ=ꢀ9500;ꢀ
-1
afterꢀ 30ꢀ min,ꢀ noꢀ furtherꢀ changeꢀ beingꢀ observedꢀ afterꢀ oneꢀ dayꢀ orꢀ TOFꢀ=ꢀ396ꢀh ).ꢀ
oneꢀweekꢀ(FigureꢀS3).ꢀꢀ
TheꢀscopeꢀofꢀapplicabilityꢀofꢀthisꢀlowꢀlevelꢀamountꢀofꢀCu(I)NP-
TheꢀXPSꢀspectraꢀshowedꢀanꢀabsorptionꢀforꢀCu(0)ꢀorꢀCu(I),ꢀalthoughꢀ PEGꢀ catalystꢀ wasꢀ exploredꢀ withꢀ CuAACꢀ ꢀ reactionsꢀ betweenꢀ
contraryꢀtoꢀUV-vis.ꢀitꢀwasꢀnotꢀpossibleꢀtoꢀdistinguishꢀbetweenꢀCu(0)ꢀ variousꢀalkynesꢀandꢀorganicꢀazidesꢀinꢀwater.ꢀGoodꢀyieldsꢀwereꢀ
andꢀ Cu(I)ꢀ usingꢀ XPS.ꢀ Onꢀ theꢀ otherꢀ hand,ꢀ itꢀ allowsꢀ distinguishingꢀ obtainedꢀ inꢀ theꢀ CuAACꢀ ofꢀ aꢀ wideꢀ varietyꢀ ofꢀ alkynesꢀ withꢀ
Cu(0/I)ꢀ fromꢀ Cu(II).ꢀ Onlyꢀ tinyꢀ tracesꢀ ofꢀ Cu(II)ꢀ dueꢀ toꢀ CuOꢀ areꢀ organicꢀazidesꢀ(TableꢀꢀS1).ꢀInꢀadditionꢀafterꢀtheꢀreactionsꢀtheꢀ
observedꢀafterꢀoneꢀweek.ꢀTheꢀCuꢀ2pꢀspectrumꢀshowedꢀtheꢀCuꢀ2p3/2ꢀ “click”ꢀ productsꢀ wereꢀ obtainedꢀ byꢀ simpleꢀ extraction–
andꢀ2p1/2ꢀpeaksꢀ(FigureꢀS4).ꢀTheꢀfittingꢀofꢀtheꢀCuꢀ2p3/2ꢀpartꢀofꢀtheꢀ washing−filtrationꢀ withoutꢀ silicaꢀ chromatography,ꢀ becauseꢀ
spectrumꢀrevealedꢀtheꢀpresenceꢀofꢀCu(I)ꢀorꢀCu(0)ꢀatꢀaroundꢀ932.1ꢀ theyꢀ areꢀ water-insolubleꢀ solids,ꢀ andꢀ theꢀ excessꢀ alkyneꢀ wasꢀ
eV,ꢀ andꢀ theꢀ smallꢀ componentꢀ atꢀ aroundꢀ 934.5ꢀ eVꢀ attributedꢀ toꢀ removedꢀbyꢀsimpleꢀwashingꢀwithꢀtheꢀsolvent.ꢀ
1
9
Cu(II). ꢀ
TheꢀcatalystꢀCu(I)NP-PEGꢀwasꢀsupportedꢀandꢀimmobilizedꢀontoꢀ
Theꢀ TEMꢀ ofꢀ Cu(I)NP-PEGꢀ (Figureꢀ 2a,ꢀ histogramꢀ inꢀ Figureꢀ S5)ꢀ SBA-15ꢀusingꢀtheꢀsol-immobilizationꢀmethod,ꢀandꢀthisꢀmaterialꢀ
showsꢀ thatꢀ theꢀ averageꢀ NPꢀ sizeꢀ isꢀ 3.2ꢀ nm,ꢀ withꢀ aꢀ maximumꢀ wasꢀdriedꢀatꢀ50°Cꢀ(ICPꢀcontent:ꢀ0.06ꢀwt%).ꢀTheꢀevaluationꢀofꢀ
distributionꢀaroundꢀ2.5-3ꢀnmꢀandꢀaꢀfewꢀNPsꢀaroundꢀ4-5ꢀnm.ꢀ theꢀ NPꢀ sizeꢀ distributionsꢀ ofꢀ theꢀ Cu(I)NP-PEGꢀ afterꢀ
BecauseꢀtheꢀcrystallinityꢀofꢀlargeꢀNPsꢀisꢀbetterꢀthanꢀthatꢀofꢀꢀꢀ
ꢀ
immobilizationꢀonꢀtheꢀsupportꢀisꢀdisplayedꢀinꢀFigureꢀS9ꢀandꢀꢀ
ꢀ
2
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
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Pleaseꢀd oC ꢀhn e omt ꢀ Ca od mj u ms tꢀmarginsꢀ
JournalꢀNameꢀ
ꢀCOMMUNICATIONꢀ
ꢀ
Tracesꢀ ofꢀ theꢀ finalꢀ 1,2,3-triazoleꢀ productꢀ wereꢀ obseVrievwedArꢀtibclyeꢀOtnhliinne-
aꢀ
DOI: 10.1039/C7CC02504A
Tableꢀ1.ꢀCuAACꢀreactionꢀ(eqꢀ1)ꢀꢀcatalyzedꢀbyꢀCuNP-PEGs.
layerꢀ chromatographyꢀ onlyꢀ afterꢀ theꢀ firstꢀ catalyticꢀ run,ꢀ andꢀ theꢀ
Catalystsꢀ Amountꢀ Conversionꢀ Yieldꢀ
TONꢀ
TOFꢀ
residualꢀsolutionꢀfromꢀotherꢀcatalyticꢀrunsꢀdidꢀnotꢀprovideꢀanyꢀmoreꢀ
tracesꢀofꢀthisꢀreactionꢀproduct,ꢀindicatingꢀthatꢀcatalystꢀleachingꢀdidꢀ
notꢀoccurꢀafterꢀtheꢀfirstꢀuseꢀofꢀtheꢀsupportedꢀcatalyst.ꢀ
b
c
d
-1
ꢀ
(%)ꢀ ꢀ
(%)ꢀ ꢀ
(h )ꢀ
Cu(I)NP-
100ꢀppmꢀ
100ꢀppmꢀ
100ꢀppmꢀ
50ꢀppmꢀ
50ꢀppmꢀ
50ꢀppmꢀ
100ꢀppmꢀ
50ꢀppmꢀ
100ꢀ
95ꢀ
9500ꢀ
6500ꢀ
4000ꢀ
396ꢀ
271ꢀ
167ꢀ
e
PEGꢀ ꢀ
Cu(0)NP-
Theꢀ catalystꢀ Cu(I)NP-PEG@SBA-15ꢀ wasꢀ alsoꢀ successfullyꢀ usedꢀ
toꢀ prepareꢀ functionalꢀ biomedicalꢀ materials.ꢀ Theꢀ “click”ꢀ
reactionꢀbetweenꢀ1-ethynylcyclohexanolꢀ(1),ꢀtheꢀprecursorꢀofꢀ
ethinamate,ꢀaꢀdepressantꢀdrugꢀthatꢀisꢀanꢀactiveꢀmetaboliteꢀofꢀ
74ꢀ
65ꢀ
PEGꢀ
Cu(0)NP-
50ꢀ
40ꢀ
PEG-1ꢀ
20
theꢀcentralꢀnervousꢀsystem, ꢀandꢀbenzylꢀazideꢀprovidedꢀ2ꢀinꢀ
goodꢀ isolatedꢀ yieldꢀ (87.8%)ꢀ withꢀ onlyꢀ 0.1%ꢀ Cuꢀ inꢀ 50%ꢀ aq.ꢀ t-
butanolꢀatꢀ35ꢀ°Cꢀforꢀ24ꢀhꢀ(eqꢀ3).ꢀAnotherꢀkeyꢀnaturalꢀproduct,ꢀ
Cu(I)NP-
80ꢀ
72ꢀ
14400ꢀ 600ꢀ
e
PEGꢀ ꢀ
Cu(0)NP-
32ꢀ
21ꢀ
4200ꢀ
-ꢀ
175ꢀ
-ꢀ
3
′-deoxy-3-azidothymidineꢀ(AZT,ꢀzidovudine,ꢀ3),ꢀisꢀaꢀnucleosideꢀ
PEGꢀ
Cu(0)NP-
analogueꢀ reverseꢀ transcriptaseꢀ inhibitor,ꢀ andꢀ itꢀ wasꢀ theꢀ firstꢀ
approvedꢀ antiviralꢀ productꢀ forꢀ theꢀ treatmentꢀ ofꢀ humanꢀ
traceꢀ
100ꢀ
84ꢀ
traceꢀ
97ꢀ
PEG-1ꢀ
21ꢀ
immunodeficiencyꢀvirusꢀ(HIV). Theꢀ3′-azi-doꢀgroupꢀofꢀAZTꢀhasꢀ
Cu(I)NP-
9700ꢀ
404ꢀ
22
f
providedꢀpotentialꢀapplicationꢀtoꢀHIVꢀRTꢀbinding. ꢀItsꢀ“click”ꢀ
functionalizationꢀhasꢀꢀbeenꢀshownꢀtoꢀbeꢀaꢀconvenientꢀtoolꢀforꢀ
PEGꢀ ꢀ
Cu(I)NP-
75ꢀ
15000ꢀ 625ꢀ
f
theꢀ synthesisꢀ ofꢀ newꢀ nucleosideꢀ inhibitorsꢀ withꢀ lowꢀ toꢀ
23,24
PEGꢀ ꢀ
aꢀ
Reactionꢀ conditions:ꢀ 0.5ꢀ mmolꢀ ofꢀ benzylꢀ azide,ꢀ 0.505ꢀ mmolꢀ ofꢀ submicromolarꢀ potenciesꢀ againstꢀ HIV-1,
ꢀ newꢀ fluorescentꢀ
b
.ꢀ ꢀ markers,ꢀandꢀcytostaticꢀagents.
25,26
phenylacetylene,ꢀ 2ꢀ mLꢀ degassedꢀ H
2
O,ꢀ 35°C,ꢀ 24ꢀ h,ꢀ underꢀ N
2
ꢀHere,ꢀtheꢀ“click”ꢀreactionꢀ
c
1
Amountꢀ ofꢀ catalystsꢀ usedꢀ inꢀ theꢀ CuAACꢀ reduction.ꢀ ꢀ Hꢀ NMRꢀ betweenꢀ zidovudineꢀ 3ꢀ andꢀ phenylacetyleneꢀ usingꢀ 0.1%ꢀ Cuꢀ
d
e
conversion.ꢀ ꢀ Isolatedꢀ yield.ꢀ ꢀ Cu(I)NP-PEGꢀ (exposedꢀ toꢀ airꢀ 30ꢀ minꢀ fromꢀCu(I)NP-PEG@SBA-15ꢀinꢀ50%ꢀt-butanolꢀatꢀ35ꢀ°Cꢀforꢀ24ꢀhꢀ
f
providedꢀ4ꢀinꢀ91.8%ꢀisolatedꢀyieldꢀ(eqꢀ4).ꢀCu(I)NP-PEG@SBA-15ꢀ
wasꢀalsoꢀappliedꢀtoꢀsynthesizeꢀ“click”-triazoleꢀfunctionalizedꢀ7-
beforeꢀcatalysis)ꢀwork-upꢀinꢀdeionizedꢀH
2
O.ꢀ ꢀCu(I)NP-PEGꢀ(exposedꢀ
toꢀairꢀ1ꢀdayꢀbeforeꢀcatalysis)ꢀwork-upꢀinꢀdeionizedꢀH O.ꢀ
2
(
2
propargyloxy)ꢀ coumarinꢀ 6ꢀ fromꢀ 5ꢀ inꢀ H O/ꢀ tert-butanol.ꢀ
Coumarinꢀderivativesꢀareꢀoftenꢀusedꢀinꢀtheꢀperfumeꢀindustry.ꢀ
Moreover,ꢀ theyꢀ areꢀ fluorophoresꢀ andꢀ haveꢀ recentlyꢀ beenꢀ
employedꢀasꢀfluorescentꢀprobesꢀtoꢀvisualizeꢀtheꢀmetabolismꢀofꢀ
revealsꢀthatꢀtheꢀaverageꢀparticleꢀsizeꢀofꢀtheꢀsupportedꢀcatalystꢀ
Cu(I)NP-PEG@SBA-15ꢀ isꢀ 2.5ꢀ nm,ꢀ i.e.ꢀ smallerꢀ thanꢀ unsupportedꢀ
Cu(I)NP-PEG.ꢀ Thisꢀ indicatesꢀ thatꢀ theꢀ SBA-15ꢀ supportꢀ preventsꢀ
Cu(I)NP-PEGꢀ aggregationꢀ andꢀ betterꢀ stabilizesꢀ veryꢀ smallꢀ Cu(I)NP-
PEG@SBA-15ꢀ thanꢀ unsupportedꢀ Cu(I)NP-PEG.ꢀ Recyclingꢀ experi-
mentsꢀ usingꢀ 300ꢀ pmꢀ ofꢀ Cu(I)NP-PEG@SBA-15ꢀ providedꢀ isolatedꢀ
yieldsꢀ largerꢀ thanꢀ 85%ꢀ duringꢀ atꢀ leastꢀ fiveꢀ successiveꢀ recyclingꢀ
experimentsꢀ(TableꢀS2),ꢀshowingꢀtheꢀgoodꢀstabilityꢀofꢀtheꢀcatalystꢀ
Cu(I)NP-PEG@SBA-15.ꢀFollowingꢀtheꢀcatalyticꢀreaction,ꢀtheꢀresidualꢀ
solutionꢀafterꢀcentrifugationꢀwasꢀusedꢀtoꢀtestꢀtheꢀCuAACꢀreaction.ꢀ
27
cysteineꢀinꢀlivingꢀcells. ꢀInꢀthisꢀcaseꢀ(eqꢀ5),ꢀ92.7%ꢀisolatedꢀyieldꢀ
wasꢀ achievedꢀ withꢀ 0.1%ꢀ Cuꢀ fromꢀ theꢀ catalystꢀ Cu(I)NP-
PEG@SBA-15.ꢀ Moreover,ꢀ noteꢀ thatꢀ theseꢀ threeꢀ functionalꢀ
“
click”ꢀreactionsꢀcatalyzedꢀbyꢀtheꢀsupportedꢀcatalystꢀCu(I)NP-
PEG@SBA-15ꢀ yieldingꢀ compoundꢀ 2,ꢀ 4ꢀ andꢀ 6ꢀ workꢀ inꢀ higherꢀ
yieldꢀ withꢀ lessꢀ reactionꢀ timeꢀ thanꢀ withꢀ theꢀ unsupportedꢀ
catalystꢀ Cu(I)NP-PEG.ꢀ Theꢀ interfacialꢀ effectꢀ withinꢀ theꢀ
supportedꢀ catalystꢀ playsꢀ anꢀ importantꢀ roleꢀ inꢀ theꢀ “click”ꢀ
functionalizationꢀofꢀtheꢀbiomedicalꢀproducts.ꢀ
Conclusionꢀ
Inꢀ conclusion,ꢀ theꢀ synthesisꢀ andꢀ purificationꢀ ofꢀ newꢀ PEG-
stabilizedꢀ homogeneousꢀ andꢀ heterogeneousꢀ nano-catalystsꢀ
CuNP-PEGꢀ forꢀ “CuAAC”ꢀ reactionsꢀ hasꢀ beenꢀ achieved.ꢀ Theꢀ
purifiedꢀ aqueousꢀ catalystꢀ Cu(0)NP-PEGꢀ performsꢀ betterꢀ thanꢀ
theꢀ crudeꢀ catalystꢀ Cu(0)NP-PEG-1ꢀ dissolvedꢀ inꢀ waterꢀ beforeꢀ
salting-outꢀ process,ꢀ becauseꢀ theseꢀ stepsꢀ helpꢀ purifyingꢀ theꢀ
side-productsꢀonꢀtheꢀCuNPꢀsurfaceꢀandꢀexposeꢀmoreꢀcatalyticꢀ
activeꢀ sitesꢀ forꢀ “click”ꢀ substrates.ꢀ Aerobicꢀ oxidationꢀ ofꢀ
Cu(0)NP-PEGꢀ toꢀ Cu(I)NP-PEGꢀ furtherꢀ largelyꢀ improvesꢀ theꢀ
catalyticꢀactivity,ꢀindicatingꢀthatꢀCu
catalyst.ꢀThisꢀshowsꢀthatꢀamongꢀCuNPsꢀandꢀCu-oxideꢀNPs,ꢀtheꢀ
highestꢀactivityꢀisꢀbyꢀfarꢀexhibitedꢀbyꢀCu OꢀNPsꢀresultingꢀfromꢀ
rapidꢀaerobicꢀoxidationꢀofꢀCu(0)NPs.ꢀBothꢀCu(0)ꢀNPsꢀandꢀCu Oꢀ
2
OꢀNPsꢀareꢀtheꢀrealꢀ“CuAAC”ꢀ
2
2
NPsꢀareꢀactive,ꢀbutꢀtheꢀpresentꢀstudyꢀhighlightsꢀtheꢀsuperiorityꢀ
ofꢀtheꢀlatter.ꢀThisꢀcatalystꢀCu(I)NP-PEGꢀwasꢀheterogenizedꢀonꢀ
SBA-15ꢀ forꢀ efficientꢀ recyclingꢀ andꢀwasꢀ successfullyꢀ appliedꢀ inꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ3ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Pleaseꢀd oC ꢀhn e omt ꢀ Ca od mj u ms tꢀmarginsꢀ
Page 4 of 4
COMMUNICATIONꢀ
CuAAC”ꢀ reactionsꢀ betweenꢀ variousꢀ azidesꢀ andꢀ alkynesꢀ
JournalꢀNameꢀ
1
0ꢀ (a)ꢀ F.ꢀ Alonso,ꢀ Y.ꢀ Moglieꢀ andꢀ G.ꢀ Radivoy,ꢀ AccV.ꢀieCwhAertmicle.ꢀORnelisn.e,ꢀ
015,ꢀ 48,ꢀ 2516;ꢀ (b)ꢀ M.ꢀ B.ꢀ Gawan ,ꢀ .ꢀ
“
2
DOI: 10.1039/C7CC02504A
de,ꢀ A.ꢀ Goswami F.X
includingꢀ functionalizationꢀ ofꢀ compoundsꢀ ofꢀ biomedicalꢀ
interest.ꢀ Theseꢀ principlesꢀ ofꢀ biometalꢀ nanocatalystꢀ designꢀ
couldꢀbeꢀextendedꢀtoꢀvariousꢀotherꢀcatalystsꢀinꢀtheꢀcloseꢀfuture.
Felpin,ꢀ T.ꢀ Asefa,ꢀ X.ꢀ X.ꢀ Huang,ꢀ R.ꢀ Silva,ꢀ X.ꢀ X.ꢀ Zou,ꢀ R.ꢀ Zborilꢀ
andꢀR.ꢀS.ꢀVarma,ꢀChem.ꢀRev.,ꢀ2016,ꢀ116,ꢀ3722.ꢀ
1ꢀ a)ꢀT.ꢀN.ꢀJin,ꢀꢀM.ꢀYanꢀandꢀY.ꢀYamamoto,ꢀChemcatchem,ꢀ2012,ꢀ4,ꢀ
ꢀ
1
1
217;ꢀ (b)ꢀ T.ꢀ M.ꢀ Vishwanathaꢀ andꢀ V.ꢀ V.ꢀ Sureshbabu,ꢀ J.ꢀ
HeteroclicꢀChem.,ꢀ2015,ꢀ52,ꢀ1823;ꢀ(c)ꢀM.ꢀd'Halluin,ꢀT.ꢀMabit,ꢀꢀN.ꢀ
Fairley,ꢀꢀV.ꢀFernandez,ꢀꢀM.ꢀB.ꢀGawande,ꢀꢀE.ꢀLeꢀGrognecꢀandꢀF.ꢀX.ꢀ
Felpin,ꢀCarbon,ꢀ2015,ꢀ93,ꢀ974;ꢀ(d)ꢀM.ꢀN.ꢀS.ꢀRad,ꢀS.ꢀBehrouz,ꢀS.ꢀJ.ꢀ
Hoseini,ꢀꢀH.ꢀNasrabadiꢀandꢀM.ꢀS.ꢀZare,ꢀHelv.ꢀChim.ꢀActa,ꢀ2015,ꢀ
Acknowledgmentꢀ
Helpfulꢀ discussionsꢀ withꢀ Missꢀ M.ꢀ Tisseraudꢀ (ISM)ꢀ andꢀ financialꢀ
supportꢀfromꢀtheꢀChinaꢀScholarshipꢀCouncilꢀ(CSC)ꢀofꢀtheꢀPeople’sꢀ
RepublicꢀofꢀChinaꢀ(grantsꢀtoꢀF.ꢀF.ꢀandꢀC.ꢀW.),ꢀtheꢀUniversitiesꢀofꢀ
Bordeaux,ꢀToulouseꢀ3,ꢀBasqueꢀCountry,ꢀandꢀSanꢀSebastian,ꢀandꢀ
theꢀCNRSꢀareꢀgratefullyꢀacknowledged.ꢀ
98,ꢀ1210.
a)ꢀZ.ꢀF.ꢀZhang,ꢀC.ꢀM.ꢀDong,ꢀC.ꢀH.ꢀYang,ꢀD.ꢀHu,ꢀJ.ꢀLong,ꢀꢀL.ꢀWang,ꢀ
H.ꢀLi,ꢀY.ꢀChenꢀandꢀD.ꢀL.ꢀKong,ꢀAdv.ꢀSyn.ꢀCatal.,ꢀ2010,ꢀ352,ꢀ1600;ꢀ
b)ꢀK.ꢀWang,ꢀX.ꢀH.ꢀBi,ꢀS.ꢀX.ꢀXing,ꢀP.ꢀQ.ꢀLiao,ꢀꢀZ.ꢀX.ꢀFang,ꢀX.ꢀY.ꢀ
Meng,ꢀQ.ꢀA.ꢀZhang,ꢀQ.ꢀLiuꢀandꢀY.ꢀJi,ꢀGreenꢀChem.,ꢀ2011,ꢀ13,ꢀ
62;ꢀ(c)ꢀA.ꢀC.ꢀCardiel,ꢀM.ꢀC.ꢀBenson,ꢀL.ꢀM.9Bishop,ꢀK.ꢀM.ꢀLouis,ꢀ
J.ꢀC.ꢀYeager,ꢀY.ꢀZ.ꢀTanꢀandꢀR.ꢀJ.ꢀHamers,ꢀACSꢀNano,ꢀ2012,ꢀ6,ꢀ310;ꢀ
d)ꢀF.ꢀAlonso,ꢀY.ꢀMoglie,ꢀG.ꢀRadivoyꢀandꢀM.ꢀYus,ꢀSynlett,ꢀ2012,ꢀ
ꢀ
1
2ꢀ
(
(
5
Notesꢀandꢀreferencesꢀ
1
(
ꢀ ꢀꢀH.ꢀC.ꢀKolb,ꢀM.ꢀG.ꢀFinnꢀandꢀK.ꢀB.ꢀSharpless,ꢀAngew.ꢀChem.ꢀInt.ꢀ
Ed.,ꢀ2001,ꢀ40,ꢀ2004.ꢀ
15,ꢀ 2179;ꢀ ꢀ (e)ꢀ A.ꢀ S.ꢀ Nia,ꢀ S.ꢀ Rana,ꢀ D.ꢀ Dohler,ꢀ X.ꢀ Noirfalise,ꢀ A.ꢀ
BelfioreꢀandꢀW.ꢀH.ꢀBinder,ꢀChem.ꢀCommun.,ꢀ2014,ꢀ50,ꢀ15374;ꢀ
(f)ꢀ A.ꢀ S.ꢀ Nia,ꢀ S.ꢀ Rana,ꢀ D.ꢀ Dohler,ꢀ F.ꢀ Jirsa,ꢀ A.ꢀ Meister,ꢀ L.ꢀ
Guadagno,ꢀ E.ꢀ Koslowski,ꢀ ꢀ M.ꢀ Bronꢀ andꢀ W.ꢀ H.ꢀ Binder,ꢀ Chem.ꢀ
Eur.ꢀ J.,ꢀ 2015,ꢀ 21,ꢀ 10763;ꢀ (g)ꢀ F.ꢀ Masoud,ꢀ A.ꢀ Mojtabaꢀ andꢀ A.ꢀ
AlirezaꢀPourvahabi,ꢀꢀCatal.ꢀCommun.,ꢀ2016,ꢀ76,ꢀ72;ꢀ(h)ꢀB.ꢀW.ꢀ
Wang,ꢀ J.ꢀ Durantini,ꢀ J.ꢀ Nie,ꢀ AE.ꢀ Lanternaꢀ andꢀ J.ꢀ C.ꢀ Scaiano,ꢀ J.ꢀ
2
ꢀ
(
2
3
a)ꢀ M.ꢀ Meldalꢀ andꢀ C.ꢀ W.ꢀ Torn
ø
e,ꢀ Chem.ꢀ Rev.,ꢀ 2008,ꢀ 108,ꢀ
952;ꢀ(b)ꢀJ.ꢀE.ꢀHeinꢀandꢀV.ꢀV.ꢀFokin,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2010,ꢀ
9,ꢀ1302;ꢀ(c)ꢀA.ꢀMandoli,ꢀMolecules,ꢀ2016,ꢀ21,ꢀ1174;ꢀ(d)ꢀC.ꢀ
Wang,ꢀD.ꢀIkhlef,ꢀS.ꢀKahlal,ꢀJ.Y.ꢀSaillardꢀandꢀD.ꢀAstruc,ꢀCoord.ꢀ
Chem.ꢀRev.,ꢀ2016,ꢀ316,ꢀ1.ꢀ
(a)ꢀH.ꢀC.ꢀKolbꢀandꢀK.ꢀB.ꢀSharpless,ꢀDrugꢀDisc.ꢀToday,ꢀ2003,ꢀ8,ꢀ
1
Rev.,ꢀ2009,ꢀ109,ꢀ4207;ꢀ(c)ꢀW.ꢀTangꢀandꢀM.ꢀL.ꢀBecker,ꢀChem.ꢀ
3
ꢀ
ꢀ
Am.ꢀChem.ꢀSoc.,ꢀ2016,ꢀ138,ꢀ13127.ꢀ
128;ꢀꢀ (b)ꢀF.ꢀAmblard,ꢀJ.ꢀH.ꢀChoꢀandꢀR.ꢀF.ꢀSchinazi,ꢀChem.ꢀ 13ꢀ (a)ꢀV.ꢀH.ꢀReddy,ꢀY.ꢀV.ꢀR.ꢀReddy,ꢀB.ꢀSridharꢀandꢀB.ꢀV.ꢀS.ꢀReddy,ꢀ
Adv.ꢀSyn.ꢀCatal.,ꢀ2016,ꢀ358,ꢀ1088;ꢀ(b)ꢀS.ꢀJang,ꢀY.ꢀJ.ꢀSa,ꢀS.ꢀH.ꢀJooꢀ
Sc.ꢀRev.,ꢀ2014,ꢀ43,ꢀ7013;ꢀ(d)ꢀV.ꢀK.ꢀTiwari,ꢀK.ꢀB.ꢀMishra,ꢀN.ꢀ
andꢀK.ꢀH.ꢀPark,ꢀCatal.ꢀCommun.,ꢀ2016,ꢀ81,ꢀ24.
ꢀ
Misra,ꢀ A.ꢀ S.ꢀ Singhꢀ andꢀ X.ꢀ Chen,ꢀ Chem.ꢀ Rev.,ꢀ 2016,ꢀ 116,ꢀ 14ꢀ N.ꢀG.ꢀConnellyꢀandꢀW.ꢀE.ꢀGeiger,ꢀChem.ꢀRev.,ꢀ1996,ꢀ96,ꢀ877.
086.
15ꢀ a)ꢀC.ꢀSchöttle,ꢀP.ꢀBockstaller,ꢀR.ꢀPopescu,ꢀD.ꢀGerthsenꢀandꢀ
a)ꢀ W.ꢀ H.ꢀ Binderꢀ andꢀ R.ꢀ Sachsenhofer,ꢀ Macromol.ꢀ Rapidꢀ
ꢀ
3
ꢀ
(
4
5
(
C.ꢀFeldmann,ꢀAngew.ꢀChem.ꢀIntꢀEd.,ꢀ2015,ꢀ54,ꢀ9866;ꢀ(b)ꢀC.ꢀ
Schöttle,ꢀ D.ꢀ E.ꢀ Doronkin,ꢀ R.ꢀ Popescu,ꢀ D.ꢀ Gerthsen,ꢀ J.ꢀ D.ꢀ
Grünwaldꢀ andꢀ C.ꢀ Feldmann,ꢀ Chem.ꢀ Commun.,ꢀ 2016,ꢀ 52,ꢀ
6316.ꢀ
Commun.,ꢀ 2007,ꢀ 28,ꢀ 15;ꢀ (b)ꢀ D.ꢀ Fournier,ꢀ R.ꢀ Hoogenboomꢀ
andꢀU.ꢀS.ꢀSchubert,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2007,ꢀ36,ꢀ1369;ꢀ(c)ꢀM.ꢀ
Meldal,ꢀMacromol.ꢀRapidꢀCommun.,ꢀ2008,ꢀ29,ꢀ1016;ꢀ(d)ꢀP.ꢀ
L.ꢀGolasꢀandꢀK.ꢀMatyjaszewski,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2010,ꢀ39,ꢀ 16ꢀ E.ꢀSeo,ꢀJ.ꢀKim,ꢀY.ꢀHong,ꢀY.ꢀS.ꢀKim,ꢀD.ꢀLeeꢀandꢀB.ꢀS.ꢀKim,ꢀJ.ꢀ
338;ꢀ(e)ꢀK.ꢀKempe,ꢀA.ꢀKriegꢀandꢀC.ꢀM.ꢀBerce,ꢀChem.ꢀSoc.ꢀ
Phys.ꢀChem.ꢀC,ꢀ2013,ꢀ117,ꢀ11686.
Rev.,ꢀ2012,ꢀ41,ꢀ176;ꢀ(f)ꢀG.ꢀDelaittre,ꢀN.ꢀK.ꢀGuimardꢀandꢀC.ꢀ 17ꢀ H.ꢀMaeda,ꢀAdv.ꢀEnzymeꢀRegul.,ꢀ2001,ꢀ41,ꢀ187.
Barner-Kowollik,ꢀAcc.ꢀChem.ꢀRes.,ꢀ2015,ꢀ48,ꢀ1296.
18ꢀ a)ꢀM.ꢀSalavati-NiasariꢀandꢀF.ꢀDavar,ꢀMater.ꢀLett.,ꢀ2009,ꢀ63,ꢀ
(a)ꢀA.ꢀH.ꢀEl-SagheerꢀandꢀT.ꢀBrown,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2010,ꢀ
9,ꢀ1388;ꢀ(b)ꢀP.ꢀThimurugan,ꢀD.ꢀMatosiukꢀandꢀK.ꢀJozwiak,ꢀ
Chem.ꢀ Rev.,ꢀ 2013,ꢀ 113,ꢀ 4905;ꢀ (c)ꢀ S.ꢀ Svenson,ꢀ Chem.ꢀ Soc.ꢀ
1
ꢀ
ꢀ
ꢀ
(
ꢀ
441;ꢀ (b)ꢀ X.ꢀ Liu,ꢀ D.ꢀ Gregurec,ꢀ J.ꢀ Irigoyen,ꢀ A.ꢀ Martinez,ꢀ S.ꢀ
Moya,ꢀR.ꢀCiganda,ꢀP.ꢀHermange,ꢀJ.ꢀRuizꢀandꢀD.ꢀAstruc,ꢀNat.ꢀ
Commun.,ꢀ2016,ꢀ7,ꢀ13152.ꢀ
3
Rev.,ꢀ 2015,ꢀ 44,ꢀ 5131;ꢀ (d)ꢀ X.ꢀ Wang,ꢀ B.ꢀ Huangꢀ andꢀ X.ꢀ Liu,ꢀ 19ꢀ J.ꢀF.ꢀMoulder,ꢀW.ꢀF.ꢀStickle,ꢀP.ꢀE.ꢀSobolꢀandꢀK.ꢀD.ꢀBomben,ꢀ
Drug.ꢀDiscov.ꢀToday,ꢀ2016,ꢀ21,ꢀ118.
Handbookꢀ ofꢀ X-rayꢀ Photoelectronꢀ Spectroscopy,ꢀ Physicalꢀ
ꢀ ꢀꢀ(a)ꢀJ.ꢀF.ꢀLutz,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2007,ꢀ46,ꢀ1018;ꢀ(b)ꢀV.ꢀ
Electronicsꢀ1995.
Castro,ꢀH.ꢀRodrigueꢀandꢀF.ꢀAbeico,ꢀACSꢀCombin.ꢀSci.,ꢀ2016,ꢀ 20ꢀ ꢀꢀH.ꢀLangecker,ꢀH.ꢀJ.ꢀSchumannꢀandꢀK.ꢀJunkmann,ꢀArch.ꢀExptl.ꢀꢀ
8,ꢀ1.ꢀ
Pathol.ꢀPharmakol.,ꢀ1953,ꢀ219,ꢀ130.ꢀ
ꢀ ꢀꢀV.ꢀV.ꢀRostovtsev,ꢀL.ꢀG.ꢀGeen,ꢀV.ꢀV.ꢀFokinꢀandꢀK.ꢀB.ꢀSharpless,ꢀ 21ꢀ W.ꢀNickel,ꢀG.ꢀBialekꢀandꢀF.ꢀGrosse,ꢀJ.ꢀBiol.ꢀChem.,ꢀ1992,ꢀ267,ꢀ
Angew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2002,ꢀ41,ꢀ2596.ꢀ
848.
C.ꢀW.ꢀTorn
e,ꢀC.ꢀChristensenꢀandꢀM.ꢀMeldal,ꢀJ.ꢀOrg.ꢀChem.,ꢀ 22ꢀ P.ꢀThirumurugan,ꢀD.ꢀMatosiukꢀandꢀK.ꢀJozwiak,ꢀChem.ꢀRev.,ꢀ
002,ꢀ67,ꢀ3057.ꢀ
2013,ꢀ113,ꢀ4905.
a)ꢀM.ꢀT.ꢀReetzꢀandꢀJ.ꢀG.ꢀdeꢀVries,ꢀChem.ꢀCommun.,ꢀ2004,ꢀ 23ꢀ L.ꢀ Zhou,ꢀ A.ꢀ Amer,ꢀ M.ꢀ Korn,ꢀ R.ꢀ Burda,ꢀ J.ꢀ Balzarini,ꢀ E.ꢀ D.ꢀ
ꢀ
6
7
ꢀ
1
ꢀ
8
9
ꢀ
ø
2
(
ꢀ
ꢀ
1
2
559;ꢀ(b)ꢀD.ꢀAstruc,ꢀF.ꢀLuꢀandꢀJ.ꢀRuiz,ꢀAngew.ꢀChem.ꢀIntꢀEd.,ꢀ
005,ꢀ44,ꢀ7852;ꢀ(c)ꢀV.ꢀPolshettiwarꢀandꢀR.ꢀS.ꢀVarma,ꢀGreenꢀ
Clercq,ꢀ E.ꢀ R.ꢀ Kernꢀ andꢀ P.ꢀ F.ꢀ Torrence,ꢀ Antiviralꢀ Chem.ꢀ
Chemother,ꢀ2005,ꢀ16,ꢀ375.ꢀ
Chemistry,ꢀ2010,ꢀ12,ꢀ743;ꢀ(d)ꢀV.ꢀS.ꢀMeyers,ꢀM.ꢀG.ꢀWeier,ꢀE.ꢀ 24ꢀ V.ꢀR.ꢀSirivolu,ꢀS.ꢀK.ꢀV.ꢀVernekar,ꢀT.ꢀIlina,ꢀN.ꢀS.ꢀMyshakina,ꢀM.ꢀ
V.ꢀCarino,ꢀD.ꢀF.ꢀYancey,ꢀS.ꢀPandeꢀandꢀR.ꢀM.ꢀCrooks,ꢀChem.ꢀ
A.ꢀParniakꢀandꢀZ.ꢀWang,ꢀJ.ꢀMed.ꢀChem.,ꢀ2013,ꢀ56,ꢀ8765.ꢀ
Sci.,ꢀ2011,ꢀ2,ꢀ1632;ꢀ(e)ꢀA.ꢀBalanta,ꢀC.ꢀGodardꢀandꢀC.ꢀClaver,ꢀ 25ꢀ D.ꢀ Baraniak,ꢀ K.ꢀ Kacprzakꢀ andꢀ L.ꢀ Celewicz,ꢀ Bioorg.ꢀ Med.ꢀ
Chem.ꢀ Soc.ꢀ Rev.,ꢀ 2011,ꢀ 40,ꢀ 4973;ꢀ (f)ꢀ A.ꢀ Corma,ꢀ A.ꢀ Leyva-
Chem.ꢀLett.,ꢀ2011,ꢀ21,ꢀ723.
PerezꢀandꢀM.ꢀSabater,ꢀJ.ꢀChem.ꢀRev.,ꢀ2011,ꢀ111,ꢀ1657;ꢀ(g)ꢀL.ꢀ 26ꢀ P.ꢀW.ꢀSzafrański,ꢀ P.ꢀKasza,ꢀM.ꢀKępczyńskiꢀandꢀM.ꢀT.ꢀCegła,ꢀ
M.ꢀBronsteinꢀandꢀZ.ꢀB.ꢀShifrina,ꢀChem.ꢀRev.ꢀ2011,ꢀ111,ꢀ5301;ꢀ
Heterocycl.ꢀCommun.,ꢀ2015,ꢀ21,ꢀ263.
h)ꢀE.ꢀGross,ꢀJ.ꢀH.ꢀC.ꢀLiu,ꢀF.ꢀD.ꢀTosteꢀandꢀG.ꢀA.ꢀSomorjai,ꢀNat.ꢀ 27ꢀ Y.ꢀYue,ꢀF.ꢀHuo,ꢀP.ꢀNing,ꢀY.ꢀZhang,ꢀJ.ꢀChao,ꢀX.ꢀMengꢀandꢀC.ꢀ
ꢀ
ꢀ
(
Chem.,ꢀ 2012,ꢀ 4,ꢀ 947;ꢀ (i)ꢀ M.ꢀ Sankar,ꢀ N.ꢀ Dimitratos,ꢀ P.ꢀ J.ꢀ
Miedziak,ꢀP.ꢀP.ꢀWells,ꢀC.ꢀJ.ꢀKielyꢀandꢀG.ꢀJ.ꢀHutchings,ꢀChem.ꢀ
Sci.ꢀ2012,ꢀ3,ꢀ20;ꢀ(j)ꢀM.ꢀHaruta,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2014,ꢀ
Yin.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2017,ꢀ139,ꢀ3181.ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
5
3,ꢀ 52;ꢀ (k)ꢀ C.ꢀ Amiens,ꢀ D.ꢀ Ciuculescu-Pradinesꢀ andꢀ K.ꢀ
Philippot,ꢀ Coord.ꢀ Chem.ꢀ Rev.ꢀ 2016,ꢀ 308,ꢀ 409;ꢀ (l)ꢀ D.ꢀ Wangꢀ
andꢀD.ꢀAstruc,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2017,ꢀ46,ꢀ816.ꢀ
4
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