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Electronic Supplementary Material (ESI) for Biomaterials ScienceThis journal is © The Royal Society of Chemistry 2013

TableS1:MassspectralcharacteristicsofintracellularmetabolitesdetectedbyGC‐MSincludingRetentionIndex,CompoundSpectrum,ReverseMatchandcorrespondingp‐Value.AnalyteName RetentionIndex CompoundSpectrum ReverseMatch p‐Value

AMP(5TMS) 3106.82129:1454169:2939192:2145230:2567236:1799243:1893258:2131280:1531299:2704315:4022337:1729382:2135

521 0.011

Arachidicacid(1TMS) 2474.84 117:9827129:5682132:5866201:2196369:21586 547 0.023

Asparticacid(2TMS) 1442.58 117:4750130:6237202:1851218:1997220:1906245:3927262:1909 520 0.026

Cholesterol(1TMS) 3197.11

77:583979:1375181:2264989:214891:1809993:1569295:26769101:4038105:22138107:19768119:25663123:10029129:91499131:18193133:19672135:13851145:30123159:25925163:13005173:13745177:7827181:11954189:7514203:11974213:19868217:12078227:6852233:10237241:5706247:28486255:24346275:14321301:10753311:5246353:71183368:117632386:1623401:1895416:3311443:26156458:67091

787 0.02

Fructose(1MeOX5TMS) 1907.96 103:3275133:1770189:1268205:1669217:4654277:1916307:4454364:1380 735 0.022

Glucitol(6TMS) 1979.41

103:3203117:2424129:1743133:2214157:1584189:2431205:8695217:7249229:1928255:1492277:1980291:1831307:3968319:13628331:1842345:1746421:1640

795 0.044

Glucose‐6‐P(6TMS) 2259.97 127:1483133:2821155:1733191:2527204:2026217:2877299:5718315:4249387:2018 441 0.045

Glutamicacid(2TMS) 1542.7284:9665116:2016130:2281158:6681174:19980186:4002201:1997230:7160248:2680258:6585276:4398

659 0.042

Glycine(3TMS) 1286.03 100:5279248:25225276:8953 274 0.023Myo‐Inositol(6TMS) 2133.85 103:3887129:8017133:9296143:3673159:1462 830 0.028

Electronic Supplementary Material (ESI) for Biomaterials ScienceThis journal is © The Royal Society of Chemistry 2013

175:2278191:34891204:25123217:84524243:2711255:1556265:20443277:1706291:17837305:102375318:62555331:2035343:3419367:9473393:6970432:14511507:5971

Myristicacid(1TMS) 1854.69 117:44054129:24249132:20264145:13871241:5799285:100937 668 0.034

Palmiticacid(1TMS) 2052.42

117:585790129:3692021132:260821145:205161159:25873171:31125185:49981201:84924213:18944227:24392243:30506269:72432285:73660299:19092313:1631756328:107850

909 0.049

Putrescine(4TMS) 1768.02 86:1202174:9038214:1337 898 0.036

Stearicacid(1TMS) 2250.32

117:746752129:488822132:339142145:295247159:37266171:43868185:71437187:46035201:135664213:26047227:34289241:41993243:30664255:29425257:55098271:29057297:102427313:116169341:2175488356:197644

864 0.037

Tyrosine(3TMS) 1965.35 179:1170208:1215218:2164 321 0.017

Electronic Supplementary Material (ESI) for Biomaterials ScienceThis journal is © The Royal Society of Chemistry 2013

TableS2:MassspectralcharacteristicsofextracellularmetabolitesdetectedbyGC‐MSincludingRetentionIndex,CompoundSpectrum,ReverseMatchandcorrespondingp‐Value.AnalyteName RetentionIndex CompoundSpectrum ReverseMatch p‐Value

Asparagine(2TMS) 1613 100:2838116:6922130:3354141:884143:1551159:14421202:731218:1855244:1261276:639 772 0.023

Cystine(4TMS) 2299 116:1080130:694132:880146:4926218:6853232:1920339:1516 577 0.040

Glutamicacid(2TMS) 1541 84:41350130:2499158:12078174:33065186:6054201:1142276:4995 805 0.035

Isoleucine(2TMS) 1304100:36833102:10012114:8384128:11162130:8176158:824842170:8423218:170112232:47390260:11352

902 0.046

Lacticacid(2TMS) 106488:69917101:34425117:1097549129:17384131:74123133:142587150:15304190:277085191:343050203:13159219:115044

748 0.015

Leucine(2TMS) 1281100:37258102:47736116:16409128:14041130:20554142:14445158:1176453218:44260232:60912260:20511

896 0.037

Methionine(2TMS) 1533 128:46582160:3463176:110013219:11400250:7499293:10209 815 0.049

Ornithine(3TMS) 177486:3364100:2308114:739130:2024142:6456186:8417200:737216:1396244:3345245:896258:1099348:3324

870 0.033

Phenylalanine(2TMS) 164977:221591:17023100:29071103:4685117:3321133:7222160:4634192:160913218:225707266:16495294:4812

915 0.035

Proline(2TMS) 1308 100:5713133:6846142:548930216:33608 881 0.033Proline,4‐hydroxy(3TMS) 1543 100:4916133:9465140:69083188:3766214:3499

230:316816304:11296332:7925 916 0.002

Serine(3TMS) 1374100:60175103:10269116:19233133:25370174:7253188:36613204:449306218:258724278:31103306:17099

920 0.030

Electronic Supplementary Material (ESI) for Biomaterials ScienceThis journal is © The Royal Society of Chemistry 2013

Threonine(3TMS) 140286:6385101:55962117:114587160:4951174:3871186:3958191:4788203:19806218:20710219:187776230:3920291:81071320:12103

917 0.000

Tryptophan(3TMS) 2251 100:2507200:2764202:72715218:3513230:1591291:8903405:702 852 0.000

Tyrosine(3TMS) 1963 179:18743218:282450280:37313354:9939382:5104 875 0.003

Urea(2TMS) 1252 78:1361130:6343173:7633189:71272204:2879 532 0.020TableS3:Swellingdegree,bulkelasticityandsurfaceroughnessoftheinvestigatedPEG‐basedgels.Fortheswellingtests,gelswereweighedandimmersedincellculturemediumat37°Cfor24h.Threeindependentmeasurementswereperformed.BulkelasticityandsurfaceroughnessweremeasuredbyrheologyandAFM,respectively,asdescribedpreviouslyinKelleheretal.,2012.22 PEG‐basedgel

SwellingDegree

[%]

BulkElasticity

[MPa]

SurfaceRoughness

[nm]

PEG 293±25 0.44±0.05 1.37±0.27

3BC 9±2 1.20±0.03 1.03±0.47

8‐PEG 285±32 0.27±0.05 0.78±0.34

Electronic Supplementary Material (ESI) for Biomaterials ScienceThis journal is © The Royal Society of Chemistry 2013