Optimization of cryo‐XPS analyses for the study of thin films of a block copolymer (PS‐PEO)

The water‐induced surface reorganization of a thin film of a block copolymer [polystyrene‐b‐poly(ethylene oxide), PS‐PEO], was studied by cryogenic X‐ray photoelectron spectroscopy (cryo‐XPS). Experimental parameters were examined with a view to optimize the analysis. The absence of artifacts due to the low temperature of analysis was checked, and the influence of the procedure used for sample hydration before analysis was investigated. Adequate timing of the different steps of the analysis and temperature program was also established. With this optimized protocol, an important reorganization of the block copolymer was detected, showing more pronounced exposure of the PEO block at the outermost surface in hydrated compared to dry environment. As this type of polymer surface is prone to be used for biomedical applications, an accurate knowledge of the chemical composition of the outermost surface in aqueous environments is crucial. The development of this technique is therefore promising for related systems. Copyright © 2011 John Wiley & Sons, Ltd.

[1]  K. Shimizu,et al.  X-ray photoelectron spectroscopy of fast-frozen hematite colloids in aqueous solutions : 3. stabilization of ammonium species by surface (hydr)oxo groups , 2011 .

[2]  Marvin Y. Paik,et al.  NEXAFS Depth Profiling of Surface Segregation in Block Copolymer Thin Films , 2010 .

[3]  Martin Müller,et al.  Protein resistance of PNIPAAm brushes: application to switchable protein adsorption. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[4]  Tao Chen,et al.  Stimulus-responsive polymer brushes on surfaces: Transduction mechanisms and applications , 2010 .

[5]  A. Shchukarev Electrical double layer at the mineral-aqueous solution interface as probed by XPS with fast-frozen samples , 2010 .

[6]  C. Neto,et al.  On the Composition of the Top Layer of Microphase Separated Thin PS-PEO Films , 2009 .

[7]  Nicolas H Voelcker,et al.  Stimuli-responsive interfaces and systems for the control of protein-surface and cell-surface interactions. , 2009, Biomaterials.

[8]  D. Fischer,et al.  Surface Engineering of Styrene/PEGylated-Fluoroalkyl Styrene Block Copolymer Thin Films , 2009 .

[9]  J. Gardella,et al.  X-ray photoelectron spectroscopy studies of water-induced surface reorganization of amphiphilic poly(2-hydroxyethyl methacrylate-g-dimethylsiloxane) copolymers using cryogenic sample handling techniques , 2008 .

[10]  M. Genet,et al.  Analysis of the oil–water interface by XPS at low temperature , 2008 .

[11]  A. Shchukarev,et al.  XPS study of the hematite–aqueous solution interface , 2008 .

[12]  A. Shchukarev,et al.  XPS of Fast-Frozen Hematite Colloids in NaCl Aqueous Solutions: I. Evidence for the Formation of Multiple Layers of Hydrated Sodium and Chloride Ions Induced by the {001} Basal Plane , 2007 .

[13]  Yves F Dufrêne,et al.  Direct measurement of hydrophobic forces on cell surfaces using AFM. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[14]  S. Darling Directing the self-assembly of block copolymers , 2007 .

[15]  A. Shchukarev XPS at solid-aqueous solution interface. , 2006, Advances in colloid and interface science.

[16]  J. Cárdenas,et al.  The influence of temperature and X-ray dose on the deprotonation of lyophilized phenylalanine during X-ray photoelectron spectroscopy , 2006 .

[17]  J. Lüning,et al.  Surface Reorganization of an Amphiphilic Block Copolymer Film Studied by NEXAFS Spectroscopy , 2006 .

[18]  J. Genzer,et al.  Surface-grafted polymer gradients : Formation, characterization, and applications , 2006 .

[19]  J. Cárdenas,et al.  Lyophilized histidine investigated using X-ray photoelectron spectroscopy and cryogenics: Deprotonation in vacuum , 2005 .

[20]  W. Norde,et al.  BSA adsorption on bimodal PEO brushes. , 2005, Journal of colloid and interface science.

[21]  S. Sjöberg,et al.  XPS with fast-frozen samples: A renewed approach to study the real mineral/solution interface , 2005 .

[22]  P. Rouxhet,et al.  Surface morphology and wetting properties of surfaces coated with an amphiphilic diblock copolymer , 2005 .

[23]  A. Shchukarev,et al.  Chemical speciation of N‐(phosphonomethyl)glycine in solution and at mineral interfaces , 2004 .

[24]  Andrey Shchukarev,et al.  XPS study of the silica–water interface , 2004 .

[25]  J. Cárdenas,et al.  Investigation of the titaniumdioxide–aqueous solution interface using XPS and cryogenics , 2003 .

[26]  W. Norde,et al.  Tethered polymer chains: surface chemistry and their impact on colloidal and surface properties. , 2003, Advances in colloid and interface science.

[27]  Steven J. Sibener,et al.  Spontaneous Spatial Alignment of Polymer Cylindrical Nanodomains on Silicon Nitride Gratings , 2002 .

[28]  A. Shchukarev,et al.  Characterization of hydrous manganite (γ‐MnOOH) surfaces—an XPS study , 2002 .

[29]  M. Toselli,et al.  Investigation of the water-induced reorganization of polycaprolactone-poly(fluoroalkylene oxide)-polycaprolactone triblock copolymer films by angle-dependent X-ray photoelectron spectroscopy , 2002 .

[30]  G. Tulevski,et al.  Synthesis and surface analysis of siloxane-containing amphiphilic graft copolymers, poly(2-hydroxyethyl methacrylate-g-dimethylsiloxane) and poly(2,3-dihydroxypropyl methacrylate-g-dimethylsiloxane) , 2002 .

[31]  P. Green,et al.  Block copolymer thin films: Pattern formation and phase behavior , 2001 .

[32]  B. T. Pickup,et al.  XPS Studies of Chain Conformation in PEG, PTrMO, and PTMG Linear Polyethers , 2000 .

[33]  P. Bassereau,et al.  Phase Transitions in Monolayers of PS−PEO Copolymer at the Air−Water Interface , 1999 .

[34]  S. Seal,et al.  Cryogenic stabilization of high vapor pressure samples for surface analysis under ultrahigh vacuum conditions , 1999 .

[35]  M. Sefton,et al.  An XPS Study of the Surface Reorientation of Statistical Methacrylate Copolymers , 1995 .

[36]  Joseph D. Andrade,et al.  Blood compatibility of polyethylene oxide surfaces , 1995 .

[37]  D. Castner,et al.  Advances in X-ray photoelectron spectroscopy instrumentation and methodology: instrument evaluation and new techniques with special reference to biomedical studies , 1994 .

[38]  B. Ratner,et al.  Observation of Surface Rearrangement of Polymers Using ESCA , 1993 .

[39]  R. A. Cayless,et al.  The SPLINT technique for sample preservation using liquid nitrogen transfer , 1993 .

[40]  A. Chilkoti,et al.  X-ray photoelectron spectroscopy of iodine-doped nonconjugated polymers , 1993 .

[41]  D. Briggs,et al.  High Resolution XPS of Organic Polymers: The Scienta ESCA300 Database , 1992 .

[42]  B. Ratner,et al.  Analysis of the organization of protein films on solid surfaces by ESCA , 1981 .

[43]  H. R. Thomas,et al.  Surface Studies on Multicomponent Polymer Systems by X-ray Photoelectron Spectroscopy. Polystyrene/Poly(ethylene oxide) Diblock Copolymers , 1979 .

[44]  A. Hoffman,et al.  Radiation‐grafted hydrogels for biomaterial applications as studied by the ESCA technique , 1978 .

[45]  E. Fluck,et al.  X-ray-photoelectron spectroscopy (ESCA) investigations in coordination chemistry, I. Solvation of SbCl5 studied in quick-frozen solutions , 1974 .

[46]  P. F. Onyon Polymer Handbook , 1972, Nature.