FTIR studies of polyimides. II. Factors affecting quantitative measurement

Measurement of imidization by IR spectroscopy has frequently been reported to give results that are either insensitive to changes in the latter part of the cure or in conflict with observations by other methods. However, an analysis of imide formation using the 1370 cm^?1 band (C? N stretch) in conjunction with the 1500 cm^?1 aromatic band as an internal standard appears capable of giving precise, internally consistent measurements for the most commonly used polyimide structures, for samples that are measured in transmission. Measurements of imide content in ultrathin films by grazing incidence reflection spectroscopy appear to be at least semiquantitative. © 1993 John Wiley & Sons, Inc.     

Styrene‐butadiene copolymers with different butadiene microstructure: Mechanical,swelling, and orientational properties

Results of equilibrium stress‐strain and swelling experiments are reported for styrene‐butadiene copolymers of varying butadiene microstructure. The orientation of polymer chains was investigated under uniaxial elongation by birefringence and infrared dichroism spectroscopies which probe orientation on a segmental scale. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2449–2456, 2000     

The Use of a Low‐Molar‐Mass Self‐Assembled Template to Direct the Crystallisation of Poly(ε‐caprolactone)

Summary: We show that small quantities of dibenzylidene sorbitol dispersed in poly(ε‐caprolactone) provide a self‐assembling nanoscale framework to yield high levels of crystal orientation. During modest shear flow of the melt, the additive forms highly extended nanoparticles which adopt a preferred alignment with respect to the flow field and, on cooling, polymer crystallisation is directed by these particles. We speculate that atomistic level epitaxy is unlikely to be the only directing influence.

SAXS pattern of PCL/DBS in the melt at 80 °C and subjected to a shear flow of 10 s⁻¹ for 1 000 shear units. The flow direction is vertical.     

The matching of electrostatic extrema: A useful method in drug design? A study of phosphodiesterase III inhibitors

Summary Ligands which bind to a specific protein binding site are often expected to have a similar electrostatic environment which complements that of the binding site. One method of assessing molecular electrostatic similarity is to examine the possible overlay of the maxima and minima in the electrostatic potential outside the molecules and thereby match the regions where strong electrostatic interactions, including hydrogen bonds, with the residues of the binding site may be possible. This approach is validated with accurate calculations of the electrostatic potential, derived from a distributed multipole analysis of an ab initio charge density of the molecule, so that the effects of lone pair and -electron density are correctly included. We have applied this method to the phosphodiesterase (PDE) III substrate adenosine-3,5-cyclic monophosphate (cAMP) and a range of nonspecific and specific PDE III inhibitors. Despite the structural variation between cAMP and the inhibitors, it is possible to match three or four extrema to produce relative orientations in which the inhibitors are sufficiently sterically and electrostatically similar to the natural substrate to account for their affinity for PDE III. This matching of extrema is more apparent using the accurate electrostatic models than it was when this approach was first applied, using semiempirical point charge models. These results reinforce the hypothesis of electrostatic similarity and give weight to the technique of extrema matching as a useful tool in drug design.     

Physicochemical aspects of microbial adhesion — Influence of antibody adsorption on the deposition ofStreptococcus sobrinus in a parallel-plate flow chamber

Deposition of the oral bacteriumStreptococcus sobrinus HG977 onto glass (water contact angle 0°) and onto FEP-Teflon (fluoroethylenepropylene; water contact angle 110°) was studied in a parallel-plate flow chamber in the presence and absence of polyclonal antibodies (pAb) and monoclonal antibodies (mAbs) adsorbed onto the cells. The zeta potentials of the bacteria ranged from −7.1 to −8.5 mV at pH 6.8 and were not affected by the presence of pAb or mAbs. Hydrophobicity (by water contact angles) increased from 30° (no antibodies) to 88° in the presence of pAb adsorbed onto the bacterial cell surface. The untreatedS. sobrinus had a greater tendency to adhere to glass (44.5 × 10⁶ cm⁻²) than to FEP-Teflon (18.3 × 10⁶ cm⁻²), in accordance with thermodynamic modelling. After preincubation ofS. sobrinus with pAb, its clear preference for adhesion to glass disappeared as expected from its increased hydrophobicity. Although forS. sobrinus preincubated with OMVU10 no difference was found in hydrophobicity in comparison to the untreated bacteria, the number of bacteria adhering to glass decreased to 10.2 ¢ 10⁶ cm⁻². Formation of bacterial aggregates was found whenS. sobrinus, preincubated with pAb or OMVU10, adhered to glass and FEP. This was also observed when untreated bacteria adhered to glass coated with OMVU10, or to FEP coaled with OMVU10 or pAb. Adhesion in these experiments is therefore thought to occur via near-neighbour collection induced by the presence of pAb or mAbs. Low numbers of bacteria were removed from glass after draining the flow cell, whereas high numbers of untreated bacteria and bacteria preincubated with OMVU10 were removed from FEP.S. sobrinus cells preincubated with pAb were not removed but piled up. It was concluded that the adhesion of untreatedS. sobrinus andS. sobrinus preincubated with pAb is in accordance with thermodynamic modelling, based on the overall wettability of the cell surfaces, whereas the adhesion ofS. sobrinus preincubated with OMVU10 may be through localized interactions, not expressed in overall surface properties.     

电沉积条件对锌镀层织构的影响

采用ＸＲＤ方法研究添加剂，络合剂，以及电流密度对锌酸盐镀锌层的织构和晶粒尺寸的影响，结果表明，添加剂ＡＡ－１的存在有利于（１０１）晶面取向；而ＤＩＥ则使镀层转变为１１０择优；两种添加剂同时存在下，可在一定的电流密度范围内获得高择优取向的锌镀层，而当又有络合剂ＴＥＡ和ＥＤＴＡ同时存在时，则可在更宽广的电流密度范围内制得日 粒细密、表面光亮、择优系数ＴＣ（１１０）在９８５以上的高择优取向锌沉积层。     

Simple approach to study biomolecule adsorption in polymeric microfluidic channels

Herein a simple analytical method is presented for the characterization of biomolecule adsorption on cyclo olefin polymer (COP, trade name: Zeonor^®) substrates which are widely used in microfluidic lab-on-a-chip devices. These Zeonor^® substrates do not possess native functional groups for specific reactions with biomolecules. Therefore, depending on the application, such substrates must be functionalized by surface chemistry methods to either enhance or suppress biomolecular adsorption. This work demonstrates a microfluidic method for evaluating the adsorption of antibodies and oligonucleotides surfaces. The method uses centrifugal microfluidic flow-through chips and can easily be implemented using common equipment such as a spin coater. The working principle is very simple. The user adds 40 L of the solution containing the sample to the starting side of a microfluidic channel, where it is moved through by centrifugal force. Some molecules are adsorbed in the channel. The sample is then collected at the other end in a small reservoir and the biomolecule concentration is measured. As a pilot application, we characterized the adsorption of goat anti-human IgG and a 20-mer DNA on Zeonor^®, and on three types of functionalized Zeonor: 3-aminopropyltriethoxysilane (APTES) modified surface with mainly positive charge, negatively charged surface with immobilized bovine serum albumin (BSA), and neutral, hydrogel-like film with polyethylene glycol (PEG) characteristics. This simple analytical approach adds to the fundamental understanding of the interaction forces in real, microfluidic systems. This method provides a straightforward and rapid way to screen surface compositions and chemistry, and relate these to their effects on the sensitivity and resistance to non-specific binding of bioassays using them. In an additional set of experiments, the surface area of the channels in this universal microfluidic chip was increased by precision milling of microscale trenches. This modified surface was then coated with APTES and tested for its potential to serve as a unique protein dilution feature.     

Local environment influence on the optical properties of block copolymers containing an epoxy-based azo-prepolymer

The aim of this contribution was the study of the influence of polymer matrix on the photo-induced orientation of azobenzene groups. Notably, an azo-prepolymer bearing hydroxyl groups was selectively confined in self-assembled phases of different block copolymers, randomly-epoxidized polystyrene-b-polybutadiene-b-polystyrene (SBSep) and polystyrene-b-poly-4-vinylpyridine (S4VP). The formation of hydrogen bonds between the azo-prepolymer and poly-4-vinylpyridine block, as well as the effect of the local environment surrounding the azo-prepolymer were investigated by Fourier transform infrared and ultraviolet–visible spectroscopies. In addition, the reversible optical storage properties of the developed materials were also studied. Birefringent properties of the systems based on S4VP were strongly enhanced by intermolecular interactions with the azo-prepolymer. Specifically, the maximum birefringence level attained by a system containing 13 wt% of azobenzene was around 2.3 × 10⁻² and its remaining birefringence was nearly three times higher than that of the neat azo-prepolymer. Furthermore, a morphological analysis of the designed materials was carried out by atomic force microscopy. Taking into account that the control of the microdomains ordering in block copolymer films is of current interest, special attention was focused on the influence of different variables on the arrangement of the block copolymer microdomains.     

Practical Study into Enhancing IgG Immobilisation on Screen-Printed Electrodes for Environmental Applications

This work is focused on the influence of pH and applied potential for the immobilisation of rabbit IgG on a carbon screen-printed electrode. The orientation of IgG molecule at the surface is fundamental for activity and reproducibility of the immunosensor. As the electrode potential is increased a particular order may be brought to the immobilised antibodies, i.e. the antibodies adapt a more favourable arrangement on the surface to facilitate better binding. The response increased when changing the pH from basic to acidic medium and the reverse trend was observed for the limit of detection (LOD). When a potential was applied to the electrode, the response generally decreased and the LOD increased in the order acidic > basic > neutral pH. The LODs obtained from antibodies immobilised at acidic pH and + 100 mV were better than the LODs obtained at other conditions.