An in situ FTIR-ATR study of polyacrylate adsorbed onto hematite at high pH and high ionic strength

FTIR-ATR was used to examine in situ the interaction of polyacrylate and hematite at pH 13. Static light scattering and mobility measurements were used to assess solution polyacrylate dimensions and hematite surface charge, respectively. Polyacrylate adsorption occurred only with the addition of electrolyte (e.g., NaCl), and it was found that excess cations, up to approximately 1 M, facilitated adsorption, above which the effect was found to plateau. At pH 13 and at low ionic strength, adsorption of polyacrylate onto hematite is facilitated by cations in solution shielding both the negative acrylate functionality of the polymer and the negative hematite surface. The shielding of the hematite surface continues to increase with increasing salt concentration up to a measured 3 M. Similarly, the shielding of the polymer increased with electrolyte concentration up to approximately 1 M salt, beyond which no further increase in shielding was observed. At this concentration the polymer assumes a finite minimum size in solution that ultimately limits the amount adsorbed. The dimension of the polymer in solution was found to be independent of monovalent cation type. Thus, at high pH and high ionic strength adsorption is determined by the degree of hematite surface charge reduction. The cation-hematite surface interaction was found to be specific, with lithium leading to greater polyacrylate adsorption than sodium, which was followed by cesium. The stronger affinity of lithium for the hematite surface over sodium and cesium is indicative of the inverse lyotropic adsorption series and has been rationalized in the past by the "structure-making-structure-breaking" model. These results provide a useful insight into the likely adsorption mechanism for polyacrylate flocculants at high pH and ionic strength onto residues in the Bayer processing of bauxite.     

Development of polyphosphate parameters for use with the AMBER force field

Accurate force fields are essential for reproducing the conformational and dynamic behavior of condensed-phase systems. The popular AMBER force field has parameters for monophosphates, but they do not extend well to polyphorylated molecules such as ADP and ATP. This work presents parameters for the partial charges, atom types, bond angles, and torsions in simple polyphosphorylated compounds. The parameters are based on molecular orbital calculations of methyldiphosphate and methyltriphosphate at the RHF/6-31+G* level. The new parameters were fit to the entire potential energy surface (not just minima) with an RMSD of 0.62 kcal/mol. This is exceptional agreement and a significant improvement over the current parameters that produce a potential surface with an RMSD of 7.8 kcal/mol to that of the ab initio calculations. Testing has shown that the parameters are transferable and capable of reproducing the gas-phase conformations of inorganic diphosphate and triphosphate. Also, the parameters are an improvement over existing parameters in the condensed phase as shown by minimizations of ATP bound in several proteins. These parameters are intended for use with the existing AMBER 94/99 force field, and they will permit users to apply AMBER to a wider variety of important enzymatic systems.     

Photoemission studies of polythiophene and polyphenyl films produced via surface polymerization by ion-assisted deposition

Conducting polymer films are grown by mass-selected, hyperthermal thiophene ions coincident on a surface with a thermal beam of organic monomers of either alpha-terthiophene (3T) or p-terphenyl (3P) neutrals. Mass spectrometry and X-ray photoelectron spectroscopy previously verified polymerization of both 3T and 3P by 200 eV C(4)H(4)S(+) during surface polymerization by ion-assisted deposition (SPIAD). The electronic structure of these films are probed here by ultraviolet photoelectron spectroscopy (UPS) and polarized near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and compared with similar spectra of evaporated films. The conducting polymer films formed by SPIAD display new valence band features resulting from a reduction in both their band gap and barrier to hole injection, which are calculated from the occupied and unoccupied valence band states measured by UPS and NEXAFS. These changes in film electronic structure result from an increase in the electron conjugation length and other changes in film structure induced by SPIAD.     

The synthesis, characterisation, phase behaviour and swelling of temperature sensitive physically crosslinked poly(1-vinyl-2-pyrrolidinone)/poly(N-isopropylacrylamide) hydrogels

Physically crosslinked complexes of polyvinyl pyrrolidinone-poly (N-isopropylacrylamide) (PVP-PNIPAAm) were prepared by photopolymerisation from a mixture of the monomers 1-vinyl-2-pyrrolidinone and N-isopropylacrylamide. IR spectroscopy and calorimetry were used to characterise the resulting xerogels. By alternating the monomer feed ratio, copolymers were synthesised to have their own distinctive lower critical solution temperature (LCST). The transition temperature of the gels was established using cloud point measurement and modulated differential scanning calorimeter (MDSC). This ability to shift the phase transition temperature of the copolymers provides excellent flexibility in tailoring transitions for specific uses. Swelling experiments were performed on the copolymer disks in distilled water at varying temperatures to establish the behaviour of the gels above and below phase transition temperature. The results obtained show that below transition temperature, the gels are water soluble but above this temperature they are slightly less water soluble; significantly less water soluble; or water insoluble; depending on the composition and LCST of the gel.     

光纤光栅原油压力传感器实验及其可靠性研究

介绍并制作了一种光纤光栅高温高压传感器,它由三种金属管组成,中央的弹性金属管将液体的压力转换为管子的机械伸长,周围金属管的长度只随温度变化。光纤光栅的两端分别固定在中央管及周围管的末端,随着压力管内液体压力的增加,光栅的中心波长随之增加,实现了对液压的传感。对该传感器的温度补偿进行了分析,设计了具有相同温度系数的压力传感光栅与温度传感光栅。并对传感器进行了高压实验和高温、高湿存储实验。结果表明,这种压力传感器在0~50 MPa之间灵敏度为31.7 pm/MPa。经过200℃高温存储16 h,及100℃沸水浸泡6 h,波长没有观察到明显衰退现象。     

Photopolymerization of thiol‐ene systems based on oligomeric thiols

Thiol oligomers were copolymerized with a triallyl ether by a photoinduced polymerization process. These oligomeric thiol‐ene systems comprise the same components as a photopolymerized thiol‐ene‐acrylate ternary system, yet the photopolymerized networks have much lower glass transition temperatures. An investigation into the effect of oligomeric thiol design on network formation was conducted by analyzing the reaction kinetics and thermal/mechanical properties of the thiol‐ene networks. Real‐time FTIR analysis shows that total conversion is >90% for all thiols investigated. Photo‐DSC analysis shows that the maximum exotherm rate is roughly equivalent for all of the thiols when the equivalent weight of the thiol is taken into account. As would be expected, the glass transition temperature and tensile strength increase with thiol functionality and lower thiol equivalent weight for thiols with functionality from 2 to 4. Films made using the oligomeric thiols have essentially the same glass transition temperatures and tensile modulus values regardless of thiol design. These results distinguish the method for generation of networks consisting of an initial Michael reaction of thiols and acrylates followed by a photoinitiated copolymerization with a multifunctional ene from the traditional photolysis of the corresponding thiol‐ene‐acrylate ternary systems with no Michael reaction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 14–24, 2009     

Transient Heat Measurements: A Transducer Model

Although often neglected in bioinstrumentation courses, direct calorimetry has important biomedical, biophysical, and clinical implications. Since direct calorimeters are usually considered somewhat esoteric, a simplified analysis of their design and operation is useful. Therefore, an electrical analog of the thermopile lattice common to most direct calorimeters was developed. This model can be used to derive the transfer function of the direct calorimeter, and through digital computer simulation, can aid in the design of specialized instruments. Engineering students can readily understand and use this model making the study of direct calorimetry practical in a teaching context.