Hydrophobic pocket modification and humanized catalytic antibodies with glutathione peroxidase activity (I) - Preparation and characterization of haptenes and conjugates

The thiol group of glutathione (GSH) was protected by 2,4-dinitrochlorobenzene (DNCB), the product S-substituted dinitrophenyl GSH(GSH-S-DNP) was alcoholized to obtain haptenes 4 and 5 respectively. As haptenes, the two GSH derivatives were characterized by means of H-1 NMR, MALDI-TOF-MS and IR, followed by individually coupling with bovine serum albumin (BSA) via glutaraldehyde. BSB-Hp4 and BSA-Hp5 were purified by Sephadex G-25 gel filtration chromatography. For each conjugate, the average haptene-BSA ratio was 12 : 1. The electrophoresis analysis showed that the average molecular weight of each conjugate was 76 500. The CD spectrum indicated that the conjugates had more a-helix content than BSA did.

Electrochemical study of interactions between DNA and viologen-thiol self-assembled monolayers

We investigated the binding characteristics of double-stranded DNA to self-assembled monolayers (SAMs) containing viologen groups formed on the surface of gold electrodes via Au-S bonds. The positive charged and hydrophobic surfaces of the viologen SAMs modified gold electrodes are suitable to bind strongly dth DNA, whose interactions to solution DNA and adsorbed DNA both lead to positive shifts (22.5 mV and 65 mV, respectively) in the first redox potential ci viologen centers, indicating that the main interaction is from a hydrophobic interaction. Meanwhile, the binding of DNA strongly affects the kinetics of electron transfer of the viologen group so that the separation of anodic and cathodic peak potentials becomes larger and the heterogeneous electron transfer constant becomes smaller.

STRUCTURE-PROPERTY RELATIONSHIP BETWEEN HALF-WAVE POTENTIALS OF ORGANIC-COMPOUNDS AND THEIR TOPOLOGY

A significant correlation was found between half-wave potentials of organic compounds and their topological indices, A(x1), A(x2), and A(x3). The simplicity of calculation of the index from the connectivity in the molecular skeleton, together with the significant correlation, indicates its practical value. Good results have been obtained by using them to predict the half-wave potentials of some organic compounds.

EFFECT OF HYDROPHOBIC OXIDES ON RADIATION CROSS-LINKING OF LOW-DENSITY POLYETHYLENE

Effect of hydrophobic oxide, containing =Si-CH=CH2 groups, on the radiation crosslinking of low density polyethylene (LDPE) has been studied. It was found that mechanical stability of irradiated LDPE containing improved SiO2 is higher than that of samples containing unimproved SiO2.

PLASMA POLYMERIZATION OF OCTAFLUOROCYCLOBUTANE AND HYDROPHOBIC MICROPOROUS COMPOSITE MEMBRANES FOR MEMBRANE DISTILLATION

In this paper, hydrophilic microporous cellulose nitrate membranes have been surface-modified by plasma polymerization of octafluorocyclobutane (OFCB). The microporous composite membranes with a hydrophilic layer sandwiched between two hydrophobic layers have been obtained. The obtained composite membranes have been used in a membrane distillation (MD) process and have exhibited good performance. The effects of polymerization conditions, such as glow-discharge power and deposition time, on the structures and MD performances of the obtained composite membranes have been investigated by SEM, X-ray microscopical analysis, and XPS. The polymerization conditions should be as mild as possible in order to prepare the hydrophobic composite membrane with good MD performance. The typical MD behaviors of the obtained hydrophobic composite membranes are in agreement with that of hydrophobic membranes directly prepared from hydrophobic polymeric materials, like PVDF, PTFE, or PP.

STUDY ON DEPOSITION POTENTIALS OF LITHIUM AND SODIUM-IONS AND DEPOLARIZATION IN BINARY CHLORIDE

Deposition potentials of Lithium and Sodium ions have been measured in binary chloride systems (LiCl-KCl, NaCl-KCl) by I-V curve method, to provide a theoretical base for preparing high purity Al-Li alloy by electrolysis in molten salt. The changes of free energy and enthalpy were calculated in terms of depolarization values on Al cathode. Thermodynamic meaning of depolarization was discussed in details and the empirical relation between binary alloy type and depolarization type was proposed. It is shown for the first time that the presence of a third element in Al-Li alloy can strengthen depolarization of Li ion at Al alloy cathode and give foundation for preparing high purity Al-Li-M ternary alloy. The effect of LiCl concentration on deposition potentials of Li ion at Al cathode in KCl-LiCl melt was studied and average active coefficient of LiCl was obtained.

Removal of endotoxin from human serum albumin solutions by hydrophobic and cationic charged membrane

A novel matrix of macropore cellulose membrane was prepared by chemical graft, and immobilized the cationic charged groups as affinity ligands. The prepared membrane Fan be used for the removal of endotoxin from human serum albumin (HSA) solutions. With a cartridge of 20 sheets affinity membrane of 47 mm diameter, the endotoxin level in HSA solution can be reduced ro 0.027 eu/mL. Recovery of HSA was over 95%.

Influence of methanol on retention of hydrophobic organic chemicals in soil leaching column chromatography

The influence of methanol in methanol-water mixed eluents on the capacity factor (P), an important parameter which could depict leaching potential of hydrophobic organic chemicals (HOCs) in soil leaching column chromatography (SLCC), was investigated. Two reference soils, GSE 17201 obtained from Bayer Landwirtschaftszentrum, Monheim, Germany and SP 14696 from LUFA, Spencer, Germany, were used as packing materials in soil columns, and isocratic elution with methanol-water mixtures at different volume fractions of methanol (phi) were tested. Shortterm exposure of the column (packed with the GSE 17201 soil) to the eluents increased solute retention by a certain (23% log-unit) degree evaluated through a correlation with the retention on the same soil column but unpreconditioned by methanol-containing eluents. Long-term exposure of soil columns to the eluents did not influence the solute retention. A log-linear equation, log k' = log k'(w) - Sphi, could well and generally describe the retention of HOCs in SLCC. For the compounds of homologous series, logk'(w), had good linear relationship with S, indicating the hydrophobic partition mechanism existing in the retention process. (C) 2002 Elsevier Science Ltd. All rights reserved.

Linear solvation energy relationships regarding sorption and retention properties of hydrophobic organic compounds in soil leaching column chromatography

The capacity factors of a series of hydrophobic organic compounds (HOCs) were measured in soil leaching column chromatography (SLCC) on a soil column, and in reversed-phase liquid chromatography on a C-18 column with different volumetric fractions (phi) of methanol in methanol-water mixtures. A general equation of linear solvation energy relationships, log(XYZ) = XYZ(0) + mV(1)/100 + spi* + bbeta(m) + aalpha(m), was applied to analyze capacity factors (k'), soil organic partition coefficients (K-oc) and octanol-water partition coefficients (P). The analyses exhibited high accuracy. The chief solute factors that control log K-oc, log P, and log k' (on soil and on C-18) are the solute size (V-1/100) and hydrogen-bond basicity (beta(m)). Less important solute factors are the dipolarity/polarizability (pi*) and hydrogen-bond acidity (alpha(m)). Log k' on soil and log K-oc have similar signs in four fitting coefficients (m, s, b and a) and similar ratios (m:s:b:a), while log k' on C-18 and log P have similar signs in coefficients (m, s, b and a) and similar ratios (m:s:b:a). Consequently, log k' values on C-18 have good correlations with log P (r > 0.97), while log k' values on soil have good correlations with log K-oc (r > 0.98). Two K-oc estimation methods were developed, one through solute solvatochromic parameters, and the other through correlations with k' on soil. For HOCs, a linear relationship between logarithmic capacity factor and methanol composition in methanol-water mixtures could also be derived in SLCC. (C) 2002 Elsevier Science Ltd. All rights reserved.

Retention behavior of hydrophobic organic chemicals as a function of temperature in soil leaching column chromatography

To study the transport mechanism of hydrophobic organic chemicals (HOCs) and the energy change in soil/solvent system, a soil leaching column chromatographic (SLCC) experiment at an environmental temperature range of 20-40 degreesC was carried out, which utilized a reference soil (SP 14696) packed column and a methanol-water (1:4 by volume ratio) eluent. The transport process quickens with the increase of column temperature. The ratio of retention factors at 30 and 40 degreesC (k'(30)/k'(40)) ranged from 1.08 to 1.36. The lower enthalpy change of the solute transfer in SLCC (from eluent to soil) than in conventional reversed-phase liquid chromatography (e.g., from eluent to C-18) is consistent with the hypothesis that HOCs were dominantly and physically partitioned between solvent and soil. The results were also verified by the linear solvation energy relationships analysis. The chief factor controlling the retention was found to be the solute solvophobic partition, and the second important factor was the solute hydrogen-bond basicity, while the least important factors were the solute polarizability-dipolarity and hydrogen-bond acidity. With the increase of temperature, the contributions of the solute solvophobic partition and hydrogen-bond basicity gradually decrease, and the latter decreases faster than the former. (C) 2002 Elsevier Science Ltd. All rights reserved.

Aqueous solutions of HEC and hmHEC: effects of molecular mass versus hydrophobic associations on hydrodynamic and thermodynamic parameters.

Aqueous solutions of amphiphilic polymers usually comprise of inter- and intramolecular associations of hydrophobic groups often leading to a formation of a rheologically significant reversible network at low concentrations that can be identified using techniques such as static light scattering and rheometry. However, in most studies published till date comparing water soluble polymers with their respective amphiphilic derivatives, it has been very difficult to distinguish between the effects of molecular mass versus hydrophobic associations on hydrodynamic (intrinsic viscosity [g]) and thermodynamic parameters (second virial coefficient A2), owing to the differences between their degrees of polymerization. This study focuses on the dilute and semi-dilute solutions of hydroxyethyl cellulose (HEC) and its amphiphilic derivatives (hmHEC) of the same molecular mass, along with other samples having a different molecular mass using capillary viscometry, rheometry and static light scattering. The weight average molecular masses (MW) and their distributions for the nonassociative HEC were determined using size exclusion chromatography. Various empirical approaches developed by past authors to determine [g] from dilute solution viscometry data have been discussed. hmHEC with a sufficiently high degree of hydrophobic modification was found to be forming a rheologically significant network in dilute solutions at very low concentrations as opposed to the hmHEC with a much lower degree of hydrophobic modification which also enveloped the hydrophobic groups inside the supramolecular cluster as shown by their [g] and A2. The ratio A2MW/[g], which takes into account hydrodynamic as well as thermodynamic parameters, was observed to be less for associative polymers compared to that of the non-associative polymers.

Large Decrease of Fluctuations for Supercooled Water in Hydrophobic Nanoconfinement

Using Monte Carlo simulations we study a coarse­grained model of a water layer confined in a fixed disordered matrix of hydrophobic nanoparticles at different particle concentrations c. For c = 0 we find a 1st order liquid­liquid phase transition (LLPT) ending in one critical point at low pressure P. For c > 0 our simulations are consistent with a LLPT line ending in two critical points at low and high pressure. For c = 25% at high P and low temperature T we find a dramatic decrease of compressibility, thermal expansion coefficient, and specific heat. Surprisingly, the effect is present also for c as low as 2.4%. We conclude that even a small presence of nanoscopic hydrophobes can drastically suppress thermodynamic fluctuations, making the detection of the LLPT more difficult.

An Integrated Neural Network-Event-Related Potentials Model of Temporal and Probability Context Effects on Event Categorization

We present a neural network that adapts and integrates several preexisting or new modules to categorize events in short term memory (STM), encode temporal order in working memory, evaluate timing and probability context in medium and long term memory. The model shows how processed contextual information modulates event recognition and categorization, focal attention and incentive motivation. The model is based on a compendium of Event Related Potentials (ERPs) and behavioral results either collected by the authors or compiled from the classical ERP literature. Its hallmark is, at the functional level, the interplay of memory registers endowed with widely different dynamical ranges, and at the structural level, the attempt to relate the different modules to known anatomical structures.

Bridge-vehicle interaction for structural health monitoring: potentials, applications, and limitations

Structural Health Monitoring (SHM) is an integral part of infrastructure maintenance and management systems due to socio-economic, safety and security reasons. The behaviour of a structure under vibration depends on structure characteristics. The change of structure characteristics may suggest the change in system behaviour due to the presence of damage(s) within. Therefore the consistent, output signal guided, and system dependable markers would be convenient tool for the online monitoring, the maintenance, rehabilitation strategies, and optimized decision making policies as required by the engineers, owners, managers, and the users from both safety and serviceability aspects. SHM has a very significant advantage over traditional investigations where tangible and intangible costs of a very high degree are often incurred due to the disruption of service. Additionally, SHM through bridge-vehicle interaction opens up opportunities for continuous tracking of the condition of the structure. Research in this area is still in initial stage and is extremely promising. This PhD focuses on using bridge-vehicle interaction response for SHM of damaged or deteriorating bridges to monitor or assess them under operating conditions. In the present study, a number of damage detection markers have been investigated and proposed in order to identify the existence, location, and the extent of an open crack in the structure. The theoretical and experimental investigation has been conducted on Single Degree of Freedom linear system, simply supported beams. The novel Delay Vector Variance (DVV) methodology has been employed for characterization of structural behaviour by time-domain response analysis. Also, the analysis of responses of actual bridges using DVV method has been for the first time employed for this kind of investigation.