Effects of dissolved organic matter surrogates on the partitioning of 17beta-estradiol and p-nonylphenol between synthetic membrane vesicles and water

Partition coefficients of two estrogenic compounds, 17beta-estradiol (E2) and p-nonylphenol (NP), between synthetic membrane vesicles (K'lipw values) and water were determined using equilibrium dialysis to evaluate the potential biological uptake of these compounds with and without the presence of dissolved natural organic matter (DOM) surrogates, Suwannee River fulvic acid, dialyzed Aldrich humic acid, and polyphenolic tannic acid. Overall, K'lipw values for E2 and NP reduced by 20-30% with the increase of DOM concentration from 0 to approximately 4 mg of C/L, a typical DOM concentration in the aquatic environment. This trend for E2 and NP is similar to that obtained by other researchers for moderately hydrophobic compounds including polycyclic aromatic hydrocarbons with three or four rings. A three-phase compartment model with three independent interactions, the sorption of E2 or NP by DOM surrogate (Koc), the sorption of DOM surrogates by membrane vesicles (KlipDOM), and the partition of E2 or NP by membrane vesicles (Klipw), was proposed, and K'lipw values for E2 or NP in the presence of DOM were calculated. The model predicted the decrease in Klipw values with the increase of DOM concentration, and the predictions using the three linear interactions agreed satisfactorily with the experimental results at relatively lower concentration of DOM.     

A Method for Systematic Assessment of Intrinsically Disordered Protein Regions by NMR

Intrinsically disordered proteins (IDPs) that lack stable conformations and are highly flexible have attracted the attention of biologists. Therefore, the development of a systematic method to identify polypeptide regions that are unstructured in solution is important. We have designed an “indirect/reflected” detection system for evaluating the physicochemical properties of IDPs using nuclear magnetic resonance (NMR). This approach employs a “chimeric membrane protein”-based method using the thermostable membrane protein PH0471. This protein contains two domains, a transmembrane helical region and a C-terminal OB (oligonucleotide/oligosaccharide binding)-fold domain (named NfeDC domain), connected by a flexible linker. NMR signals of the OB-fold domain of detergent-solubilized PH0471 are observed because of the flexibility of the linker region. In this study, the linker region was substituted with target IDPs. Fifty-three candidates were selected using the prediction tool POODLE and 35 expression vectors were constructed. Subsequently, we obtained ¹⁵N-labeled chimeric PH0471 proteins with 25 IDPs as linkers. The NMR spectra allowed us to classify IDPs into three categories: flexible, moderately flexible, and inflexible. The inflexible IDPs contain membrane-associating or aggregation-prone sequences. This is the first attempt to use an indirect/reflected NMR method to evaluate IDPs and can verify the predictions derived from our computational tools.     

Multifunctional Initiator with Platinum-Acetylide Dendritic Core for Living Polymerization of Isocyanides

A novel multifunctional initiator has been developed by peripheral modification of a Pt-acetylide dendrimer. Pd–Pt μ-ethynediyl units were introduced to the first-generation dendrimer by a divergent method. The dendritic initiator was applicable to the living polymerization of aryl isocyanides, producing high molecular weight polymers with a narrow polydispersity index in quantitative yields. The ³¹P NMR spectrum of the resulting polymer suggested that all Pd–Pt μ-ethynediyl units in the dendritic molecule actually functioned as an initiator.     

Avalanche breakdown voltage of GaAs hyperabrupt junctions

The avalanche breakdown voltage of a GaAs hyperabrupt junction diode is calculated by using unequal ionization rates for electrons and holes, and shown graphically as a function of the parameters which characterize the impurity profile of the diode. The breakdown voltage decreases abruptly at the critical point of the characteristic length L_c which varies in accordance with the impurity concentration N₀ at X = 0. For example, the critical length L_c is 7.7 × 10⁻⁶ cm and 3.3 × 10⁻⁵ cm for N₀ = 1 × 10¹⁸ cm⁻³ and 1 × 10¹⁷ cm⁻³, respectively. The breakdown voltage of a diode with extremely short or long characteristic length can be estimated from the results for corresponding abrupt junctions. The experimental results agree well with the calculated ones.     

Electrical characterization of poly(amide-imide) for application in organic field effect devices

The admittance spectra and current–voltage (I–V) characteristics are reported of metal–insulator–metal (MIM) and metal–insulator–semiconductor (MIS) capacitors employing cross-linked poly(amide–imide) (c-PAI) as the insulator and poly(3-hexylthiophene) (P3HT) as the active semiconductor. The capacitance of the MIM devices are constant in the frequency range from 10 Hz to 100 kHz, with tan δ values as low as 7 × 10⁻³ over most of the range. Except at the lowest voltages, the I–V characteristics are well-described by the Schottky equation for thermal emission of electrons from the electrodes into the insulator. The admittance spectra of the MIS devices displayed a classic Maxwell–Wagner frequency response from which the transverse bulk hole mobility was estimated to be ∼2 × 10⁻⁵ cm² V⁻¹s⁻¹ or ∼5 × 10⁻⁸ cm² V⁻¹s⁻¹ depending on whether or not the surface of the insulator had been treated with hexamethyldisilazane (HMDS) prior to deposition of the P3HT. From the maximum loss observed in admittance-voltage plots, the interface trap density was estimated to be ∼5 × 10¹⁰ cm⁻² eV⁻¹ or ∼9 × 10¹⁰ cm⁻² eV⁻¹ again depending whether or not the insulator was treated with HMDS. We conclude, therefore, that HMDS plays a useful role in promoting order in the P3HT film as well as reducing the density of interface trap states. Although interposing the P3HT layer between the insulator and the gold electrode degrades the insulating properties of the c-PAI, nevertheless, they remain sufficiently good for use in organic electronic devices.     

Nanogrinding of multi-layered thin film amorphous Si solar panels

Nanogrinding was performed on the cross-sections of amorphous Si thin film solar panels, which are nanoscale multi-layer structures consisting of hard and brittle materials. The deformed structures of the panel cross-sectional surfaces after grinding were investigated using electron and atomic force microscopy. The nanogrinding results were compared with those obtained from polishing and nanoscratching, demonstrating that the three processes had produced consistent surface characteristics. Though nanogrinding produced nanometric surface roughness with ductile material removal, but could cause cracking, edge chipping and delamination at thin film interfaces. The results of this work are of value for developing the efficient machining process for thin film solar panels and other brittle multi-layer materials.     

Surface-catalyzed transformations of aqueous endosulfan

We report the effect of suspended solids on the oxidation and hydrolysis of the insecticide endosulfan (alpha and beta isomers) and its degradation products: endosulfan diol, endosulfan sulfate, endosulfan ether, and endosulfan lactone in 0.001 M NaHCO3 buffer (pH 8.15). Suspensions of sea sand, TiO2, alpha-Fe2O3, alpha-FeOOH, Laponite, and SiO2 all catalyzed the hydrolysis of endosulfan to the less toxic endosulfan diol. Suspended creek sediment (Bread and Butter Creek SC, 4% OC) inhibited endosulfan hydrolysis. Heterogeneous and homogeneous rate constants of endosulfan hydrolysis were measured and indicate that beta-endosulfan hydrolyzes faster than alpha-endosulfan. This observation was explained by a more stable transition state for beta-endosulfan that was confirmed with ab initio molecular orbital calculations (STO-6G) on the anionic intermediates of endosulfan hydrolysis. Rates of endosulfan hydrolysis over the different surfaces corresponded to their tritium-exchange site-density and suggest a mechanism involving surface coordination prior to nucleophilic attack. The oxidation of alpha-endosulfan and beta-endosulfan to the persistent pollutant endosulfan sulfate was not observed in this study.     

Application of nonlinear fitting and selection of the most fitted equation by AIC in stability test of pharmaceutical ingredients

We proposed a method for objectively selecting the most fitted rate equation among candidate rate equations based on chemical kinetics by both nonlinear regression analysis and Akaike's information criterion (AIC), to express the decrease of pharmaceutical ingredient as an appropriate equation. Pseudo-zero, first, and second-order rate equations were prepared as candidates beforehand, and AIC was introduced for selecting the most fitted rate equation among the candidates. We compared the proposed method to the Weibull method that expressed any decrease patterns as a single equation.

We quantified the contents of thiamine nitrate (VB1) and taurine after storage for one, three, and six months under 40°C-75% relative humidity by high-pressure liquid chromatography. Decrease patterns of each sample were most fitted to one of the candidate rate equations, that is, pseudo-zero, first, and second-order rate equations, respectively, and the degree of fit in the most fitted equation was superior to that of the Weibull method, except for the pseudo-first-order rate equation.

Moreover, we confirmed that the proposed method was considerably precise for estimating the stability of pharmaceuticals by comparing estimated residual rates and confidence intervals to experimental data.