Equations of state for pure and mixture square-well fluids. II. Equations of state

New coordination number models for square-well (SW) fluids are incorporated with the generalized van der Waals partition function to develop equations of state for both pure and mixture SW fluids. The equations of state have been extensively tested with the Monte Carlo simulation data, of which three sets (18 data points) for the pure SW fluids are produced in this work. The results show that, without any parameters, our model reasonably describes not only the PVT behaviors but also the second and third virial coefficients of the model fluids. In addition, a comprehensive comparison has been made between our models and the other equations of state derived from the Lee-Chao and Lee-Sandler coordination number correlations.     

磺胺二甲嘧啶的极谱伏安行为

本文考察了磺胺二甲嘧啶在多种底液中的极谱伏安行为，发现其在ＢｒｉｔｏｎＲｏｂｉｎｓｏｎ（ＢＲ）缓冲溶液（ｐＨ２．２）中产生一个良好的还原峰，峰电位为－０．８５Ｖ（ｖｓ．ＳＣＥ），峰电流与磺胺二甲嘧啶浓度在１×１０－７３×１０－４ｍｏｌ／Ｌ范围内呈良好的线性关系，检出限为９×１０－８ｍｏｌ／Ｌ，大多数金属离子和无机阴离子不干扰测定，可望用于定量测定用多种电化学方法研究了该还原峰电流的性质，结果表明，它是具有吸附性质的不可逆还原峰     

Formation of nitrogen‐containing heterocycles using di(imidazole‐1‐yl)methanimine

A mild and efficient synthesis of five‐ and six‐membered nitrogen containing heterocyclic compounds, in which di(imidazole‐1‐yl)methanimine serves as a one‐carbon source, is reported.     

Control of mesoporous structure of aerogels derived from cresol-formaldehyde

Polycondensation of a cresol mixture (C(m)) with formaldehyde (F) in basic aqueous solutions leads to formation of highly cross-linked C(m)F aquagels that can be supercritically dried with carbon dioxide to form organic C(m)F aerogels. Aerogels synthesized with different catalyst contents and reactant concentrations are characterized by low-temperature nitrogen adsorption. The present experimental results suggest that the C(m)F aerogels are typical mesoporous materials and have almost no micropores in bulk. The microstructure of the organic C(m)F aerogels can be controlled and tailored effectively by varying synthesis conditions during the initial sol-gel process. C(m)F organic aerogels with specific surface area as high as 627 m(2)/g and corresponding pore volume 2.06 ml/g have been obtained with a dominant pore size of 30 nm. C(m)F organic aerogels with peaky pore size distributions concentrated at 11 nm have also been prepared.     

Antihypertensive Effect of Angiotensin‐Converting Enzyme Inhibitory Peptide Obtained from Hen Ovotransferrin

Angiotensin I‐converting enzyme (ACE) inhibitory peptide was isolated from the hen ovotransferrin hydrolysate using chymotryptic hydrolysis by two steps of reverse‐phase high‐performance liquid chromatography. The amino sequence of this novel peptide was identified as Lys‐Val‐Arg‐Glu‐Gly‐Thr‐Thr‐Tyr that inhibited ACE activity in vitro in a concentration‐dependent manner with an effective concentration (IC₅₀) of 102.8 μM. Also, this inhibition was identified as noncompetitive using the Lineweaver‐Burk plot. Moreover, the antihypertensive action of this novel peptide was investigated by an intravenous injection into spontaneously hypertensive rats (SHR). A dose‐dependent reduction of systolic blood pressure by this peptide was observed after 40 min of treatment and it decreased the blood pressure markedly at the maximal dose (1 nmol/mL/kg). The maximal blood pressure lowering activity of this peptide was calculated as 163% of captopril (10 pmol/mL/kg) that was used as positive control. In conclusion, the obtained data suggests that Lys‐Val‐Arg‐Glu‐Gly‐Thr‐Thr‐Tyr has an ability to inhibit ACE activity and decrease the systolic blood pressure in hypertensive animals.     

Does core size matter in the kinetics of ligand exchanges of monolayer-protected Au clusters?

This paper compares the kinetics of exchanges of phenylethanethiolate ligands (PhC2S-) of the monolayer-protected clusters (MPCs) Au(38)(SC2Ph)(24) and Au(140)(SC2Ph)(53) with p-substituted arylthiols (p-X-PhSH), where X = NO(2), Br, CH(3), OCH(3), and OH. First-order rate constants at 293 K for exchange of the first ca. 25% of the ligands on the molecule-like Au(38)(SC2Ph)(24) MPC, measured using (1)H NMR, vary linearly with the in-coming arythiol concentration; ligand exchange is an overall second-order reaction. Remarkably, the second-order rate constants for ligand exchange on Au(38)(SC2Ph)(24) are very close to those of corresponding exchange reactions on the larger nanoparticle Au(140)(SC2Ph)(53) MPCs. These are the first results that quantitatively show that the chemical reactivity of different sized nanocrystals is almost independent of size; presumably, this is because the locus of the initial ligand exchanges is a common kind of site, thought to be the nanocrystal vertexes. The rates of later stages of exchange (beyond ca. 25%) differ for Au(38) and Au(140) cores, the latter being much slower presumably due to its larger terrace-like surface atom content. The reverse exchange reaction was studied for Au(38)(p-X-arylthiolate)(24) MPCs (X = NO(2), Br, and CH(3)), where the in-coming ligand is now phenylethanethiol. Remarkably, the rate constants of both forward and reverse exchanges display identical substituent effects, which implies a concurrent bonding of both in-coming and leaving ligands to the Au core in the rate-determining step, as in an associative mechanism. X = NO(2) gives the fastest rates, and the ratio of forward and reverse rate constants gives an equilibrium constant of K(EQ,PE) = 4.0 that is independent of X.     

The relative influences of acidity and polarity on responsiveness of small organic molecules to analysis with negative ion electrospray ionization mass spectrometry (ESI-MS)

The purpose of the work presented here was to evaluate the influence of solution composition and analyte characteristics on responsiveness to analysis with negative ion electrospray ionization mass spectrometry. The responses of a series of structurally diverse acidic molecules were compared in various solvents. Response was generally observed to be higher in methanol than acetonitrile and response for all analytes was poorer when water was mixed with the organic solvent. A positive correlation between negative ion ESI-MS response and log P was observed when either acetonitrile or methanol was used as the electrospray solvent. This result was expected because analytes with significant nonpolar character should be particularly responsive to ESI-MS analysis due to their higher affinity for electrospray droplet surfaces. It was also predicted that highly acidic analytes would be most responsive to analysis with negative ion ESI-MS due to their tendency to form negative ions. However, for the analytes studied here, acidity was found not to have a consistent influence on ESI-MS response. Many of the highly acidic molecules were quite polar and, consequently, were poorly responsive. Furthermore, the deprotonated molecular ion was detected for a number of molecules with very high pKa values, which would not be expected to form negative ions in the bulk solution. Ultimately, these results indicate that acidity is not a conclusive parameter for prediction of the relative magnitudes of negative ion ESI-MS response among a diverse series of analytes. Analyte polarity does; however, appear to be useful for this purpose.