Molecular orbital treatments of hydrogen bonded systems. 2. Dimers of water and HCN

Calculations were performed to investigate the reliabilities of the CNDO/2, PRDDO, and MNDO approximate molecular orbital methods. Systems selected for study included the linear, cyclic, and bifurcated dimers of water as well as the linear and cyclic dimers of HCN. The PRDDO method was found to provide the most consistently accurate reproduction of ab initio and experimental data. CNDO/2 performed fairly well in a number of cases but yielded extremely poor results for the cyclic dimers of both H₂O and HCN. Hydrogen bond strengths were consistently underestimated by MNDO which also furnished erroneously large intermolecular separations. In addition, MNDO calculations indicate the bifurcated water dimer to be most stable in contrast to other quantum mechanical and experimental information.See Ref. [1] for Paper 1 of this series.     

Theoretical Study of Weakly Bound Dimers between Hydrogen Fluoride and Some Polar Molecules

Weakly bound linear and bent dimers, FH—X (where X = CO, OC, CNH, NCH, N₂O and ON₂), are investigated using the DFT B3LYP and ab initio MP2 methods with the same basis sets (6–311++G(3df,2pd)). The strengths of the H—C or H—N H‐bonds in dimers FH—CO, FH—CNH, and FH—N₂O are compared with those of the H—O or H—N H‐bonds in dimers FH—OC, FH—NCH, and FH—ON₂. The results obtained for the H‐bond distances, the elongation effect of the HF bond, the red shift of the HF stretching frequency, and the energy difference between the dimer and the charge transfer reveal that the H‐bonds of the first group of dimers are stronger than those of the second. The Gibbs energies calculated for the six dimer formations indicate that the weakly bound dimers are unstable at room temperature (T = 298 K) (FH—X's → FH + X's, ΔG < 0).     

Partial Molar Volumes of Amino Acids and Peptides in Aqueous Salt Solutions at 25°C and a Correlation with Stability of Proteins in the Presence of Salts

Partial molar volumes for a homologous series of amino acids and peptides have been measured in aqueous 1M sodium acetate, sodium thiocyanate, and sodium sulfate at 25^°C. These data have been utilized in conjunction with the data in water to deduce partial molar volumes of transfer V _2,m ⁰(tr) from water to these aqueous salt solutions. The volumes of transfer for the amino acids and peptides are found to be positive. The interpretation is that this result arises from the dominant interaction of the sodium salts with the charged centers of amino acids and peptides. Thermal denaturation of the structurally homologous proteins lysozyme and -lactalbumin has been studied in the presence of these salts. Significant thermal stabilization of hen egg-white lysozyme has been observed in the presence of sodium acetate and sodium sulfate. However, the thermal stabilization observed for -lactalbumin is very small in the presence of these salts and sodium thiocyanate leads to a lowering of its thermal denaturation temperature. The rise in the surface tension of aqueous salt solutions with salt concentration has been correlated with the calorimetric and volumetric measurements. The results show that V _2,m ⁰(tr) depends less on the type of electrolyte than on the ionic strength of the solution. The V _2,m ⁰(tr) values correlate very well with the increase in the surface tension of aqueous salt solutions, indicating significant role of surface tension in interactions of amino acids, peptides, or protein with the salts.     

Comparison between ab Initio and Modified INDO-MO Calculations of N20

Both STO-3G ab initio and s-p separation-type-modified INDO semiempirical methods were applied to molecular-orbital calculation of the N₂₀ molecule. From these two methods, the optimized bond distances between the nearest N atoms (d_n-n) and the most calculated thermodynamic data are close to each other. The positive values of ΔH_a° and ΔG_a° for the atomization reaction in this work prove that N₂₀ is stable. In contrast to conventional INDO and MINDO/3, but similar to former AMI and MNDO calculations, both ΔH_r° and ΔG_r° are positive in the formation reaction, which indicates that N₂₀ belongs to the category of high-energy molecules.     

Aggregation effects on evaporation and the air/water interface of dodecyltrimethylammonium hydroxide solutions

 The system dodecyltrimethylammonium hydroxide (DTAOH)–water was studied by surface tension, ion-selective electrodes and evaporation in an electrobalance. Results confirmed earlier conclusions about a stepwise aggregation mechanism in DTAOH solutions. The aggregation process started at a total concentration C _T=(2.51±0.10)×10^-4 mol dm^-3) which probably corresponds to the formation of dimers. At C _T= (1.300±0.041)×10^-3 mol dm^-3 there was a change in the surface and evaporation behavior, corresponding to the formation of small, fully ionized aggregates which grew with increasing concentration. At C _T= (1.108±0.010)×10^-2 mol dm^-3 the formation of true micelles with hydroxide counterions in the Stern layer did not change significantly the evaporation and adsorption behavior. This means that between this concentration and C _T=(3.02±0.28)× M28.8n10^-2 mol dm^-3, the changes in structure were gradual. At the latter concentration there was a sudden change in the monolayer state at the air/water interface, with a strong surfactant desorption, and a major change in evaporation behavior. The changes are compatible with the formation of few, large aggregates reducing the total concentration of kinetically independent solute units, which in turn increased the activity of the solvent. This phenomenon is in agreement with literature information. The reduction in the evaporation rate of water was mainly due to the reduction of the water activity, caused by colligative effects. The reduction of the effective area available for evaporation had only a slight effect in water evaporation. Received: 9 January 1997 Accepted: 19 October 1997     

Nucleation of the β-modification of isotactic polypropylene

The effects of the organic pigments C.I.P. RED 177 and C.I.P. Yellow 83 as nucleating agents on the crystallization of polypropylene were studied by DSC. The anthraquinone pigment exerted a significant effect, resulting in structural modifications with lower melting point, and particularly the -modification. The DSC curves exhibit four transition regions, with the following temperature intervals: I. 415–417 K, II. 423–425 K, III. 430–432 K and IV. 438–439 K. For evaluation of the -nucleation effect of pigments, the ratio (H ₁+H ₂)/(H ₃+H ₄) was suggested.     

Simultaneous quantitative measurement of a new platelet activating factor antagonist (BN 50730) and its two main metabolites in human plasma and urine by LC-MS

Summary A simple and sensitive assay has been developed for the quantitative measurement of a new platelet activating factor antagonist (BN50730), and its two main metabolites (BN50727 and BN50922), at the picomole level in human plasma and urine. The three compounds of interest and the internal standard (BN50765) were measured by combined LC-negative chemical ionization MS. A simple solid-liquid extraction procedure was used to isolate the parent drug and the two metabolites. The MS was tuned to monitor the intense ionm/z 333 generated in the ion source by a dissociative capture process. The assay was on 1 ml plasma or 0.1 ml urine and the quantitation limit was calculated as 1 ng·ml^–1. The very low relative standard deviations and mean percentages of error calculated for within-day or between-day repeatability assays demonstrate the ruggedness of the technique for routine determination in biological fluids. Some preliminary results on the pharmacokinetics of the parent drug and its two main metabolites illustrate the applicability of this method.     

Li2Br(NH2): Das erste ternäre Alkalimetallamidhalogenid

Li₂Br(NH₂): The First Ternary Alkali Metal Amide Halide The pseudobinary system LiNH₂/LiBr was investigated by X-ray methods. The crystal structure of the compound Li₂Br(NH₂) was solved by single crystal data: Li₂Br(NH₂): Pnma, Z = 8, a = 12.484(2) Å, b = 7.959(1) Å, c = 6.385(1) Å, Z(F_o) with (F_o)² ≧ 3σ(F_o)² = 348, Z (parameter) = 51, R/R_w = 0.019/0.021 Li₂Br(NH₂) crystallizes in a new type of structure. To one another isolated chains of [Li₂Li_4/2(NH₂)₂²⁺] show the motif of closest rod packing. They are connected via bromide ions in a distorted cubic primitive arrangement.     

Synthesis and characterization of MCM-48 tubular membranes

MCM-48 membranes have been prepared on alumina supports of different pore sizes. A battery of characterization techniques has been used to study the physical properties and the quality of the membranes prepared. The highest quality membranes were prepared on supports with pore size of up to 60 nm. The MCM-48 membranes were tested in the separation of gas phase mixtures and a cyclohexane/O₂ selectivity higher than 270 was obtained. The selective separation of organic compounds from inert components is a result of the cooperative effects of capillary condensation in MCM-48 pores and of the specific interactions of the permeating compounds and the membrane material.     

Crystal Structures of [Ni(Phen)(i‐Bu2PS2)2] and [Ni(Phen)3](i‐Bu2PS2)2 Complexes and Interaction between Coordinated 1,10‐Phenanthroline Molecules

Single crystals of [Ni(Phen)(iBu₂PS₂)₂] (I) and [Ni(Phen)₃](iBu₂PS₂)₂ (III) compounds were grown, and their structures were determined by Xray diffraction analysis (CAD4 diffractometer, MoK radiation, 3336 F _hkl , R = 0.0373 for I and 2575 F _hkl for III). The crystals of complex I have a triclinic unit cell with the following parameters: a = 11.097(1) , b = 14.903(2) , c = 22.650(3); = 75.18(1)°, = 80.50(1)°, = 75.07(1)°, V = 3479.2(7)³, Z = 4, _calc = 1.255 g/cm³, and space group 1; the crystals of III have a monoclinic unit cell with the following parameters: a = 19.010(3), b = 15.481(1) , c = 17.940(3); = 97.58(1)°, V = 5233.5(12)³, Z = 4, _calc = 1.292 g/cm³, and space group C2/c. The structure of complex I is built from mononuclear molecules, and the structure of III, from [Ni(Phen)₃]²⁺ complex cations and i Bu₂PS₂ ^- outersphere anions. The NiN₂S₄ coordination polyhedra in the structure of I and NiN₆ in the structure of III are distorted octahedra. Based on structural data, the interaction between the coordinated Phen molecules of complexes I, [Ni(Phen)₂(iBu₂PS₂)](iBu₂PS₂) (II), and III is considered, as well as the packing modes of these complexes.