Water's hydrogen bonds in the hydrophobic effect: a simple model

We propose a simple analytical model to account for water's hydrogen bonds in the hydrophobic effect. It is based on computing a mean-field partition function for a water molecule in the first solvation shell around a solute molecule. The model treats the orientational restrictions from hydrogen bonding, and utilizes quantities that can be obtained from bulk water simulations. We illustrate the principles in a 2-dimensional Mercedes-Benz-like model. Our model gives good predictions for the heat capacity of hydrophobic solvation, reproduces the solvation energies and entropies at different temperatures with only one fitting parameter, and accounts for the solute size dependence of the hydrophobic effect. Our model supports the view that water's hydrogen bonding propensity determines the temperature dependence of the hydrophobic effect. It explains the puzzling experimental observation that dissolving a nonpolar solute in hot water has positive entropy.     

Studies on molecular interactions of β-cyclodextrin and antiulcer agent

The search for the lowest energy conformation of complex {β-cyclodextrin (β-CD)+chlorambucil} were carried out by molecular mechanics method. Theoretical calculations of molecular interactions of complex were carried out using the molecular orbital method. The correlation between energy changes and molecular structures are discussed. The large interaction energies calculated by the molecular orbital method bears out the inclusion phenomenon.     

How to utilize the true performance of monolithic silica columns

Ways of utilizing the true separation efficiency of monolithic silica (MS) columns were studied. The true performance of MS columns, both regular-sized (rod-type clad with PEEK resin, 4.6 mm ID, 10 cm) and capillary sized (in 100 or 200 microm ID fused silica capillary, 25-140 cm) was evaluated by calculating the contribution of extra-column effects. HETP values of 7-9 microm were observed for solutes having retention factors (kvalues) of up to 4 for rod columns and up to 15 for a capillary column. The high permeability of MS columns allowed the use of long columns, with several connected together in the case of rod columns. Narrow-bore connectors gave good results. Peak variance caused by a column connector ranges from 50 to 70% of that caused by one rod-type column for up to three connectors or four columns in 80% methanol, but the addition of a 4th or 5th connector to add a 5th and 6th column, respectively, caused a much greater increase in peak variance, especially for long-retained solutes, which is greater than the variance caused by one rod column. Rod columns seem to show slightly lower efficiency at a pressure higher than 10 MPa or so. The use of acetonitrile-water as a mobile phase better preserved the ability of individual rod columns to generate up to 100,000 theoretical plates with 14 columns connected. Methods for eliminating extra-column effects in micro-HPLC were also studied. Split injection and on-column detection resulted in optimum performance. A long MS capillary measuring 140 cm produced 160,000 theoretical plates. The column efficiency of a capillary column was not affected by the pressure, showing advantages over the rod columns that exhibited peak broadening caused by connectors and pressure.     

Solvent decompositions and physical properties of decomposition compounds in Li-ion battery electrolytes studied by DFT calculations and molecular dynamics simulations

The density functional theory (DFT) calculations have been performed for the reduction decompositions of solvents widely used in Li-ion secondary battery electrolytes, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonates (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC), including a typical electrolyte additive, vinylene carbonate (VC), at the level of B3LYP/6-311+G(2d,p), both in the gas phase and solution using the polarizable conductor calculation model. In the gas phase, the first electron reduction for the cyclic carbonates and for the linear carbonates is found to be exothermic and endothermic, respectively, while the second electron reduction is endothermic for all the compounds examined. On the contrary, in solution both first and second electron reductions are exothermic for all the compounds. Among the solvents and the additive examined, the likelihood of undergoing the first electron reduction in solution was found in the order of EC > PC > VC > DMC > EMC > DEC with EC being the most likely reduced. VC, on the other hand, is most likely to undergo the second electron reduction among the compounds, in the order of VC > EC > PC. Based on the results, the experimentally demonstrated effectiveness of VC as an excellent electrolyte additive was discussed. The bulk thermodynamic properties of two dilithium alkylene glycol dicarbonates, dilithium ethylene glycol dicarbonate (Li-EDC) and dilithium 1,2-propylene glycol dicarbonate (Li-PDC), as the major component of solid-electrolyte interface (SEI) films were also examined through molecular dynamics (MD) simulations in order to understand the stability of the SEI film. It was found that film produced from a decomposition of EC, modeled by Li-EDC, has a higher density, more cohesive energy, and less solubility to the solvent than the film produced from decomposition of PC, Li-PDC. Further, MD simulations of the interface between the decomposition compound and graphite suggested that Li-EDC has more favorable interactions with the graphite surface than Li-PDC. The difference in the SEI film stability and the behavior of Li-ion battery cycling among the solvents were discussed in terms of the molecular structures.     

Substitution reactions in the secondary ion mass spectrometry of N-methylpyridinium halides

Secondary ion mass spectra of N-methylpyridinium halides (C⁺X^?, where C⁺ is a pyridinium cation and X^? is a halogen anion) exhibit the C⁺ ions, a series of cluster ions ((C⁺)_n(X^?)_n–1) and, furthermore, remarkable [CX – R]⁺ ions (R = H or Me). The mechanism of the formation of [CX – R]⁺ ions was investigated by the use of deuterated compounds and B/E and B²/E constant linked-scan measurements. A possible explanation is proposed in which the ions are produced through substitution reactions between species constituting the C₂X⁺ cluster ions in the gas phase.     

Stereoselective synthesis of atropisomeric korupensamines A and B utilizing planar chiral arene chromium complex

Naphthyl tetrahydroisoquinoline alkaloids, atropisomeric korupensamines A and B and ent-korupensamine B, were synthesized by syn-selective cross-coupling of a planar chiral arene chromium complex with naphthylboronic acid and subsequent axial isomerization or tricarbonylchromium migration to the inverted arene face as a key step. Palladium(0)-catalyzed cross-coupling of planar chiral arene chromium complex 12 with naphthylboronic acid 9 gave syn-biaryl coupling product 13. syn-Biaryl chromium complex 13 was heated in 1:1 mixture of di-n-butyl ether and 1,2-dichloroethane to give a face-inverted anti-biaryl chromium complex 14 without axial isomerization. Korupensamine A was synthesized from the syn-biaryl chromium complex 13 via o-formyl syn-biaryl chromium complex 10, and ent-korupensamine B was prepared from the face-inverted anti-biaryl chromium complex 14. On the other hand, difluoro-substituted syn-biaryl chromium complex 40 with a formyl group afforded anti-biaryl chromium complex 41 containing a rotated central bond by heating in xylene. The chromium-complexed fluorine atom was easily substituted with an isopropoxy group by nucleophilic substitution. Use of these reactions allowed (+)-2-bromo-3,5-difluorobenzaldehyde chromium complex (37) as a single chiral source to be converted to atropisomeric korupensamines A and B, respectively.     

Molecular structure and photoreaction of poly(methylpropylsilane)

The molecular structure and photoreaction of poly(methylpropylsilane) (PMPrS) are investigated. The ²⁹Si-NMR spectra reveal that PMPrS is a linear polymer with no blanches. Fine multiple splitting of ²⁹Si-NMR is observed at room temperature. This multiple splitting is thought to be due to molecular conformation. The photo-oxidation reaction of the PMPrS film is found to be caused by light irradiation at the UV absorption band, 330 nm. Quantum efficiencies of scission and crosslink related to photodegradation are evaluated. There is little difference in either the molecular structure or photoreactivities between the high and the low molecular weight portions of the bimodal molecular weight distributions of PMPrS.     

π-Cyclopentadienyls of nickel(II) : XIII. The preparation and properties of the compounds π-C5H5NiPBu3SC(S)X (X = OR,R and NRH) and π-C5H5NiPBu3SC(O)NRH

Compounds of the type π-C₅H₅NiPBu₃SC(S)X (X = R, OR and NRH) are obtained from reactions between [π-C₅H₅Ni(PBu₃)₂]⁺Cl^? and SC(S)X^? in aqueous solution. Compounds such as π-C₅H₅NiPBu₃SC(S)NRH are also obtained by reactions of π-C₅H₅NiPBu₃SH with RNCS.Reactions of C₆H₅NCS with π-C₅H₅NiPBu₃SEt or [π-C₅H₅NiPBu₃S(CH₂)_n]₂ (n = 1, 2 and 3) give π-C₅H₅NiPBu₃[SC(NC₆H₅)SC₂H₅] or [π-C₅H₅NiPBu₃ {SC(NC₆H₅)S(CH₂)_n}]₂ respectively.Similar reactions of π-C₅H₅NiPBu₃SH and RNCO given π-C₅H₅NiPBu₃SC(O)NRH.Treatment of π-C₅H₅NiPBu₃SC(S)R with HCl gives π-C₅H₅NiSC(S)R.     

Resonant pumping far-infrared NH3 laser

A far-infrared (FIR) NH₃ laser was resonantly pumped with a line-tunable infrared (IR) NH₃ laser. The number of the observed FIR laser lines amounted to 33. Most of them belonged toaR(J,K) rotation-inversion transition in (0, 1, 0, 0) vibrational state. The line tunability of sealed-off FIR NH₃ laser was almost achieved in 90, 115, 150, and 220 m wavelength regions by the selective line tuning of the pumping IR NH₃ laser.