(N,N-Diisopropylcarbamoyloxy)-methyl p-tolyl sulfone: preparation and application for the syntheses of 1,2-diols

1-(N,N-Diisopropylcarbamoyloxy)-1-tosyl-methane (CbOCH₂Ts, Cb=N,N-diisopropylcarbamoyl) was readily prepared from p-TolSH, paraformaldehyde and CbCl. With the dual activation of CbO- and Ts-substitutions, deprotonation of CbOCH₂Ts could be effected not only by n-BuLi, but also by Grignard reagents. Upon deprotonation, the title compound adds to various carbonyl structures. By choosing proper organometallic reagents for consecutive steps, the addition intermediate undergoes in situ conversions to efficiently yield regioselectively O-Cb protected and unprotected 1,2-diols.     

Synthesis,crystal structure,and photoluminescence of zinc complex [Zn(Qina)<Subscript>2</Subscript>(DMSO)<Subscript>2</Subscript>] · 2DMSO

A novel complex [Zn(Qina)₂(DMSO)₂] · 2DMSO (I) (Qina = quinaldic acid, DMSO = dimethyl sulfoxide) has been synthesized and characterized by X-ray diffraction, elementary analysis, and IR spectrum. The unit cell parameters for complex I: a = 8.2884(11), b = 22.015(3), c = 9.0685(12) Å, β = 100.61(0)°, V = 1626.41(40) ų, Z = 2, space group, P2₁/n. In the complex I, the Zn(II) atom was six-coordinated to form a distorted octahedral geometry by two Qina ligands and two dimethyl sulfoxide molecules. The crystal structure is stabilized by hydrogen bonds, C - H... π, π-π stacking interaction between adjacent complexes. The binding of the complex I with calf thymus DNA has been investigated by fluorescence spectroscopic studies. The result suggested that the complex intercalates into DNA base pairs.     

表面活性剂吸附的电泳研究

实验测定了溴代烷基三甲胺的吸附对单分散聚苯乙烯胶乳电泳速度的影响.在Stern双电层模型的基础上,从电泳数据求得了吸附等温线,改进了计算吸附位数与吸附自由能的方法,并讨论了可能的吸附机构.     

Antifungal activity of crown ethers

Some crown ethers were found to show significant antifungal activity against some wood-decay fungi, phytopathogenic fungi and eumycetes,Trichophytons for dermatomycosis. Their toxicity was evaluated by the paper disc method as well as by determining the values of ED₅₀, i.e., the concentration which inhibits the mycelium growth by 50%. The fungi examined areTyromyces palustris, Picnoporous coccineus, Coriolous versicolor, Pyricularia filamentosa, Fusarium sp., Trichophyton rubrum, Trichophyton sp., etc. Among the 26 crown ethers tested, 3,5-di-t-butyl-benzo-15-crown-5 showed relatively high activity, the highest ED₅₀ value of which being 8 M or 3 ppm. Other alkylbenzocrown ethers, dicyclohexyl crown ethers and Kryptofix 22DD also showed considerable activity. On the other hand, unsubstituted crown ethers, benzocrown ethers with a polar substituent, Kryptofix 222B and Kryptofix 221 were inactive.     

Fused Mesoionic Heterocycles: Synthesis of 1,2,4-triazolo(4,3-b)-1,2,4-triazole derivatives

A number of mesoionic compounds derivatives of the bicyclic system 1,2,4-triazolo(4,3-b)-1,2,4-triazole have been prepared from 4-amino-1-methyl-3,5-bis(methylthio)-1,2,4-triazolium iodide and aryl isothiocyanates.     

The kinetics of tritium-hydrogen exchange in xanthosine,theobromine and monomethylated derivatives of xanthine

Tritium exchange at C-8 of xanthosine, theobromine, 1-, 3- and 7-methylxanthine in water has been studied. The rates of detritiation of these compounds have been determined over a pH range at constant temperature. Several mechanisms of exchange involving various ionic forms of substrate operating at different pH have been suggested.     

Amorphous structures in the immiscible Ag-Ni system

Vapor quenching in the phase-separating Ag-Ni system creates alloys that appear homogeneously amorphous under conventional probes. However, an atomic-level structural analysis based on extended x-ray absorption fine structures in combination with reverse Monte Carlo and molecular dynamics simulations demonstrates that these new phases are characterized by nonuniform, spinodal-like structures on an extremely fine scale. This heterogeneous nature of the structure is directly responsible for the unexpectedly low heat (and temperature) of crystallization observed in calorimetric measurements.     

Unusual aryl-porphyrin rotational barriers in peripherally crowded porphyrins

Previous studies of 5,10,15,20-tetraarylporphyrins have shown that the barrier for meso aryl-porphyrin rotation (DeltaG++(ROT)) varies as a function of the core substituent M and is lower for a small metal (M = Ni) compared to a large metal (M = Zn) and for a dication (M = 4H(2+)) versus a free base porphyrin (M = 2H). This has been attributed to changes in the nonplanar distortion of the porphyrin ring and the deformability of the macrocycle caused by the core substituent. In the present work, X-ray crystallography, molecular mechanics (MM) calculations, and variable temperature (VT) (1)H NMR spectroscopy are used to examine the relationship between the aryl-porphyrin rotational barrier and the core substituent M in some novel 2,3,5,7,8,10,12,13,15,17,18,20-dodecaarylporphyrins (DArPs), and specifically in some 5,10,15,20-tetraaryl-2,3,7,8,12,13,17,18-octaphenylporphyrins (TArOPPs), where steric crowding of the peripheral groups always results in a very nonplanar macrocycle. X-ray structures of DArPs indicate differences in the nonplanar conformation of the macrocycle as a function of M, with saddle conformations being observed for M = Zn, 2H or M = 4H(2+) and saddle and/or ruffle conformations for M = Ni. VT NMR studies show that the effect of protonation in the TArOPPs is to increase DeltaG++(ROT), which is the opposite of the effect seen for the TArPs, and MM calculations also predict a strikingly high barrier for the TArOPPs when M = 4H(2+). These and other findings suggest that the aryl-porphyrin rotational barriers in the DArPs are closely linked to the deformability of the macrocycle along a nonplanar distortion mode which moves the substituent being rotated out of the porphyrin plane.