Total surface areas of Group IVA organometallic compounds: Predictors of toxicity to algae and bacteria

There is a high correlation between molecular surface area (TSA) of triorganotin and triorganolead compounds and their toxicity towards a bacterium (Escherichia coli) and an alga (Selenastrum capricornutum). Parallel attempts to correlate other Group IVA organometals incorporating silicon or germanium were unsuccessful. It was further demonstrated, however, that a high correlation was obtainable between certain series of compounds with the same organic substituent but different metal centers involving all Group IVA elements. In both instances, the inability to obtain a quantitative structure-activity relationship (QSAR) for all systems studied appears to be a function of the solubility of the compounds. While organotin TSA values have been found to correlate well with their toxicities toward various organisms, this study clearly suggests that this type of QSAR can be readily extended to include other organometal systems, provided that there is no solubility problem and the toxicity is a function of the hydrophobicity of the organometal compounds.     

Quantum-Chemical Evaluation of the Protolytic Properties of Thiophenols

The enthalpies and free energies of proton affinity (PA) were calculated by the PM3 method for 27 thiophenoxide anions. For thiophenols, linear correlation has been found between the PAs and the values of pK _a measured by different authors in aqueous acetone, aqueous ethanol, and methanol media. The dependences found permit one to predict a priori the protolytic properties of thiophenols. The differential effects of aqueous ethanol media with different ethanol contents on thiophenol acidity were evaluated based on quantum-chemical data.Original Russian Text Copyright © 2004 by A. N. Pankratov and A. V. Shalabai__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 800–806, September–October, 2004.     

Effect of reaction conditions on the molecular weight and polydispersity of linear poly(arylene ether phosphine oxide)s prepared from an AB monomer

A thorough study of the polymerization behavior of 4‐fluoro‐4′‐hydroxytriphenyl‐phosphine oxide, 2 , under nucleophilic aromatic substitution reactions has been carried out. The synthesis of 2 was achieved in excellent yields by the reaction of bis(4‐fluorophenyl)phenylphosphine oxide, 1 , with one equivalent of potassium hydroxide in DMSO/water. The structure and purity of 2 were confirmed via ¹H, ¹³C, and ³¹P NMR spectroscopy along with elemental analysis. Polymerization reactions of 2 in NMP or DMSO at 180 °C provided the corresponding linear poly(arylene ether phosphine oxide)s, PAEPOs, with number average molecular weights, M_n, ranging from 11,700 to 36,500 Da. All of the polymer samples were completely soluble in chloroform, tetrahydrofuran, DMSO, NMP, and DMAc. The polymerization reactions were accompanied by a competing intramolecular process that resulted in the formation of cyclic oligomeric species that were removed via a final precipitation from methanol. Analysis using ³¹P NMR spectroscopy and size exclusion chromatography (SEC) confirmed that the majority of the lower molecular weight cyclic species were removed via this process. The polymer samples formed tough films when chloroform solutions were slowly evaporated on a glass slide. The PAEPO samples prepared in this study exhibited excellent thermal stability with T_d (5%) values between 503 and 542 in air while the glass transition temperatures ranged from 223 to 237 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2099–2106, 2006     

Structure–activity studies on the fungitoxicity of some triorganotin(IV) compounds

Seventeen triorganotin(IV) compounds, with the general formula R₃SnX, containing symmetrical and unsymmetrical combinations of alkyl and aryl groups on tin and with a wide variation in the non-carbon-bonded anionic (X) residues, were examined along with three formally pentacoordinated adducts of triaryltin chlorides with triphenylphosphine oxide for their antifungal activity against nine plant pathogenic and saprophytic fungi. The in vitro tests included inhibitory studies on radial growth, mycelial growth, spore germination, and germ tube elongation. A significant finding was the dependence of fungitoxicity on the nature of the X group in both the tributyltin and triaryltin series, in contrast to earlier published reports on the negligible influence of the X groups on overall toxicity relative to the R group. This suggests that the X group is significantly involved in transporting the biocide to the reactive sites, and that the X group which tends to confer increased solubility to the triorganotin compound gives rise to increased activity. In studies of R group variations, tri-iso-butyltin bromide was found to be much less fungitoxic than tri-n-butyltin compounds, a result which is reconcilable in terms of increased steric encumbrance at the tin site in the former case. The steric factor is also implicated in the reduced activities observed for tris(p-tolyl)tin and tris(p-chlorophenyl)tin compounds relative to (Ph₃SnX) towards most of the fungi screened in this study. In general, it was also noted that the triaryltins were more selective in their antifungal action than the trialkyltins, which exhibited broad spectral activity when applied at the concentration level of 10 μg cm^?3.     

氮杂冠醚与碱金属离子配位反应的研究

滴定量效法是研究反应热化学和热力学的重要手段之一．用这种方法对冠醚与金属离子的配位反应热力学性质进行研究一直受到很大关注【且S习．但是对氨杂冠林，尤其是一系列结构相似的氨杂冠醚体系进行系统的热力学性质研究的报导不多．前文K则曾报导了用自组装的消定量热计对银（I）－a吹体系和铜（11）·N，N’一问位取代革基乙二胺体系的配位反应热化学研究结果·本文报导从（对位取代革基）k杂15冠5卜RPW15CS，R＝CIZH；CHa；CHso）与碘化钠和碘化钾在25T、无水乙过溶液中进行配位反应的消定量效研究结果．讨论了配体上取代基的电…     

Two-photon absorption in quadrupolar pi-conjugated molecules: influence of the nature of the conjugated bridge and the donor-acceptor separation

Quadrupolar-type substitution of pi-conjugated chromophores with donor and acceptor groups has been shown to increase their two-photon absorption (TPA) response by up to two orders of magnitude. Here, we apply highly correlated quantum-chemical calculations to evaluate the impact of the nature of conjugated bridge and the charge-transfer distance on that enhancement. We compare chromophores with phenylenevinylene-, thienylenevinylene-, polyene-, and indenofluorene-type backbones substituted by dimethylamino and cyano groups. In all compounds, we find a strongly TPA-active A(g) state (either 2A(g) or 3A(g)) in the low-energy region, as well as a higher lying TPA-active state (mA(g)) at close to twice the energy of the lowest lying one-photon allowed state; the smaller energy detuning in the mA(g) states results in very large TPA cross sections delta. We also investigate the influence of the degree of ground-state polarization on TPA. Independent of the nature of the backbone and the donor-acceptor separation, delta displays the same qualitative evolution with a maximum before the cyanine-like limit; the highest TPA cross sections are calculated for distirylbenzene- and polyene-based systems.     

Inhibitory study of some novel Schiff base derivatives on Staphylococcus aureus by microcalorimetry

The effect of a series of novel Schiff base compounds on Staphylococcus aureus was studied by microcalorimetric method at 37 °C The results showed that all of the organic compounds had the capacity to inhibit the growth of S. aureus in different extent. And the extent and duration of the inhibitory effect on the growth of S. aureus, judged from the rate constant (k), varied with the different structure of the Schiff base compounds. According to the power-time curves, the multiplication rate constant and inhibition ratio were calculated. The growth rate constant of S. aureus (in log phase) in the presence of Schiff base compounds decreased with the increasing of the concentrations of these compounds regularly. The experimental results revealed that the hydrophilicity of Schiff bases had a great influence on their antibacterial activity. Of these Schiff bases, the greater their hydrophilicity, the higher their antibacterial activity. The antibacterial structure-activity relationship (SAR) of Schiff base derivatives was also briefly discussed.