Hydrogen Sulfide Metabolite,Sodium Thiosulfate: Clinical Applications and Underlying Molecular Mechanisms

Thiosulfate in the form of sodium thiosulfate (STS) is a major oxidation product of hydrogen sulfide (H₂S), an endogenous signaling molecule and the third member of the gasotransmitter family. STS is currently used in the clinical treatment of acute cyanide poisoning, cisplatin toxicities in cancer therapy, and calciphylaxis in dialysis patients. Burgeoning evidence show that STS has antioxidant and anti-inflammatory properties, making it a potential therapeutic candidate molecule that can target multiple molecular pathways in various diseases and drug-induced toxicities. This review discusses the biochemical and molecular pathways in the generation of STS from H₂S, its clinical usefulness, and potential clinical applications, as well as the molecular mechanisms underlying these clinical applications and a future perspective in kidney transplantation.     

Copolymerization in UF/pMDI adhesives networks

Kinetic evidence in thermomechanical analysis experiments and carbon‐13 nuclear magnetic resonance spectroscopy (¹³C NMR) evidence indicates that the strength of a joint bonded with UF (urea–formaldehyde)/polymeric 4,4'‐diphenylmethane diisocyanate (pMDI) glue mixes is improved by coreaction of the methylol groups of UF resins with pMDI to form a certain number of methylene cross‐links. The formation of these methylene cross‐links is predominant, rather than formation of urethane bridges which still appear to form but which are in great minority. This reaction occurs in presence of water and under the predominantly acid hardening conditions, which is characteristic of aminoplastic resins (thus, in presence of a hardener). Coreaction occurs to a much lesser extent under alkaline conditions (hence, without UF resins hardeners). The predominant reaction is then different in UF/pMDI adhesive systems than that observed in phenol‐formaldehyde (PF)/pMDI adhesive systems. The same reaction observed for UF/pMDI system at higher temperatures has also been observed in PF/pMDI systems, but only at lower temperatures. The water introduced in the UF/pMDI mix by addition of the UF resin solution has been shown not to react with pMDI to an extent such as to contribute much, if at all, to the increase in strength of the hardened adhesive. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3681–3688, 2002     

Layered silicate nanocomposites based on various high‐functionality epoxy resins. Part II: The influence of an organoclay on the rheological behavior of epoxy prepolymers

The effect of an organically surface modified layered silicate on the viscosity of various epoxy resins of different structures and different functionalities was investigated. Steady and dynamic shear viscosities of the epoxy resins containing 0–10 Wt% of the organoclay were determined using parallel plate rheology. Viscosity results were compared with those achieved through addition of a commonly used micronsized CaCO₃ filler. It was found that changes in viscosities due to the different fillers were of the same order, since the layered silicate was only dispersed on a micron‐sized scale in the monomer (prior to reaction), as indicated by X‐ray diffraction measurements. Flow activation energies at a low frequency were determined and did not show any significant changes due to the addition of organoclay or CaCO₃. Comparison between dynamic and steady shear experiments showed good agreement for low layered silicate concentrations below 7.5 wt%, i.e. the Cox‐Merz rule can be applied. Deviations from the Cox‐Merz rule appeared at and above 10 wt%, although such deviations were only slightly above experimental error. Most resin organoclay blends were well predicted by the Power Law model, only concentrations of 10 wt% and above requiring the Herschel‐Buckley (yield stress) model to achieve better fits. Wide‐angle X‐ray measurements have shown that the epoxy resin swells the layered silicate with an increase in the interlayer distance of approximately 15 Å, and that the rheology behavior is due to the lateral, micron‐size of these swollen tactoids.     

Chemical synthesis and physiological activity of sulfonium analogues of platelet activating factor

Phosphatidylsulfocholine (PSC), the sulfonium analogue of phosphatidylcholine (PC), occurs naturally in some diatoms. The replacement of the −N⁺(CH₃)₃ group by a −S⁺(CH₃)₂ results in an increase in the polar head group size in PSC relative to that of PC, consistent with the observed increase in permeability of PSC bilayers towards urea. It was of interest to see whether replacement of the −N⁺(CH₃)₃ group in platelet activating factor (PAF) by an −S⁺(CH₃)₂ group leads to any change in platelet aggregation or other physiological activity. Synthesis of the sulfonium analogue of PAF was carried out by suitable modifications of known procedures. The PAF-sulfonium analogue was found to have almost the same platelet aggregating activity as PAF itself, in the concentration range 1–20 μM, but a much lower activity in the range 0.01–1 μM. The analogue had little or no effect on the platelet aggregation activity of PAF when added in the concentration range 0.01–1 μM and had about half the hypotensive activity of PAF towards hypertensive CDF male rats. The sulfonium analogue, however, was much more cytotoxic to HL-60 cells than PAF itself, in the concentration range 0–15 μM; replacement of the acetate group by a benzyl group increased the cytotoxicity to the level of that of the methoxy analogue of PAF. Thus, replacement of the −N⁺(CH₃)₃ group by a −S⁺(CH₃)₂ group in the polar head group region of PAF results in a relatively small change in its platelet aggregation activity and a decrease in its hypotensive activity, but greatly increases its antitumor activity. Based on a paper presented at the Third International Conference on Platelet-Activating Factor and Structurally Related Alkyl Ether Lipids, Tokyo, Japan, May 8–12, 1989.     

Dynamic light scattering and ultrasonic investigations during the cure reaction of an epoxy resin

Brillouin scattering (BS), photon correlation spectroscopy (PCS), and ultrasonic (US) measurements were conducted to study the curing process of diglycidyl ether of bisphenol A with butane-1,4-diol at a curing temperature of 100°C. The experimental techniques probe the primary glass-rubber transition during the curing reaction. The primary relaxation time τ obtained from the BS and US velocity and absorption increases with curing time and hence the BS experiment measures τ at earlier stages of cure than the US experiment. The relaxation times at a different extent of reaction and for different measuring temperatures are consistent with BS, US, PCS, and DSC measurements and conform to a single reduced Vogel–Fulcher–Hesse–Tamann equation. Furthermore, the US experiments show evidence of secondary relaxations in the epoxy system.     

A novel technique for the preparation of secondary fatty amides

A technique for the synthesis of monosubstituted fatty amides at low temperature and ambient pressure was developed. This method involved the condensation of an amine with a triacylglycerol. The primary amine (ethyl,n-butyl,n-hexyl andn-octyl were tested) acted as reagent and solvent for the fatty substrates. No additional organic solvent or catalyst was added. Tallow, vegetable oils and fish oil all served well as substrates, as did pure tripalmitin. The rate of amidation was dependent upon temperature and the ratio of fat to amine. In a series of experiments conducted with tallow andn-butylamine at a fat:amine molar ratio of 1:16, amidation could be carried out at 20°C, producingn-butyltallowamide in 83% yield in 24 hr. When the fat:amine molar ratio was reduced to 1:8, and the temperature raised to 45°C, the amide yield was 87.6% in 24 hr. When the reaction was carried out at the boiling point ofn-butylamine (78°C) and at a fat:amine ratio of 1:8, the amide yield was 93.2% in 4 hr. The reaction progressed more rapidly with higher molecular weight amines. The identity and purity of the amides was assessed by thin-layer chromatography and confirmed by elemental analyses and infrared and C¹³ nuclear magnetic resonance spectroscopy.     

HEAT TRANSFER IN PARTIALLY MISCIBLE TERNARY SYSTEMS

In the study of mass transfer between partially miscible liquids, temperature perturbations have been found to have an important effect in the generation of interfacial activity. Micro- and macro-generated interfacial convection usually occurs in combination with one another even in fairly simple heat or mass transfer events. These combinations are responsible for the enhancement of mass transfer rates. In an effort to acquire a better understanding of the heat transfer effects in ternary liquid-liquid systems, temperature difference profiles were measured when contacting two partially miscible phases. A vertical and a rotational transfer cell were designed to contact the partially miscible phases without inducing external disturbances. Five thermocouples were immersed in the bottom liquid phase at predetermined positions below the interface. In order to understand the influence of the convection generated, the vertical cell was designed to hinder convection in one phase, while the rotational cell permits convection in both phases. The experimental results showed larger temperature differences in the rotational cell after the contact of the phases. Also, systems which were initially unsaturated presented larger heat effects than those in which the partially miscible solvents were initially saturated. Several parameters indicating the importance of heat effects in the ternary systems studied are reported.     

THE IRREVERSIBLE ADSORPTION OF PLUTONIUM HEXAFLUORIDE†

The room temperature adsorption of PuF_6(g) on a solid substrate was compared to the adsorption of UF6(g) on the same surface. Significantly more PuF_6(g) was adsorbed at pressures in the range of 1.2 to 0.2torr, accompanied by the evolution of molecular fluorine. The adsorbed UF₆ was easily desorbed by reducing the pressure. Most of the adsorbed PuF₆ remained on the surface when subjected to the same treatment.     

Aplysia sea hare assimilation of secondary metabolites from brown seaweed,Stypopodium zonale

JuvenileAplysia dactylomela were found feeding in abundance on the tropical brown algaStypopodium zonale, a seaweed previously shown to contain numerous unique terpene-quinone natural products. Lipid extracts of these herbivorous mollusks were shown by TLC and HPLC-NMR analyses to contain appreciable quantities of twoS. zonale metabolites as well as one new but closely related compound. Spectroscopic analyses of the new compound in concert with functional group modifications identified this new compound as 3-keto epitaondiol. A careful analysis of the seaweed extract failed to locate this ketone, and thus, it most likely represents anAplysia-biotransformed compound. This is the first clear reported observation of metabolite transfer between an alga of the phylum Phaeophyta and a sea hare.