The Synthesis and Properties of Diazaphenanthrene Aldehydes and their Simple Analogues

The synthesis of seven diazaphenanthrene aldehydes and their oximes via oxidation of corresponding methylderivatives is given and the n.m.r. spectra of the aldehydes are discussed. The synthesis of three new methyl diazaphenanthrenes by the Skraup method is presented.     

Use of the radiofrequency-intermodulation distortion technique to investigate intrinsic nonlinearity at the electrode-electrolyte interface

We report on investigations of nonlinear radiofrequency responses of electrolytes with Na(+) and Cl(-) ions placed within gold electrodes of a capacitor. The sample was part of a frequency-adjustable inductance-capacitance-resistance (LCR) parallel resonant circuit, and measurements were carried out using the two frequencies intermodulation distortion technique. We employed double layer model to analyze the observed nonlinearities and their dependence on ionic concentration. Electrode-electrolyte interface polarization was found to be a predominant cause of this intrinsic nonlinearity and to be dependent on electrolytic ion concentration. We also measured and calculated coefficients of resistive and capacitive components of the observed nonlinearity.     

Unlocking the Latent Antimicrobial Potential of Biomimetically Synthesized Inorganic Materials

Inspired by biomineralization, biomimetic approaches utilize biomolecules and synthetic analogs to produce materials of controlled chemistry, morphology, and function under relatively benign conditions. A common characteristic of biological and biomimetic mineral‐forming processes is the generation of mineral/biomolecule nanocomposites. In this work, it is demonstrated that a facile chemical reaction may be utilized to halogenate the nitrogen‐containing moieties of the organics entrapped within bio‐inorganic composites to yield halamine compounds. This process provides rapid and potent bactericidal activity to biomimetically and biologically produced materials that otherwise lack such functionality. Additionally, bio‐inorganic composites containing the chlorinated peptide protamine are effective in rapidly neutralizing Bacillus spores (≥99.97% reduction in colony forming units within 10 min). The straightforward nature of the described process, and the efficacy of halamine compounds in neutralizing biological and chemical agents, provide new applicability to biogenic and biomimetic materials.     

Linear polythioesters. XV. Products of interfacial polycondensation of 1,4-dimercapto-tetramethylbenzene with some aliphatic and aromatic acid dichlorides

New polythioesters by interfacial polycondensation of 1,4-dimercaptomethyl–tetramethylbenzene with oxalyl, succinyl, adipoyl, suberoyl, sebacoyl, and isomeric phthaloyl dichlorides were obtained. To define the optimal conditions for interfacial polycondensation, the influence of the following factors on yield and value of reduced viscosity were studied: type of organic phase, concentration of hydrogen chloride acceptor, the quantitative ratio of aqueous to organic phase, molar ratio of reagents rate of acid chloride addition, contribution of benzyltriethylammonium chloride as a catalyst, and the temperature of the reaction. Thorough studies were carried out only for polycondensation of the dithiol with adipoyl, sebacoyl, and isophthaloyl chlorides. The structure of polythioesters obtained under the model conditions was determined by elementary analysis and infrared spectra. Initial decomposition temperature, mass loss in percentage at the same temperature, maximum rate of decomposition, and mass loss percentage at 100–400°C were defined from the curves of thermogravimetric analysis. Chemical resistance of the polythioesters was determined by treatment with some organic solvents, mineral acids (concentrated and 10%) and sodium hydroxide (10% and 50%). The molecular weight was not measured because of the low solubility of the polythioesters.     

Biological Availability and Preliminary Selenium Speciation in Selenium-Enriched Mycelium of Lentinula edodes (Berk.)

Our goal is to obtain a new food supplement — a chemopreventive preparation derived from selenium (Se)-enriched Lentinula edodes mycelium. In the present study the bioavailability of selenium from Se-enriched mycelium preparations was tested in vitro and in vivo. Three different preparations of selenated mycelium were compared: dried mycelium, lyophilized mycelium, and lyophilized-autolyzed mycelium. In vitro, estimated Se bioavailabilities were 60%, 82%, and 98%, respectively. In vivo bioavailability was determined in rats. As reference, sodium selenite and Se yeast formulations were used at an Se-equivalent dose. The pharmacokinetic data for tested mycelial preparations suggest a rapid but incomplete Se absorption, and rapid elimination, without risk of accumulation. The speciation of selenium in Se-enriched mycelial cultures was carried out by specific oxido-reduction reactions. For tested mycelium the main part of Se was in the 0 and IV oxidation states in inorganic form or combined in a lipid or carbohydrate structure, about 47% was in the –II state in Se-amino acids or in other undefined water- or alcohol soluble organic compounds. Differences in pharmacokinetic data for Se yeast and L. edodes mycelial formulations probably arise from differences in Se speciation. Our data suggest that formulations of selenized Lentinula edodes mycelium could be used in chemoprevention as food supplements.     

Effectiveness of a polyamide film releasing lactic acid on the growth of E. coli O157:H7, Enterobacteriaceae and Total Aerobic Count on vacuum-packed beef

The suitability of a polyamide 6 monolayer film containing lactic acid for use as an antimicrobial package for fresh beef cuts was studied. The release of lactic acid in an aqueous environment was immediate (within 1 h) and was from approx. 55 μg lactic acid/cm² film at 0–8 °C to approx. 67 μg lactic acid/cm² film at 12–20 °C. Beef was contaminated with an Escherichia coli O157:H7 isolate with known minimum inhibitory concentration against lactic acid (0.09% v/v), then wrapped with the lactic-acid polyamide film and vacuum packaged. During storage at 12 °C, the numbers of E. coli were 1 log unit lower than that of a control (untreated polyamide film) and decreased by an additional 1 log during storage for 14 days.     

Study on the Reactions of 3-Benzoyl-2,4,5-pyrrolidinetrione with aliphatic diamines,phenylhydrazine, semicarbazide and guanidine derivatives

3-Benzoyl-2,4,5-pyrrolidinetrione ( 1a , b ) with aliphatic diamines, phenylhydrazine, semicarbazide, and guanidine derivatives yields mono and binary salts ( 4 , 7 , 10 , 11 - 14 ), enamines ( 2 , 3 ), imine ( 5 ), pyrrolo[3,4-c]pyrazole ( 6 ) and pyrrolo [3,4-e][1,4]diazepine ( 8 ), respectively. The influence of the reagents basicity on the route of cyclocondensation is studied.     

Different degrees of malnutrition and immunological alterations according to the aetiology of cirrhosis: a prospective and sequential study

Objectives

In this work we investigated how immunological dysfunction and malnutrition interact in alcoholic and viral aetiologies of cirrhosis.

Methods

To investigate the matter, 77 cirrhotic patients divided in three aetiologies [Alcohol, HCV and Alcohol + HCV) and 32 controls were prospectivelly and sequentially studied. Parameters of humoral immunity (Components 3 and 4 of seric complement and immunoglobulins A M, G and E) and of cellular immunity (total leukocytes and lymphocytes in peripheral blood, T lymphocytes subpopulations, CD4+ and CD8+, CD4+/CD8+ ratio and intradermic tests of delayed hypersensitivity), as well as nutrititional parameters: anthropometric measures, serum albumin and transferrin were evaluated.

Results

Multiple statistical comparisons showed that IgM was higher in HCV group; IgG was significantly elevated in both HCV and Alcohol + HCV, whereas for the Alcohol group, IgE was found at higher titles. The analysis of T- lymphocytes subpopulations showed no aetiologic differences, but intradermic tests of delayed hypersensitivity did show greater frequency of anergy in the Alcohol group. For anthropometric parameters, the Alcohol +HCV group displayed the lowest triceps skinfold whereas creatinine – height index evaluation was more preserved in the HCV group. Body mass index, arm muscle area and arm fat area showed that differently from alcohol group, the HCV group was similar to control.

Conclusion

Significant differences were found among the main aetiologies of cirrhosis concerning immunological alterations and nutritional status: better nutrition and worse immunology for HCV and vice-versa for alcohol.

     

The binding mode of progesterone to its receptor deduced from molecular dynamics simulations

An unambiguous understanding of the binding mode of human progesterone to its receptor still eludes experimental search. According to the X-ray structure of the ligand-binding domain, only one (O3) of the two keto groups at the ligand ends (O3 and O20) should play a role. This result is in conflict with chemical intuition and the results of site-directed mutagenesis experiments. Herein, we report classical molecular dynamics simulations that reveal the dynamic nature of the binding in solution, elucidate the reasons why X-ray studies failed to determine the role of O20, and clarify the effects of the mutations. The predictive power of the force field is ensured by the consistent introduction of a first-principles representation of the ligand.