Chloryl nitrate: a novel product of the OClO + NO3 + M recombination

The products of the reaction of OClO with NO3 were investigated between 220 and 298 K using a flow reactor and infrared, visible, and ultraviolet analysis. At temperatures below 250 K new infrared and ultraviolet absorption features were observed and assigned to the novel compound chloryl nitrate (O2ClONO2). Additionally, ClO and NO2 were observed as reaction products, indicating the existence of a second reaction channel. O2ClONO2 formation predominates at temperatures below 230 K. The reaction rate constant at 220 K is estimated to be on the order of 10(-14) cm3 molecule-1 s-1 in 1-5 Torr of helium. These observations suggest that O2ClONO2 may exist in the terrestrial stratosphere.     

Optimization of simulated moving bed plants with low efficient stationary phases: separation of fructose and glucose

An optimization procedure for simulated moving bed (SMB) plants with low efficient stationary phases is presented. The new aspect is that the desorbent consumption can be cut by 70% by running the plant with lower internal liquid flows and a corresponding larger switch time while the productivity is kept constant. This concept was validated by the separation of fructose and glucose in water on a calcium resin with an eight-column SMB plant. The separation can be predicted well by a true moving bed (TMB) and a simulated moving bed simulation. Adsorption isotherms were determined up to 300 kg/m3 for glucose and 500 kg/m3 for fructose from 25 to 80 degrees C. Experimental SMB runs were performed over a wide range of feed concentrations (10-350 kg/m3) and temperatures (25-80 degrees C). The strong influence of the delay volume is pointed out. For an experimental run with high feed concentration a complete set of data is presented. To reduce biological growth separation at 80 degrees C is recommended.     

An application of activation analysis of aluminum in biological materials

The behavior of aluminum compounds in animals was made clear by using non-destructive neutron activation analysis instead of radiotracer method. Basic aluminum sucrose sulfate (BASS) and dried aluminum hydroxide gel (DAHG) were orally administered to rats. The residual BASS and DAHG on gastric walls of rats were determined by neutron activation analysis. It was obtained the following results that BASS was found at the longer time in the stomach. For reason, it is seemed that BASS is hydrolyzed in gastric juice. And it could not find the aluminum in liver, kidney and spleen.     

Chemical studies on nitrogen heterocyclic skeleton of the Daphniphyllum alkaloids

From a biogenetic point of view, a great variety of related alkaloids isolated from the plant Daphniphyllaceae are related to one another by bond formation or fission. Thus, daphnialcohol acetate (6), a derivative of the degradation products of daphniphylline (1), was subjected to von Braun degradation followed by acid-catalyzed recyclization to give an isomer (8) of daphnialcohol, which has a new type of nitrogen heterocyclic skeleton. Furthermore, daphnilactone-B (3) was converted into a daphniphylline-type compound (19) via a plausible intermediate (21).     

Polymers for DNA delivery

Nucleic acid delivery has many applications in basic science, biotechnology, agriculture, and medicine. One of the main applications is DNA or RNA delivery for gene therapy purposes. Gene therapy, an approach for treatment or prevention of diseases associated with defective gene expression, involves the insertion of a therapeutic gene into cells, followed by expression and production of the required proteins. This approach enables replacement of damaged genes or expression inhibition of undesired genes. Following two decades of research, there are two major methods for delivery of genes. The first method, considered the dominant approach, utilizes viral vectors and is generally an efficient tool of transfection. Attempts, however, to resolve drawbacks related with viral vectors (e.g., high risk of mutagenicity, immunogenicity, low production yield, limited gene size, etc.), led to the development of an alternative method, which makes use of non-viral vectors. This review describes non-viral gene delivery vectors, termed "self-assembled" systems, and are based on cationic molecules, which form spontaneous complexes with negatively charged nucleic acids. It introduces the most important cationic polymers used for gene delivery. A transition from in vitro to in vivo gene delivery is also presented, with an emphasis on the obstacles to achieve successful transfection in vivo.     

Protonation et hydrolyse d'enamine. Epimerisation des immoniums intermediaires

At pH 5 (AcOHAcONa) protonation of the enamine of 3,6,6-trimethylnorpinane 2-one (3-methylnopinone) yields the cis immonium ion 6 (X  OAc), which isomerizes to the thermodynamically more stable trans immonium ion 6′ (X  OAc). Under more strongly acid conditions (aqueous hydrochloric or perchloric acids), the enamonium salts 7 (X  Cl or ClO₄) are formed; these isomerize, with a rate increasing with decreasing acidity to the cis immonium salts 6, stable under these conditions. Epimerization of the cis salt 6 (X  Cl), occurs in ethereal hydrogen chloride, the rate increasing also with decreasing acidity. At pH 5, hydrolysis of the enamine yields 3-methylnopinone, the proportion of the less thermodynamically stable trans isomer increasing with a rise in reaction temperature.     

Silicon clusters: chemistry and structure

The chemical reactions of size selected silicon cluster ions (containing up to 70 atoms) have been studied with a number of different reagents using injected ion drift tube techniques. Both kinetic and equilibrium measurements have been performed as a function of temperature, and the influence of cluster annealing on chemical reactivity explored. Unlike metal clusters, where bulk behavior appears to be approached with around 30 atoms, large silicon clusters (n up to 70) are much less reactive than bulk silicon surfaces. These results suggest that the clusters in the size range examined here are not small crystals of bulk silicon, but have compact, high coordination number structures with few dangling bonds.     

Facile chemoselective synthesis of dehydroalanine-containing peptides

Useful methodology is described for the synthesis of dehydroalanine residues (II) within peptides. The unnatural amino acid (Se)-phenylselenocysteine (I) can be incorporated into growing peptide chains via standard peptide synthesis procedures. Subsequent oxidative elimination affords a dehydroalanine at the desired position. The oxidation conditions are mild and tolerate functionalities commonly found in peptides, including variously protected cysteine residues. To illustrate its utility, cyclic lanthionines have been synthesized by this method.     

Molar volumes and ion pairing of lithium halides in alcohols

The concentration dependence of the apparent molar volumes of lithium halides (and electrolytes in general) in alcohols (and solvents permitting association in general) is, in the first instance, due to changes in the degree of association and to the inherent difference between the apparent molar volumes of the ions and of the ion pairs. Previous publications on the molar volumes of electrolytes in organic solvents, disregarding altogether ion pairing, appear to be incorrect. Data from the literature for lithium chloride and lithium bromide in normal primary alcohols and several branched alcohols from C₁ to C₈ and data from our laboratory for lithium halides in 1-hexanol and 2-ethyl-1-hexanol served for the determination of φ _V and φ _E . Electrical and structural contributions to the values of these functions for the ions and for the ion pairs are discussed.