Heterovalent selectivity and the combinatorial advantage

Libraries of monovalent compounds can be reacted with each other to give libraries of bivalent ones. If those reactions are efficient, and if the products do not need to be purified, large numbers of bivalent compounds can be produced rapidly, and one might say there is a "combinatorial advantage" to doing so. However, selective formation of heterobivalent products must be possible otherwise statistical mixtures will form. This tutorial review describes methods that will give heterobivalent compounds almost exclusively. Although there are relatively few methods that will give that desired selectivity, such methods are becoming increasingly important as the potential applications of bi- and multivalent compounds emerge.     

A fluorimetric kinetic method for the determination of tonin activity in rat submaxillary glands

A method for the kinetic determination of tonin activity in rat submaxillary gland extracts is described. The method is based on the fluorogenic reaction of o-phthalaldehyde with the dipeptide histidyl-leucine generated in the enzymatic hydrolysis of angiotensin I. The reaction is monitored by fluorescence at 440 nm. At pH 7.5, the method allows the determination of 2–15 nmol/ml histidyl-leucine with relative standard deviation of 6%.     

Aqueous biphasic olefin hydroformylation catalyzed by water-soluble rhodium complexes

Catalysis with water-soluble rhodium complexes, RhCl(CO)(TPPMS)₂, [TPPMS = P(C₆H₅)₂(C₆H₄SO₃)] (1), RhCl(CO)(TPPDS)₂, [TPPDS = P(C₆H₅)(C₆H₄SO₃)₂] (2) and RhCl(CO)(TPPTS)₂, [TPPTS = P(C₆H₄SO₃)₃] (3) in hydroformylation of 1-hexene, 2-pentene, 2,3-dimethyl-1-butene, cyclohexene and several mixtures of these olefins have been studied, under moderate reaction conditions (T: 50–150 °C; pCO/pH₂ = 1; total p: 14–68 bar; Substrate/Catalyst: 600/1) in biphasic toluene/water media. The catalytic system shows high activity but low selectivity. The linear and branched oxygenated products obtained are equally useful in naphtha upgrading, as observed in the real El Palito naphtha tried. The catalysts can be recycled several times without significant activity loss.     

Diels-Alder Reactions of 2-Oxazolidinone Dienes in Polar Solvents Using Catalysis or Non-conventional Energy Sources

Summary. The (Z)-N-substituted 4-methylene-5-propylidene-2-oxazolidinone dienes were prepared by a one-step synthesis, starting from 2,3-hexanedione and isocyanates. Diels-Alder cycloadditions of these dienes were carried out in the presence of the dienophiles methyl vinyl ketone, methyl propiolate, and a captodative olefin, under conditions such as solvents of high polarity, Lewis acid catalysis, and non-conventional energy sources. The reactions carried out either with mixtures of H₂O/MeOH or under BF₃·Et₂O catalysis yielded the highest regio- and stereoselectivities. The use of ionic liquids, microwaves, and ultrasound did not significantly increase the selectivity.     

Development and implementation of the k0-standardization and other parametric methods of INAA in Cuba. Part I

This paper explains chronologically the implementation of thek ₀-standardization and other parametric methods in Cuba. Fundamental and applied results in the determination of the most important parameters are obtained, using the IBR-2 at Dubna and Triga Mark III at Mexico reactor facilities. Some modifications in the Stoughton-Halpering convention, and its comparison with the modified Westcott and Høgdahl method are presented. The application of the described methods at the CS-ISCTN low flux facility, using the big samples techniques, is presented.     

Toward Understanding the Molecular Recognition of Fungal Chitin and Activation of the Plant Defense Mechanism in Horticultural Crops

Large volumes of fruit and vegetable production are lost during postharvest handling due to attacks by necrotrophic fungi. One of the promising alternatives proposed for the control of postharvest diseases is the induction of natural defense responses, which can be activated by recognizing molecules present in pathogens, such as chitin. Chitin is one of the most important components of the fungal cell wall and is recognized through plant membrane receptors. These receptors belong to the receptor-like kinase (RLK) family, which possesses a transmembrane domain and/or receptor-like protein (RLP) that requires binding to another RLK receptor to recognize chitin. In addition, these receptors have extracellular LysM motifs that participate in the perception of chitin oligosaccharides. These receptors have been widely studied in Arabidopsis thaliana (A. thaliana) and Oryza sativa (O. sativa); however, it is not clear how the molecular recognition and plant defense mechanisms of chitin oligosaccharides occur in other plant species or fruits. This review includes recent findings on the molecular recognition of chitin oligosaccharides and how they activate defense mechanisms in plants. In addition, we highlight some of the current advances in chitin perception in horticultural crops.     

Platinum(II)-Based Optical Probes for Imaging Quadruplex DNA Structures via Phosphorescence Lifetime Imaging Microscopy

G-quadruplex DNA is a non-canonical structure that forms in guanine-rich regions of the genome. There is increasing evidence showing that G-quadruplexes have important biological functions, and therefore molecular tools to visualise these structures are important. Herein we report on a series of new cyclometallated platinum(II) complexes which, upon binding to G-quadruplex DNA, display an increase in their phosphorescence, acting as switch-on probes. More importantly, upon binding to G-quadruplexes they display a selective and distinct lengthening of their emission lifetime. We show that this effect can be used to selectively visualise these structures in cells using Phosphorescence Lifetime Imaging Microscopy (PLIM).     

A direct carbon-13 and nitrogen-15 NMR study of europium(III) complexation-nitrate and europium(III)-isothiocyanate complexation in aqueous solvent mixtures

A direct, low-temperature nuclear magnetic resonance spectroscopic study of europium(III)-nitrate contact ion-pairing has been completed, and preliminary results for europium(III)-isothiocyanate have been obtained. In water-acetone-Freon mixtures, at –110°C to –120°C, four¹⁵N NMR signals are observed for coordinated nitrate ion. Area evaluations of the signals and their concentration dependence indicate the formation of Eu(NO₃)²⁺, Eu(NO₃) ₂ ¹⁺ , and two higher complexes, possibly the tetra-, with either the penta-or hexanitrato. This correlates well with similar¹⁵N NMR results obtained for Ce(III), Pr(III), Nd(III), and Sm(III). As a result of a higher dielectric constant, complex formation is significantly less in water-methanol mixtures, wheein only three complexes form with Eu(NO₃) ₂ ¹⁺ dominating at the highest anion concentrations. Competitive complexing experiments in water-methanol also were made by³⁵Cl NMR chemical shift and linewidth measurements, as well as¹⁵N NMR. Initial experiments with the Eu³⁺-NCS^– system show four coordinated anion signals, displaced from the bulk anion peak by about –250 ppm and –2,500 ppm in the¹³C and¹⁵N NMR spectra, respectively. Area evaluations are consistent with the presence of Eu(NCS)²⁺ through Eu(NCS) ₄ ^1- in these solutions. A consideration of the chemical shifts identified the nitrogen atom as the site of binding in the NCS^–. A discussion of these preliminary results, as well as those for several other metal-ions, will be presented.     

Ordered mesoporous silicates of MCM-41 type as support of pt catalysts for the enantioselective hydrogenation of 1-phenyl-1,2-propanedione

Summary Platinum catalysts (1 wt.%) supported on MCM-41 type and SiO₂have been prepared, characterized and evaluated in the enantioselective hydrogenation of 1-phenyl-1,2-propanedione at 298 K and 20 bar of hydrogen pressure, using cinchonidine (CD) as chiral modifier. Chemisorption and TEM results revealed that both catalysts posses similar metal dispersion, however, significant differences in the catalytic behavior were observed. With dichloromethane as solvent, high hydrogenation rates and ee values around 47% were obtained for the Pt/MCM-41 catalyst. This fact is attributed to a confinement effect. The initial reaction rate is strongly dependent on the CD concentration, and the reaction rate (or ee) vsCD concentration plot exhibits bell-type curves. The main products were (R) -1-hydroxy-1-phenylpropanone and (S) -1-hydroxy-1-phenylpropanone.</o:p>