Mixing of electronic states in molybdenum complexes involved in nitrogen activation

The mechanism for nitrogen activation by molybdenum complexes is a complicated one, involving as it does the coupling of a quartet molybdenum reactant with a singlet nitrogen molecule, passing via a series of quartet and doublet encounter complexes to a triplet intermediate, with the subsequent spin crossing to the singlet surface which then leads via a singlet transition state to the final pair of singlet products. We have investigated in detail a variety of levels of theory to describe the crossing of these electronic surfaces and have calculated both lower-bound and actual minimum energy crossing points for the key spin inversion processes.     

S‐Alkylation of Soft Scorpionates

The alkylation reactions of soft scorpionates are reported. The hydrotris(S‐alkyl‐methimazolyl)borate dications (alkyl=methyl, allyl, benzyl), which were prepared by the reaction of Tm^Me anion and primary alkyl halides, have been isolated and structurally characterised. The reaction is, however, not universally successful. DFT analysis of these alkylation reactions (C?S versus B? H alkylation) indicates that the observed outcome is driven by kinetic factors. Extending the study to incorporate alternative imine thiones (mercaptobenzothiazole, bz; thiazoline, tz) led to the structural characterisation of di[aquo‐μ‐aquohydrotris(mercaptobenzothiazolyl)boratosodium], which contains sodium atoms in the κ³‐S,S,S coordination mode. Alkylation of Na[Tbz] and Na[tzTtz] leads to decomposition resulting in the formation of the simple S‐alkylated heterocycles. The analysis of the species involved in these reactions shows an inherent weakness in the B? N bond in soft scorpionates, which has implications for their use in more advanced chemistry.     

A rapid and convenient method for preparative separation of three indissolvable polyphenols from Euphorbia pekinensis by the flexible application of solvent extraction combined with counter‐current chromatography

A rapid and convenient method was established to preparatively isolate the three ellagic acid types of compounds, which were the main polyphenols in Euphorbia pekinensis, by flexibly applying solvent extraction combined with counter‐current chromatography (CCC). The total extract (extracted using 95% ethanol) of E. pekinensis was pretreated by two simple steps before CCC isolation, following the procedure: the total extract was extracted by classical solvent extraction using petroleum ether and ethyl acetate, respectively, and then the ethyl acetate extract was suspended using 95% ethanol, after being allowed to stand overnight, the sediment was obtained. Partial sediment (100 mg) was then directly separated by CCC with a two‐phase solvent system composed of chloroform‐95% ethanol‐water‐85% formic acid (50:50:50:5, v/v/v/v). About 22 mg of 3,3′‐dimethoxy ellagic acid (1), 12 mg of 3,3′‐di‐O‐methyl‐4‐O‐(β‐d ‐xylopyranosyl)ellagic acid (2), and 35 mg of ellagic acid (3) with purities of 96.0, 95.2, and 95.4% were obtained respectively in one step within 4 h. After being purified by washing with methanol, the purities of the three compounds obtained were all above 98%. The purities were determined by HPLC and their chemical structures were further identified by ¹H and ¹³C NMR spectroscopy. The recoveries were calculated as 84.6, 85.7, and 89.5%, respectively. The result demonstrated that the present isolation method was rapid, economical and efficient for the preparative separation of polyphenols from E. pekinensis.     

A Simple Strategy for the Preparation of 6-Substituted 3H-Benzoxazol-2-ones and 3H-Benzothiazol-2-ones

The double metallation of 6-bromo-3H-benzothiazol-2-one and 6-bromo-3H-benzoxazol-2-one with methyl magnesium bromide and alkyllithium bases is described. Alkylation with a variety of electrophiles occurs at the 6-position of the heterocycles in good yields.      

Radioimmunoassay of PCBs in Milk and Blood

A radioimmunoassay was developed capable of determining Aroclor 1260 in milk at levels of from 20 to 80 ppb and in blood from 2 to 16 ppb. The values obtained by radioimmunoassay correlate well with those determined by gas-liquid chromatography (r² = 0.96 for milk and 0.99 for blood) but were lower. Antiserum was produced in rabbits and was specific for 2, 2′, 4, 4′, 5, 5′-hexachlorobiphenyl. It cross-reacted with congeners and isomers in Aroclor 1254 and 1260 to the extent that a 20% decrease in binding was observed with 0.1 ng of either mixture. The method requires preliminary cleanup of the extract on alumina and utilizes 25 % dimethyl sulfoxide in the assay medium to promote solubilization of the substrates.     

Conformational Analysis of the 1,3‐Oxaphosphorinanes Formed from α,β‐Unsaturated Aldehydes and the (Hydroxymethyl)phosphines RP(CH2OH)2 (R = Ph or CH2OH)

Equimolar reactions of cinnamaldehyde or its 3,5‐dimethoxy‐4‐hydroxy derivative (sinapaldehyde) with RP(CH₂OH)₂ (R = Ph or CH₂OH) were studied in MeOH or CD₃OD at room temperature by NMR spectroscopy. In MeOH, nucleophilic attack of the phosphine at the C?C bond, with concomitant loss of CH₂O, affords the tertiary phosphine HOCH₂P(R)CH(Ar)CH₂CHO ( 3 ) that rapidly converts mainly into a 1,3‐oxaphosphorinane derivative ( 5 ) formed as a mixture of four diastereomers. Conformational analysis reveals that the Ar group in these is exclusively in an equatorial position while the OH and R groups can be equatorial‐oriented or axial‐oriented. In CD₃OD, 1,3‐oxaphosphorinanes monodeuterated in the C5 position are obtained as a mixture of eight diastereomers where the dominate diastereomers have an axial D‐atom. Diastereomeric ratios depend on the nature of the Ar and R groups.     

Interphotoreceptor Retinoid‐Binding Protein Protects Retinoids from Photodegradation

Retinol degrades rapidly in light into a variety of photoproducts. It is remarkable that visual cycle retinoids can evade photodegradation as they are exchanged between the photoreceptors, retinal pigment epithelium and Müller glia. Within the interphotoreceptor matrix, all‐trans retinol, 11‐cis retinol and retinal are bound by interphotoreceptor retinoid‐binding protein (IRBP). Apart from its role in retinoid trafficking and targeting, could IRBP have a photoprotective function? HPLC was used to evaluate the ability of IRBP to protect all‐trans and 11‐cis retinols from photodegradation when exposed to incandescent light (0 to 8842 μW cm^?2); time periods of 0–60 min, and bIRBP: retinol molar ratios of 1:1 to 1:5. bIRBP afforded a significant prevention of both all‐trans and 11‐cis retinol to rapid photodegradation. The effect was significant over the entire light intensity range tested, and extended to the bIRBP: retinol ratio 1:5. In view of the continual exposure of the retina to light, and the high oxidative stress in the outer retina, our results suggest IRBP may have an important protective role in the visual cycle by reducing photodegradation of all‐trans and 11‐cis retinols. This role of IRBP is particularly relevant in the high flux conditions of the cone visual cycle.     

A New and Facile Synthesis of Novel Pyrazolothienopyrimidines and Imidazopyrazolothienopyrimidines

4‐Amino‐3‐methyl‐1‐phenyl‐1H‐thieno[2,3‐c]pyrazole‐5‐carboxamide ( 5 ), which was synthesized by an innovative method, was used as a versatile precursor for synthesizing pyrazolothienopyrimidines and imidazopyrazolothienopyrimidines compounds. Reaction of amino thienopyrazole carboxamide 5 with triethyl orthoformate afforded thienopyrazolopyrimidine 6 . Chlorination of the latter compound, using phosphorus oxychloride afforded the chloro pyrazolothienopyrimidine 7 , which underwent nucleophilic substitution reactions with various primary and secondary amines to give the alkyl (aryl) amino pyrimidine compounds 8a–d . On the other hand, the reaction of chloropyrimidine 7 with thiourea afforded the pyrimidine thione compound 9 , which was alkylated with α‐halogentaed compounds to afford the S‐alkylated derivatives 10a–c . Also, chloroacetylation of the amino carboxamide 5 using chloroacetyl chloride yielded the chloromethyl pyrazolothienopyrimidine 12 , which underwent nucleophilic substitu‐ tion reactions with various primary and secondary amines to afford the alkyl (aryl) aminomethyl compounds 13a–f . The latter Compounds underwent Mannich reaction to give imidazopyrimidothieno‐ pyrazoles 14a–c . The newly synthesized compounds and their derivatives were fully characterized by elemental and spectral analysis.     

The influence of ionic strength on the interaction of viruses with charged surfaces under environmental conditions

The influence of ionic strength on the electrostatic interaction of viruses with environmentally relevant surfaces was determined for three viruses, MS2, Q beta, and Norwalk. The virus is modeled as a particle comprised of ionizable amino acid residues in a shell surrounding a spherical RNA core of negative charge, these charges being compensated for by a Coulomb screening due to intercalated ions. A second model of the virus involving surface charges only is included for comparison. Surface potential calculations for each of the viruses show excellent agreement with electrophoretic mobility and zeta potential measurements as a function of pH. The environmental surface is modeled as a homogeneous plane held at constant potential with and without a finite region (patch) of opposite potential. The results indicate that the electrostatic interaction between the virus and the oppositely charged patch is significantly influenced by the conditions of ionic strength, pH and size of the patch. Specifically, at pH 7, the Norwalk virus interacts more strongly with the patch than MS2 (approximately 51 vs approximately 9kT) but at pH 5, the Norwalk-surface interaction is negligible while that of MS2 is approximately 5.9kT. The resulting ramifications for the use of MS2 as a surrogate for Norwalk are discussed.