Palladium salicylaldimine complexes containing boronate esters

Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na₂PdCl₄ afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC₆H₄C(O)H) with H₂NC₆H₄Bpin (pin=1,2-O₂C₂Me₄) afforded the boron-containing Schiff bases, 2-HOC₆H₄C(H)=NC₆H₄Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na₂PdCl₄ afforded complexes of the type PdL₂ (4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus.     

Experimental and theoretical studies of rate coefficients for the reaction O(3P)+CH3OH at high temperatures

Rate coefficients of the reaction O((3)P) + CH(3)OH in the temperature range of 835-1777 K were determined using a diaphragmless shock tube. O atoms were generated by photolysis of SO(2) with a KrF excimer laser at 248 nm or an ArF excimer laser at 193 nm; their concentrations were monitored via atomic resonance absorption excited by emission from a microwave-discharged mixture of O(2) and He. The rate coefficients determined for the temperature range can be represented by the Arrhenius equation, k(T) = (2.29 +/- 0.18) x 10(-10) exp[-(4210 +/- 100)T] cm(3) molecule(-1) s(-1); unless otherwise noted, all the listed errors represent one standard deviation in fitting. Combination of these and previous data at lower temperature shows a non-Arrhenius behavior described as the three-parameter equation, k(T) = (2.74 +/- 0.07) x 10(-18)T(2.25 +/- 0.13) exp[-(1500 +/- 90)T] cm(3)molecule(-1) s(-1). Theoretical calculations at the Becke-3-Lee-Yang-Parr (B3LYP)6-311 + G(3df,2p) level locate three transition states. Based on the energies computed with coupled clusters singles, doubles (triples) [CCSD(T)]/6-311 + G(3df,2p)B3LYP6-311 + G(3df,2p), the rate coefficients predicted with canonical variational transition state theory with small curvature tunneling corrections agree satisfactorily with the experimental observations. The branching ratios of two accessible reaction channels forming OH + CH(2)OH (1a) and OH + CH(3)O (1b) are predicted to vary strongly with temperature. At 300 K, reaction (1a) dominates, whereas reaction (1b) becomes more important than reaction (1a) above 1700 K.     

Stereochemically stable double-helicate dinuclear complexes of bis(dipyrromethene)s: a chiroptical study

Helical zinc(II) complexes of bis(dipyrromethene)s bearing homochiral amide substituents were synthesized. Analysis of the products by chiral HPLC showed two diastereomeric major products and showed that dipyrromethene double-nuclear helicates are stereochemically stable and do not interconvert. Circular dichroism (CD) studies showed that the complexation reactions had proceeded with modest diastereomeric excesses. Analysis of an analogous symmetric zinc(II) bis(dipyrromethene) lacking homochiral substituents that could act as chromophores discounted induced CD by the chiral auxiliaries.     

Stereoselective 1,2-cis glycosylation of 2-O-allyl protected thioglycosides

The technique of intramolecular aglycon delivery (IAD), whereby a glycosyl acceptor is temporarily appended to a hydroxyl group of a glycosyl donor is an attractive method that can allow the synthesis of 1,2-cis glycosides in an entirely stereoselective fashion. 2-O-Allyl protected thioglycoside donors are excellent substrates for IAD, and may be glycosylated stereoselectively through a three-step reaction sequence. This sequence consists of quantitative yielding allyl bond isomerisation, to produce vinyl ethers that can then undergo N-iodosuccinimide mediated tethering of the desired glycosyl acceptor, and subsequent intramolecular glycosylation, to yield either alpha-glucosides or beta-mannosides accordingly. Although attempted one-pot tethering and glycosylation is hampered by competitive intermolecular reaction with excess glycosyl acceptor, this problem can be simply overcome by the use of excess glycosyl donor. Allyl mediated IAD is a widely applicable practical alternative to other IAD approaches for the synthesis of beta-mannosides, that is equally applicable for alpha-gluco linkages. It is advantageous in terms of both simplicity of application and yield, and in addition has no requirement for cyclic 4,6-protection of the glycosyl donor.     

Determination of capsaicinoids in salsa by liquid chromatography and enzyme immunoassay

Two simple and rapid methods were developed to monitor pungency of salsa in production. Capsaicin (C) and dihydrocapsaicin (DHC) were quantitated in 17 commercially available tomato-based salsas by enzyme immunoassay (EIA) and liquid chromatography (LC) with fluorescent detection. Samples were extracted with methanol and the extracts were subjected to solid-phase extraction (SPE) using polystyrene-divinylbenzene columns. Analysis of SPE eluates showed good correlation (r2 = 0.953) between LC and EIA, with a slightly high bias for EIA. Salsa fortified with C and DHC from 0.118 to 103.2 microg/g resulted in recoveries of 90-112% (C) and 76-97% (DHC). Limits of detection by LC were 0.1 microg/g for each capsaicinoid and 0.1 microg/g by EIA for total capsaicinoids. The LC on-column response was linear from 0.2 to 100 ng for both C and DHC, whereas the working range for EIA was 0.1-2.0 ppm. Pungency varied between different salsa brands labeled mild, medium, and hot.     

The role of vanadium bromoperoxidase in the biosynthesis of halogenated marine natural products

Halogenated natural products are frequently reported metabolites in marine seaweeds. These compounds span a range from halogenated indoles, terpenes, acetogenins, phenols, etc., to volatile halogenated hydrocarbons that are produced on a very large scale. In many cases these halogenated marine metabolites possess biological activities of pharmacological interest. Given the abundance of halogenated marine natural products found in marine organisms and their potentially important biological activities, the biogenesis of these compounds has intrigued marine natural product chemists for decades. Over a quarter of a century ago, a possible role for haloperoxidase enzymes was first suggested in the biogenesis of certain halogenated marine natural products, although this was long before haloperoxidases were discovered in marine organisms. Since that time, FeHeme- and Vanadium-haloperoxidases (V-HPO) have been discovered in many marine organisms. The structure and catalytic activity of vanadium haloperoxidases is reviewed herein, including the importance of V-HPO-catalyzed bromination and cyclization of terpene substrates.     

The use of comet assay data with a simple reaction mechanism to evaluate the relative effectiveness of free radical scavenging by quercetin, epigallocatechin gallate and N-acetylcysteine in UV-irradiated MRC5 lung fibroblasts

Comet assay data (tail DNA %) have been gathered for the concentration dependent role of three antioxidants (AOs); quercetin (Q), epigallocatechin gallate (EGCG) and N-acetylcysteine (NAC) in reducing UV-induced damage to DNA in normal fetal lung fibroblasts (MRC5). All three compounds demonstrate a concentration dependent reduction maximum with a pro-oxidant effect at higher (though not cytotoxic) concentrations. Manipulation of a simple 4-step reaction mechanism for free radical (FR) scavenging by AOs produced rate constant ratios which allowed the relative effectiveness (Q > EGCG > NAC) of the AOs to be evaluated.     

Dinuclear zinc(II) double-helicates of homochirally substituted bis(dipyrromethene)s

[structure: see text] A series of bis(dipyrromethene)s substituted with aromatic amide and aliphatic ester homochiral auxiliaries have been prepared and complexed with zinc(II) ions to form double-helical dinuclear complexes. CD analysis of the crude complexes revealed that the helicates formed in a diastereoselective manner. The helicates have been resolved into their constituent M and P helices by HPLC, indicating that the helical sense of the complexes is stable to racemization.