Synthesis of 2-Chloromethyl-5-aryl-, 2-Chloromethyl-5-(5-methyl-2-furyl)-, and 2-Chloromethyl-5-(1,5-dimethyl-2-pyrrolyl)-1,3,4-oxadiazoles from Tetrazole Derivatives

Acetylation of 5-aryltetrazoles, 5-(5-methyl-2-furyl)tetrazole, and 5-(1,5-dimethyl-2-pyrrolyl)tetrazole with chloroacetyl chloride was studied.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 5, 2005, pp. 787–789.Original Russian Text Copyright © 2005 by Baranov, Tsypin, Malin, Laskin.     

Synthesis and photophysics of one mononuclear Mn(III) and one dinuclear Mn(III,III) complex covalently linked to a ruthenium(II) tris(bipyridyl) complex

The preparation of donor (D)-photosensitizer (S) arrays, consisting of a manganese complex as D and a ruthenium tris(bipyridyl) complex as S has been pursued. Two new ruthenium complexes containing coordinating sites for one (2a) and two manganese ions (3a) were prepared in order to provide models for the donor side of photosystem II in green plants. The manganese coordinating site consists of bridging and terminal phenolate as well as terminal pyridyl ligands. The corresponding ruthenium-manganese complexes, a manganese monomer 2b and dimer 3b, were obtained. For the dimer 3b, our data suggest that intramolecular electron transfer from manganese to photogenerated ruthenium(III) is fast, k(ET) > 5 x 10(7) s(-)(1).     

A top-down approach to protein structure studies using chemical cross-linking and Fourier transform mass spectrometry

In a preliminary communication we described a top-down approach to the determination of chemical cross-link location in proteins using Fourier transform mass spectrometry (FT-MS). We have since extended the approach to use a series of homobifunctional cross-linkers with the same reactive functional groups, but different cross-linker arm lengths. Correlating cross-linking data across a series of related linkers allows the distance constraint derived from a cross-link between two reactive side chains to be determined more accurately and increases the confidence in the assignment of the cross-links. In ubiquitin, there are seven lysines with primary amino groups and the amino terminus. Disuccinimidyl suberate (DSS, cross-linker arm length = 11.4 A), disuccinimidyl glutarate (DSG, cross-linker arm length = 7.5 A) and disuccinimidyl tartrate (DST, cross- linker arm length = 5.8 A) are homobifunctional cross-linking reagents that react specifically with primary amines. Using tandem mass spectrometry (MS/MS) on the singly, internally cross-linked precursor ion of ubiquitin, we found cross-links with DSS and DSG between the amino terminus and Lys 6, between Lys 6 and Lys 11, and between Lys 63 and Lys 48. Using disuccinimidyl tartrate (DST), the shortest cross-linker in the series, only the cross-links between the amino terminus and Lys 6, and between Lys 6 and Lys 11 were observed. The observed cross-links are consistent with the crystal structure of ubiquitin, if the lysine side chains and the amino terminus are assumed to have considerable flexibility. In a separate study, we probed the reactivity of the primary amino groups in ubiquitin using the amino acetylating reagent, N-hydroxy succinimidyl acetate (NHSAc), and a top-down approach to localize the acetylated lysine residues. The reactivity order obtained in that study (M1 approximate, equals K6 approximate, equals K48 approximate, equals K63) > K33 > K11 > (K27, K29), shows that the cross-link first formed in ubiquitin by reaction with DSS and DSG occurs between the most reactive residues.     

Capillary electrophoretic separation of sugars in fruit juices using on-line mid infrared Fourier transform detection

Fourier Transform infrared spectroscopy has been coupled to on-line capillary electrophoresis (CE) for the separation and detection of natural sugars in orange fruit juices. The CE separation electrolyte comprised 50 mM sodium carbonate buffer adjusted to pH 12.3 with NaOH. Galactose was selected as an internal standard. To ensure tight connections between the custom-made IR-transparent flow cell (optical path length was 15 [micro sign]m) and the fused silica capillaries, commercially available O-rings were used. The scanner of the spectrometer was operated at a HeNe laser modulation frequency of 320 kHz, recording interferograms in a double-sided, forward-backward mode with 8 cm(-1) spectral resolution. For each spectrum 64 interferograms (512 for the background) were co-added and a Blackman-Harris 3-term apodization function was performed. A low-pass filter at 1828 cm(-1) was inserted in the IR beam to increase the light throughput in the spectral region of interest (1800 cm(-1)-900 cm(-1)). Using these features a new spectrum could be obtained every two seconds. Sucrose, glucose and fructose were structurally identified and quantified in orange juice samples. The limits of detection (3S/N) for all analytes were in the low millimolar range (0.7-1.9 mM) or, in absolute amounts, the low nanogram range (1.5-3.2 ng). The resolution ranged between 1.14 to 3.15 and the RSD of the proposed method was 1.8-4.4%.     

Influence of crosslinker identity and position on gas-phase dissociation of lys-lys crosslinked peptides

A systematic study of the dissociation patterns of crosslinked peptides analyzed by tandem mass spectrometry is reported. A series of 11-mer peptides was designed around either a polyalanine or polyglycine scaffold with arginine at the C terminus. One or two lysine residues were included at various locations within the peptides to effect inter- or intra-molecular crosslinking, respectively. Crosslinked species were generated with four commonly used amine-specific chemical crosslinking reagents: disuccinimidyl suberate (DSS), disuccinimidyl tartarate (DST), dithiobis(succinimidylpropionate) (DSP), and disuccinimidyl glutarate (DSG). The influence of precursor charge state, location of crosslink, and specific crosslinking reagent on the MS/MS dissociation pattern was examined. Observed trends in the dissociation patterns obtained for these species will allow for improvements to software used in the automated interpretation of crosslinked peptide MS/MS data.     

Reformulation of general relativity as a gauge theory

The starting point is a spinor affine space-time. At each point, two-component spinors and a basis in spinor space, called “spin frame,” are introduced. Spinor affine connections are assumed to exist, but their values need not be known. A metric tensor is not introduced. Global and local gauge transformations of spin frames are defined with GL(2) as the gauge group. Gauge potentials B_μ are introduced and corresponding fields F_μν are defined in analogy with the Yang-Mills case. Gravitational field equations are derived from an action principle. Incases of physical interest SL(2, C) is taken as the gauge group, instead of GL(2). In the special case of metric space-times the theory is identical with general relativity in the Newman-Penrose formalism. Linear combinations of B_μ are generalized spin coefficients, and linear combinations of F_μν are generalized Weyl and Ricci tensors and Ricci scalar. The present approach is compared with other formulations of gravitation as a gauge field.     

Investigation of the combustion of fumes of organochlorine wastes in oxygen environment

An experimental study of the kinetic stage of combustion fumes of organochlorine wastes. We obtained the data on the normal speed of propagation of the flame, and other parameters of the flame front. Also we found an effective constant of the reaction rate and determined requirements for reactors of a high-temperature oxidation of organochlorine waste.     

Field theory onR×S 3 topology. III: The Dirac equation

A Dirac-type equation on R×S ³ topology is derived. It is a generalization of the previously obtained Klein-Gordon-type, Schrödinger-type, and Weyl-type equations, and reduces to the latter in the appropriate limit. The (discrete) energy spectrum is found and the corresponding complete set of solutions is given as expansions in terms of the matrix elements of the irreducible representations of the group SU ₂ . Finally, the properties of the solutions are discussed.     

Molecular modeling of interfaces between cellulose crystals and surrounding molecules: Effects of caprolactone surface grafting

A technical problem in cellulosic nanocomposite materials is the weak interaction between hydrophilic cellulose and hydrophobic polymer matrices. One approach to solve this difficulty is to chemically graft monomers of the matrix polymer onto the cellulose surface. An important question is to understand the effect such surface modification has on the interfacial properties. Semi-empirical approaches to estimate work of adhesion based on surface energies do not provide information on specific molecular interactions. Details about these interactions were obtained using molecular dynamics (MD) simulation. Cellulose interfaces with water and caprolactone medium were modeled with different amounts of grafted caprolactone. The modification lead to an increased work of adhesion between the surface and its surrounding medium. Furthermore, the MD simulations showed that the interaction between cellulose, both modified and non-modified, and surrounding medium is dominated by Coulomb interactions, predominantly as hydrogen bonds.