Structure-Reactivity Correlations of Benzoin Alkyl Ethers. Structures of 2-Methoxy-1,2-diphenylethanone (I) and 2-Isopropoxy-1,2-diphenylethanone (II)

(I): C15H1402, Mr---226.27, triclinic, Pi,a=8.441 (2), b= 10.276 (1), c= 15.342 (2)A, a=91.02 (2), ~ t= 79.26 (2), y= 105.88 (2) °, V=1256.8 (4)A 3, Z=4, D,,= 1.209 (flotation in KI),D x - 1.195 g cm -3, #(Mo, 2 = 0.7107/~) = 0.44 cm -~,F(000) = 480, T= 293 K, R -- 0.060 for 1793 significant reflections. (II): C~THlsO2, Mr= 254.83, orthorhombic, Pca21, a=8.476 (1); b= 16.098 (3), c=10.802(3)A, V=1473.9 (5) A s, Z=4, Dm=1.161 (flotation in KI), Dx= 1.148gem -3, /~(Mo, 2=0.7107 A) =0.41 cm -~, F(000) = 544, T= 293 K, R = 0.071 for 867 significant reflections. Both (I) and (II) crystallize in a cisoid conformation for the carbonyl group and alkoxy groups. Compounds (I) and (II) are photostable on irradiation in the solid state in spite of the favourable conformation of the functional groups for intramolecular H abstraction. Absence of photoreaction of (I)and (II) in the solid state is rationalized in the light of unfavourable intramolecular geometry.

A Triggering Mechanism for Enhanced Star-Formation in Colliding Galaxies

We propose a physical mechanism to explain the origin of the intense burst of massive-star formation seen in colliding/merging, gas-rich, field spiral galaxies. We explicitly take account of the different parameters for the two main mass components, H-2 and H I, of the interstellar medium within a galaxy and follow their consequent different evolution during a collision between two galaxies. We also note that, in a typical spiral galaxy-like our galaxy, the Giant Molecular Clouds (GMCs) are in a near-virial equilibrium and form the current sites of massive-star formation, but have a low star formation rate. We show that this star formation rate is increased following a collision between galaxies. During a typical collision between two field spiral galaxies, the H I clouds from the two galaxies undergo collisions at a relative velocity of approximately 300 km s-1. However, the GMCs, with their smaller volume filling factor, do not collide. The collisions among the H I clouds from the two galaxies lead to the formation of a hot, ionized, high-pressure remnant gas. The over-pressure due to this hot gas causes a radiative shock compression of the outer layers of a preexisting GMC in the overlapping wedge region. This makes these layers gravitationally unstable, thus triggering a burst of massive-star formation in the initially barely stable GMCs.The resulting value of the typical IR luminosity from the young, massive stars from a pair of colliding galaxies is estimated to be approximately 2 x 10(11) L., in agreement with the observed values. In our model, the massive-star formation occurs in situ in the overlapping regions of a pair of colliding galaxies. We can thus explain the origin of enhanced star formation over an extended, central area approximately several kiloparsecs in size, as seen in typical colliding galaxies, and also the origin of starbursts in extranuclear regions of disk overlap as seen in Arp 299 (NGC 3690/IC 694) and in Arp 244 (NGC 4038/39). Whether the IR emission from the central region or that from the surrounding extranuclear galactic disk dominates depends on the geometry and the epoch of the collision and on the initial radial gas distribution in the two galaxies. In general, the central starburst would be stronger than that in the disks, due to the higher preexisting gas densities in the central region. The burst of star formation is expected to last over a galactic gas disk crossing time approximately 4 x 10(7) yr. We can also explain the simultaneous existence of nearly normal CO galaxy luminosities and shocked H-2 gas, as seen in colliding field galaxies.This is a minimal model, in that the only necessary condition for it to work is that there should be a sufficient overlap between the spatial gas distributions of the colliding galaxy pair.

Quantitative and compositional changes in myelin of undernourished and protein malnourished rat brains

Effects of undernutrition and protein malnutrition on the quantitative and qualitative changes in myelin isolated from rat brain at 3 and 8 weeks of age were investigated. Undernutrition during suckling period was induced by increasing the litter size, and continued from the 3rd to the 8th week by limited food intake, or the rats were rehabilitated with adequate food. Protein malnutrition was induced by feeding the lactating dams 5% protein diet as against 25% protein diet in controls. The protein malnourished rats were rehabilitated from the 3rd to the 8th week with the normal 25% protein diet. Undernutrition produced 16% and 35% reductions in the myelin content at 3 and 8 weeks of age, respectively, and was only partially restored on rehabilitation. Protein malnutrition caused more drastic reduction of 27% in the myelin content at 3 weeks, which was also partially restored on rehabilitation. The specific activity of 2′,3′-cyclic nucleotide 3′-phosphohydrolase was not affected by undernutrition, whereas protein malnutrition caused a 25% reduction at 3 weeks, which was totally reversed by rehabilitation. Undernutrition had not altered the relative composition of myelin proteins, but protein malnutrition resulted in a significant reduction in the proteolipid protein at 3 weeks of age, which could be reversed by rehabilitation.

Synthesis, spectral and structural studies on metal complexes of Schiff bases involving vitamin B6 and histamine

Six metal complexes of Schiff bases involving Vitamin B6 and the decarboxylated amino acid histamine have been synthesised and characterized. Crystal structures have been determined for [CuL1(H2O)Br]-NO31(L1= pyridoxylidenehistamine) and [Cu2L22(NO3)2]·6H2O 2(L2= 5′-phosphopyridoxylidenehistaminate). The crystal structure of complex 1[space group P[1 with combining macron], a= 8.161(2), b= 10.368(2), c= 11.110(2)Å, α= 105.18(1), β= 102.12(1), γ= 72.10(1)° and Z= 2; R= 0.072, R′= 0.083] consists of square-pyramidally co-ordinated copper with the tridentate Schiff base in the zwitterionic form, whereas in 2[space group P[1 with combining macron], a= 8.727(1), b= 10.308(1), c= 12.845(2)Å, α= 110.00(1), β= 78.94(1), γ= 114.35(1)° and Z= 1; R= 0.035, R′= 0.034] the copper has the same co-ordination geometry but the tetradentate Schiff-base ligand exists as a monoanion. The conformational parameters deduced from such structures are important for understanding the stereochemical aspects of Vitamin B6-catalysed model reactions involving histidine.

Inelastic response of beams under sinusoidal and random loads

A new analytical model has been suggested for the hysteretic behaviour of beams. The model can be directly used in a response analysis without bothering to locate the precise point where the unloading commences. The model can efficiently simulate several types of realistic softening hysteretic loops. This is demonstrated by computing the response of cantilever beams under sinusoidal and random loadings. Results are presented in the form of graphs for maximum deflection, bending moment and shear

Traditionally Protected Forests´ Role within Transforming Natural Resource Management Regimes in Taita Hills, Kenya

In Taita Hills, south-eastern Kenya, remnants of indigenous mountain rainforests play a crucial role as water towers and socio-cultural sites. They are pressurized due to poverty, shortage of cultivable land and the fading of traditional knowledge. This study examines the traditional ecological knowledge of Taitas and the ways it may be applied within transforming natural resource management regimes. I have analyzed some justifications for and hindrances to ethnodevelopment and participatory forest management in light of recently renewed Kenyan forest policies. Mixed methods were applied by combining an ethnographic approach with participatory GIS. I learned about traditionally protected forests and their ecological and cultural status through a seek out the expert method and with remote sensing data and tools. My informants were: 107 household interviewees, 257 focus group participants, 73 key informants and 87 common informants in participatory mapping. Religious leaders and state officials shared their knowledge for this study. I have gained a better understanding of the traditionally protected forests and sites through examining their ecological characteristics and relation to social dynamics, by evaluating their strengths and hindrances as sites for conservation of cultural and biological diversity. My results show that, these sites are important components of a complex socio-ecological system, which has symbolical status and sacred and mystical elements within it, that contributes to the connectivity of remnant forests in the agroforestry dominated landscape. Altogether, 255 plant species and 220 uses were recognized by the tradition experts, whereas 161 species with 108 beneficial uses were listed by farmers. Out of the traditionally protected forests studied 47 % were on private land and 23% on community land, leaving 9% within state forest reserves. A paradigm shift in conservation is needed; the conservation area approach is not functional for private lands or areas trusted upon communities. The role of traditionally protected forests in community-based forest management is, however, paradoxal, since communal approaches suggests equal participation of people, whereas management of these sites has traditionally been the duty of solely accredited experts in the village. As modernization has gathered pace such experts have become fewer. Sacredness clearly contributes but, it does not equal conservation. Various social, political and economic arrangements further affect the integrity of traditionally protected forests and sites, control of witchcraft being one of them. My results suggest that the Taita have a rich traditional ecological knowledge base, which should be more determinately integrated into the natural resource management planning processes.

Ball wear and its control in the grinding of a lead-zinc sulphide ore

Marked ball grinding tests were carried out in the laboratory with a lead-zinc sulphide ore under different experimental conditions using high carbon low alloy steel (cast and forged) and high chrome cast iron balls. Relative ball wear as a function of grinding period and milling conditions was evaluated for the different types of ball materials. The role of corrosion and abrasion-erosion in the wear of grinding media is brought out. Methods to minimise ball wear through control of mill atmosphere and addition of reagents are discussed.

Bioleaching of sulphides under applied potentials

The influence of applied DC potentials on the activity and growth of Thiobacillus ferrooxidans, as well as on the dissolution behaviour of some base metal sulphides is discussed with reference to bioleaching. Selective bioleaching of zinc from sphalerite could be achieved under an applied potential of −500 mV (saturated calomel electrode) from binary mineral mixtures containing the zinc mineral and chalcopyrite or pyrite. On the other hand, bioleaching of pyrite and chalcopyrite was found to be enhanced under positive potentials of +400 mV and +600 mV, respectively. Probable mechanisms in the electrobioleaching of sulphides are examined with respect to galvanic, microbiological and applied potential effects.

Effect of microstructure and hardness on the grinding abrasive wear resistance of a ball bearing steel

Grinding media wear appears to be non-linear with the time of grinding in a laboratory-scale ball mill. The kinetics of wear can be expressed as a power law of the type w=atb, where the numerical constant a represents wear of a particular microstructure at time t = 1 min and b is the wear exponent which is independent of the particle size prevailing inside a ball mill at any instant of time of grinding. The wear exponent appears to be an indicator of the cutting wear mechanism in dry grinding: a plot of the inverse of the normalised wear exponent (Image ) versusHs (where Hs is the worn surface hardness of the media) yields a curve similar to that of a wear resistance plot obtained in the case of two-body sliding abrasive wear. This method of evaluating the cutting wear resistance of media is demonstrated by employing 15 different microstructures of AISI-SAE 52100 steel balls in dry grinding of quartz in a laboratory-scale ball mill.

Identification of tropomyosin as the major shrimp allergen and characterization of its IgE-binding epitopes

The major heat-stable shrimp allergen (designated as Sa-II), capable of provoking IgE-mediated immediate type hypersensitivity reactions after the ingestion of cooked shrimp, has been shown to be a 34-kDa heat- stable protein containing 300 amino acid residues. Here, we report that a comparison of amino acid sequences of different peptides generated by proteolysis of Sa-II revealed an 86% homology with tropomyosin from Drosophila melanogaster, suggesting that Sa-II could be the shrimp muscle protein tropomyosin. To establish that Sa-II is indeed tropomyosin, the latter was isolated from uncooked shrimp (Penaeus indicus) and its physicochemical and immunochemical properties were compared with those of Sa-II. Both tropomyosin and Sa-II had the same molecular mass and focused in the isoelectric pH range of 4.8 to 5.4. In the presence of 6 M urea, the mobility of both Sa-II and shrimp tropomyosin shifted to give an apparent molecular mass of 50 kDa, which is a characteristic property of tropomyosins. Shrimp tropomyosin bound to specific IgE antibodies in the sera of shrimp-sensitive patients as assessed by competitive ELISA inhibition and Western blot analysis. Tryptic maps of both Sa-II and tropomyosin as obtained by reverse phase HPLC were superimposable. Dot-blot and competitive ELISA inhibition using sera of shrimp-sensitive patients revealed that antigenic as well as allergenic activities were associated with two peptide fractions. These IgE-binding tryptic peptides were purified and sequenced. Mouse anti-anti-idiotypic antibodies raised against Sa-II specific human idiotypic antibodies recognized not only tropomyosin but also the two allergenic peptides, thus suggesting that these peptides represent the major IgE binding epitopes of tropomyosin. A comparison of the amino acid sequence of shrimp tropomyosin in the region of IgE binding epitopes (residues 50-66 and 153-161) with the corresponding regions of tropomyosins from different vertebrates confirmed lack of allergenic cross-reactivity between tropomyosins from phylogenetically distinct species.

Molecular structure of electron donor-acceptor complexes of metallotetraphenylporphyrins with trinitrobenzene

The metallotetraphenylporphyrins, MTPPs, where M=Co(II), Cu(II) and Ag(II) form one to one molecular complexes in solution with 1,3,5-trinitrobenzene (TNB). The crystal structure of CoTPP.TNB.2CH3OH revealed that the mean separation between the porphyrin and TNB planes is 3·27 Å and the centre of the aryl ring of TNB is displaced by 0·90 Å from the centre of the porphyrin plane. Extended Huckel molecular orbital calculations suggest that acceptor orbitals are predominantly nitro-group based rather than an aryl π framework. The contribution of the metal orbitals in the donation is also seen as predicted by the structural data. Electrochemical redox measurements in solution provide evidence for charge-transfer stabilisation in these complexes.

Bacteriophage therapy for Staphylococcus aureus bacteremia in streptozotocin-induced diabetic mice

The protective effect of bacteriophage was assessed against experimental Staphylococcus aureus lethal bacteremia in streptozotocin (STZ) induced-diabetic and non-diabetic mice. Intraperitoneal administrations of S. aureus (RCS21) of 2 x 10(8) CFU caused lethal bacteremia in both diabetic and non-diabetic mice. A single administration of a newly isolated lytic phage strain (GRCS) significantly protected diabetic and nondiabetic mice from lethal bacteremia (survival rate 90% and 100% for diabetic and non-diabetic bacteremic groups versus 0% for saline-treated groups). Comparison of phage therapy to oxacillin treatment showed a significant decrease in RCS21 of 5 and 3 log units in diabetic and nondiabetic bacteremic mice, respectively. The same protection efficiency of phage GRCS was attained even when the treatment was delayed up to 4 h in both diabetic and non-diabetic bacteremic mice. Inoculation of mice with a high dose (10(10) PFU) of phage GRCS alone produced no adverse effects attributable to the phage per se. These results suggest that phages could constitute valuable prophylaxis against S. aureus infections, especially in immunocompromised patients. (C) 2010 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.