Preparatively useful transformations of steroids and morphine alkaloids byMucor piriformis

A versatile fungus isolated in our laboratory and identified as Mucor piriformis has been shown to effect novel and preparatively useful transformations in steroids and morphine alkaloids. The organism very effectively carries out hydroxylation of various C-19 and C-21 steroids at 7 and 14-positions. Although the organism is capable of catalysing hydroxylation at 6 beta and 11 alpha-positions, these are not the major activities. The 14 alpha-hydroxylase appears to have a broad substrate specificity. However, steroids with a bulky substitution at C-17 alpha-position or without the 4-en-3-one group are not accepted as substrates by the 14 alpha-hydroxylase system. Studies have demonstrated how various C-19 and C-21 steroids can be modified to yield new structures which are either difficult to prepare by traditional methods or hitherto unknown. The organism also very efficiently and selectively carries out the N-dealkylation of thebaine and its N-variants. Interestingly, the nor-compound formed does not get further metabolized. Since thebaine is very often used as a starting material to synthesize various morphine agonists as well as antagonists, and one of the steps involved in their preparation is the N-dealkylation reaction, the microbial process could certainly offer an alternative approach.

Reactivity and catalytic activity of layered YBA2CU3O7-delta (123) type defect perovskites

The chemical modifications of structure, reactivity and catalytic properties of layered triple perovskite oxides, related to the YBa2Cu3O7-delta (123) system, have been briefly reviewed. These oxides form a versatile family of materials with wide-ranging chemical and physical properties. The multiple sites available for chemical doping, and the ability to reversibly intercalate oxygen at the defect sites have rendered these oxides important model systems in the area of oxide catalysis. An attempt has been made to comprehend the hitherto known catalytic reactions and correlate them to various factors like structure, oxygen diffusional limitations, different geometries adopted by various substituents, oxidative non-stoichiometry and activation energy for oxygen desorption. In particular, results on the enhanced catalytic activity of cobalt-substituted 123 oxide systems towards the selective catalytic oxidation of ammonia to nitric oxide and carbon monoxide to carbon dioxide are presented.

Synthesis, Crystal Structure, and Magnetic Properties of a Ferromagnetically Coupled Angular Trinuclear Copper(11) Complex [Cu3(02CMe)4(bpy)s(HzO)](PF)62

The synthesis, X-ray crystal structure, and magnetic properties of an angular trinuclear copper(II) complex [Cu3(O2CMC)4(bpy)3(H2O)](PF6)2 (1), obtained from a reaction of Cu2(O2CMe)4(H2O)2 With 2,2'-bipyridine (bpy) and NH4PF6 in ethanol, are reported. Complex 1 crystallizes in triclinic space group P1BAR with a = 11.529(1) angstrom, b = 12.121(2) angstrom, c = 17.153(2) angstrom, alpha = 82.01(1)-degrees, beta = 79.42(1)-degrees, gamma = 89.62(1)-degrees, and Z = 2. A total of 6928 data with I > 2.5sigma(I) were refined to R = 0.0441 and R(w) = 0.0557. The structure consists of a trinuclear core bridged by four acetate ligands showing different bonding modes. The coordination geometry at each copper is distorted square-pyramidal with a CuN2O2...O chromophore. The Cu...Cu distances are 3.198(1) angstrom, 4.568(1) angstrom, and 6.277(1) angstrom. There are two monoatomic acetate bridges showing Cu-O-Cu angles of 93.1(1) and 97.5(1)-degrees. Magnetic studies in the temperature range 39-297 K show the presence of a strong ferromagnetically coupled dicopper(II) unit (2J = +158 cm-1) and an essentially isolated copper(II) center (2J' = -0.4 cm-1) in 1. The EPR spectra display an axial spectrum giving g(parallel-to) = 2.28 (A(parallel-to) = 160 X 10(-4) cm-1) and g(perpendicular-to) = 2.06 (A(perpendicular-to) = 12 X 10(-4) cm-1) for the normal copper and two intense isotropic signals with g values 2.70 and 1.74 for the strongly coupled copper pair. The structural features of 1 compare well with the first generation models for ascorbate oxidase.

Asymmetric synthesis of steroidal Tröger's base analogues. X-Ray molecular structure of methyl 3?,12?-{6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-bisacetoxy}-5?-cholan-24-oate

Cyclization of compound 5c in trifluoroacetic acid/hexamethylenetetramine produces Tröger's base analogue 6c in 75% yield with 70% diastereoselectivity.

A total synthesis of 11-O-methyldebenzoyltashironin

A concise total synthesis of 11-O-methyldebenzoyltashironin is reported in which oxidative dearomatization-IMDA-RCM triad constitutes the key ring forming steps, while an unorthodox DIBAL-H mediated stereo- and regioselective reductive epoxide openings and implementation of the vinyl bromide-carbonyl equivalency concept were pivotal to the success of this endeavor. (C) 2011 Elsevier Ltd. All rights reserved.

Structure, Spectra and Redox Behaviour of Copper(11) Complexes of Bis( benzimidazoly1)diamine Ligands

The linear quadridentate ligand N,N'-bis(benzimidazoI-2-ylethyl)ethane-l,2-diamine (L') and its 1 - methylbenzimidazole analogue (L2) and homologues form 1 : 1 complexes with Cu(CIO,),; L' also forms complexes of the types CuL'X, where X = NO,, PF,, Br or CI and CuL'(X)Y where X = CI or Br and Y = CIO, or Br. Deep blue CuL1Br,*2H20 crystallizes in the monoclinic space group C2/c with Z = 4, a = 9.91 9(2), b = 16.626(3), c = 14.1 02(3) le\ and p = 94.39(2)". The structure was solved by Patterson and Fourier difference methods and refined by the least-squares technique to R = 0.064 for 2195 independent reflections with / > 1.50(/). The molecule lies on a two-fold axis symmetrically around Cu". The co-ordination around Cu" is found to be square planar with two amino nitrogens and two benzimidazole nitrogens forming the equatorial plane [CU-N 1.983(3) and 2.037(4) A]. The bromides are at longer distances [3.349(1) A] in axial sites. Ligand field and EPR spectra indicate that one bromide or chloride ion is axially co-ordinated to Cu" in [CuL1l2+. This ion exhibits quasi-reversible redox behaviour. Electrochemical studies of the dihalides in methanol have established the presence of [CuL'X,], [CuL'(X)]+ and [CuL'I2+ in equilibrium. In complexes with 565 [CuL4I2+ [L4 = N,Nbis( benzimidazol-2-ylmethyl)ethane-l,2-diamine] and 555 [CuL3] [L3 = N,N'-bis(1 -methylbenzimidazol- 2-ylmethyl)propane-l,3-diamine] chelate rings, Cull does not seem to lie in the N, square plane, as revealed by their low A values and irreversible electrochemical behaviour. The Cu"-Cu' redox potentials in methanol are in the order [CuL1I2+ < [CuL3I2+ < [CuL4I2+; this illustrates that sixmembered chelate rings are suitable to stabilize Cu", when CU-N 0 interactions are favourable.

Synthesis, properties and crystal structures of diastereomeric areneruthenium(II) chiral Schiff-base complexes

Diastereomers (SRu,Sc)-1a and (RRu,Sc)-1b, in a ratio of 85: 15 and formulated as [Ru(η-MeC6H4Pri-p)Cl(L*)], have been prepared by treating [{Ru(η-MeC6H4Pri-p)Cl2}2] with the sodium salt of (S)-α-methylbenzylsalicylaldimine (HL*) in tetrahydrofuran at –70 °C. The reaction of 1(1a+1b) with AgClO4 in acetone followed by an addition of PPh3 or 4-methylpyridine (4Me-py) leads to the formation of adducts [Ru(η-MeC6H4Pri-p)(PPh3)(L*)]ClO42[(SRu,Sc)2a, (FRu,Sc)2b] and [Ru(η-MeC6H4Pri-p)(4Me-py)(L*)]ClO43[(SRu,Sc)3a, (RRu,Sc)3b] in the diastereomeric ratios (SRu,Sc) : (RRu,Sc) of 2 : 98 and 76 : 24, respectively. Complex 1 crystallises with equal numbers of 1a and 1b molecules in an asymmetric unit of monoclinic space group P21 with a= 10.854(1), b= 17.090(1), c= 12.808(4)Å, β= 110.51(1)°, and Z= 4. The structure was refined to R= 0.0552 and R′= 0.0530 with 2893 reflections having I[gt-or-equal] 1.5σ(I). The absolute configurations of the chiral centres in the optically pure single crystal of the PPh3 adduct have been obtained from an X-ray study. Crystals of formulation [Ru(η-MeC6H4Pri-p)-(PPh3)(L*)]2[ClO4][PF6]·1.5 CHCl3, obtained in presence of both ClO4 and PF6 anions, belong to the non-centric triclinic space group P1 with a= 10.852(2), b= 14.028(1), c= 15.950(2)Å, α= 91.51(1), β= 105.97(1), γ= 106.11(1)°, and Z= 2. The final residuals were R= 0.0713, R′= 0.0752 with 7283 reflections having I[gt-or-equal] 2.5σ(I). The crystal structures of 1a,1b, and the PPh3 adduct (2b,2b′) consist of a ruthenium(II) centre bonded to a η-p-cymene, a bidentate chelating Schiff base, and a unidentate ligand (Cl or PPh3). The chirooptical properties of the complexes have been studied using 1H NMR and CD spectral data. The presence of a low-energy barrier for the intermediate involved in these reactions, showing both retention as well as inversion of the metal configuration, is discussed.

Organometallic Chemistry of Diphosphazanes. 11. Reactions of fac-[Mo(CO)3(MeCN){.eta.2-Ph2PN(Pri)PPh(DMP)}] (DMP = 3,5-Dimethyl-1-Pyrazolyl) with Diphosphazanes and Diphosphinoalkanes and Oxidative Addition with Iodine

The use of fac-[Mo(CO)(3)(MeCN)(eta(2)-L(1))] (1a) {L(1) = Ph(2)PN(Pr-i)PPh(DMP)}(2) as a precursor to metalloligands and bimetallic, heterotrimetallic, and heptacoordinated complexes is reported. The reaction of 1a with diphosphazane, dppa, or a diphosphinoalkane such as dppm or dppe yields the fac-eta(1)-diphosphine substituted metalloligands, fac-[Mo(CO)(3)(eta(2)-L(1))(eta(1)-PXP)] {PXP = dppa (2), dppm (3), and dppe (4)}. These undergo isomerization to yield the corresponding mer-diphosphine complexes (5-7). Oxidation of the uncoordinated phosphorus atom of the mer-eta(1)-dppm-substituted complex eventually provides mer-[Mo(CO)(3)-(eta(2)-L(1)){eta(1)-Ph(2)PCH(2)P(O)Ph(2)}](8). The structure of the latter complex has been confirmed by single crystal X-ray diffraction {triclinic system, P ($) over bar 1; a = 11.994(3), b = 14.807(2), c = 15.855(3) Angstrom; alpha = 114.24(1), beta = 91.35(2), and gamma = 98.95(1)degrees; Z = 2, 4014 data (F-0 > 5 sigma(F-0)), R = 0.066, R(W) = 0.069}. Treatment of the dppe metalloligand 7 with [PtCl2(COD)] yields the heterotrimetallic complex cis-[PtCl2{mer-[Mo(CO)(3)(eta(2)-L(1))(eta(1)-dppe]}(2)] (9). Attempts to prepare a related trimetallic complex with the dppm-containing metalloligand were unsuccessful; only the tetracarbonyl complex cis-[Mo(CO)(4)(eta(2)-L(1))] (1b) and cis-[PtCl2(eta(2)-dppm)] were obtained. Reaction of la with dppe in the ratio 2:1 yields the mer-mer dinuclear complex [{mer-[Mo(CO)(3)(eta(2)-L(1))]}(2)(mu-dppe)] (10) bridged by dppe. Oxidation of 1a with iodine yields the Mo(II) heptacoordinated complex [MoI2(CO)(2)(eta(3)-L(1))] (11) with tridentate PPN coordination. The same Mo(II) complex 11 is also obtained by the direct oxidation of the tetracarbonyl complex cis-[Mo(CO)(4)(eta(2)-L(1))] (1b) with iodine. The structure of 11 has been confirmed by X-ray diffraction studies {monoclinic system, Cc; a = 10.471(2), b = 19.305(3), c = 17.325(3) Angstrom; beta = 95.47(2)degrees; Z = 4, 3153 data (F-0 > 5 sigma(F-0)), R = 0.049, R(W) = 0.051}. This complex exhibits an unusual capped-trigonal prismatic geometry around the metal. A similar heptacoordinated complex 12 with a chiral diphosphazane ligand {L(3) = (S,R)-P(h)2PN-(*CHMePh)*PPh(DMP)} has also been synthesized.

Structural and optical properties of nonpolar (11-20) a-plane GaN grown on (1-102) r-plane sapphire substrate by plasma-assisted molecular beam epitaxy

We report the structural and optical properties of a-plane GaN film grown on r-plane sapphire substrate by plasma-assisted molecular beam epitaxy. High resolution X-ray diffraction was used to determine the out-of-plane and in-plane epitaxial relation of a-plane GaN to r-plane sapphire. Low-temperature photoluminescence emission was found to be dominated by basal stacking faults along with near-band emission. Raman spectroscopy shows that the a-GaN film is of reasonably good quality and compressively strained. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecane-8,11-dione

NaBH4 reduction of a cage dione proceeds in a stereospecific fashion to give the endo,endo-diol. This reactivity is related to the crystal structure.

OPSM - Opportunistic Power Save mode for Infrastructure IEEE 802.11 WLAN

We focus on the energy spent in radio communication by the stations (STAs) in an IEEE 802.11 infrastructure WLAN. All the STAs are engaged in web browsing, which is characterized by a short file downloads over TCP, with short duration of inactivity or think time in between two file downloads. Under this traffic, Static PSM (SPSM) performs better than CAM, since the STAs in SPSM can switch to low power state (sleep) during think times while in CAM they have to be in the active state all the time. In spite of this gain, performance of SPSM degrades due to congestion, as the number of STAs associated with the access point (AP) increases. To address this problem, we propose an algorithm, which we call opportunistic PSM (OPSM). We show through simulations that OPSM performs better than SPSM under the aforementioned TCP traffic. The performance gain achieved by OPSM over SPSM increases as the mean file size requested by the STAs or the number of STAs associated with the AP increases. We implemented OPSM in NS-2.33, and to compare the performance of OPSM and SPSM, we evaluate the number of file downloads that can be completed with a given battery capacity and the average time taken to download a file.

Experimental validation of analytical performance models for IEEE 802.11 networks

We consider the simplest IEEE 802.11 WLAN networks for which analytical models are available and seek to provide an experimental validation of these models. Our experiments include the following cases: (i) two nodes with saturated queues, sending fixed-length UDP packets to each other, and (ii) a TCP-controlled transfer between two nodes. Our experiments are based entirely on Aruba AP-70 access points operating under Linux. We report our observations on certain non-standard behavior of the devices. In cases where the devices adhere to the standards, we find that the results from the analytical models estimate the experimental data with a mean error of 3-5%.

Slow orientational dynamics of water molecules at a micellar surface

The dynamics of water molecules near an aqueous micellar interface is studied in an atomistic molecular dynamics simulation of cesium pentadecafluorooctanoate (CsPFO) in water. The dipolar orientational time correlation function (tcf) and the translational diffusion of the water molecules are investigated. Results show that both the reorientational and the translational motion of water molecules near the micelle are restricted. In particular, the orientational tcf exhibits a very slow component in the long time which is slower than its bulk value by 2 orders of magnitude. This slow decay seems to be related to the slow decay often observed in experiments. The origin of the slow decay is analyzed.

Sustainable biomass production for energy in selected Asian countries

This paper presents a synthesis of assessment of sustainable biomass production potential in six Asian countries-China, India, Malaysia, Philippines, Sri Lanka and Thailand, and is based on the detailed studies carried out in these countries under the Asian Regional Research Programme in Energy, Environment and Climate (ARRPEEC). National level studies were undertaken to estimate land availability for biomass production, identify and evaluate the biomass production options in terms of yield per hectare and financial viability, estimate sustainable biomass production for energy, and estimate the energy potential of biomass production in the six Asian countries. Sustainable biomass production from plantation is estimated to be in the range of 182.5-210.5, 62-310, 0.4-1.7, 3.7-20.4, 2.0-9.9 and 11.6-106.6 Mt yr(-1) for China, India, Malaysia, Philippines, Sri Lanka and Thailand, respectively. The maximum annual electricity generation potential, using advanced technologies, from the sustainable biomass production is estimated to be about 27, 114, 4.5, 79, 254 and 195 percentage of the total electricity generation in year 2000 in China, India, Malaysia, Philippines, Sri Lanka and Thailand, respectively. Investment cost for bioenergy production varies from US$381 to 1842 ha(-1) in the countries considered in this study; investment cost for production of biomass varies from US$5.1 to 23 t(-1). (C) 2003 Elsevier Ltd. All rights reserved.