Structural flexibility in the biocatalyst-mediated functionalization of ring `A' in salannin, a tetranortriterpene from Azadirachta indica

Nocardia sp. quantitatively converts salannin 1 and 3-de-O-acetylsalannin 2 (C-seco limonoids) into 3-deacetoxy-1-de[(E)-2-methylbut-2-enoyloxy]salannin-1-en-3-one 10, a novel and potentially bioactive compound with an alpha,beta-unsaturated ketone moiety in ring `A'. In order to establish the sequence of events involved in this transformation and the structural specificity of this bacterial system, several new derivatives of salannin 1 have been prepared. These studies have indicated that the transformation is initiated by deacetylation at C-3, followed by oxidation of the secondary hydroxy group to 3-keto, which appears to facilitate the elimination of the tigloyloxy/acetoxy group at C-1 with the formation of an olefinic linkage between C-1 and C-2. The organism very efficiently transforms some of the derivatives of salannin into their corresponding compounds possessing an enone systemin ring `A', an essential pre-requisite for various biological activities. Some of the C-seco limonoids prepared in the present study, viz. 10, 1,2-didehydro-1,3-dideoxy-3-oxosalannic acid 18, 3-deacetoxy-1-de[(E)-2-methylbut-2-enoyloxy]-20,21,22,23-tetrahydrosal annin-1-en-3-one 15 and 1,2-didehydro-1,3-dideoxy-3-oxosalannol 23 were hitherto not known.

A combined experimental and theoretical study of the charge-transfer compound between C60Br8 and tetrathiafulvalene

C60Br8, unlike C60Br6 and C60Cl6, forms a solid charge-transfer compound with tetrathiafulvalene (TTF), the composition being C60Br8(TTF)(8). The unique complex-forming property of C60Br8 can be understood on the basis of the electronic structures of the halogenated derivatives of C-60. Molecular orbital calculations show that the low LUMO energy of C60Br8 compared with the other halogen derivatives renders the formation of the complex with TTF favourable, the four virtual LUMOs being able to accept 8 electrons. The Raman spectrum of C60Br8(TTF)(8) shows a marked softening of the bands (-46 cm(-1) on average) with respect to C60Br8 suggesting that indeed 8 electrons are transferred per C60Br8 molecule, one from each TTF molecule. The complex is weakly paramagnetic and shows a magnetic transition around 80 K.

Processing and compressive strength of Al-Li-SiCp composites fabricated by a compound billet technique

Al-Li-SiCp composites were fabricated by a simple and cost effective stir casting technique. A compound billet technique has been developed to overcome the problems encountered during hot extrusion of these composites. After successful fabrication hardness measurement and room temperature compressive test were carried out on 8090 Al and its composites reinforced with 8, 12 and 18vol.% SiC particles in as extruded and peak aged conditions. The addition of SiC increases the hardness. 0.2% proof stress and compressive strength of Al-Li-8%SiC and Al-Li-12%SiC composites are higher than the unreinforced alloy. in case of the Al-Li-18%SiC composite, the 0.2% proof stress and compressive strength were higher than the unreinforced alloy but lower than those of Al-Li-8%SiC and Al-Li-12%SiC composites. This is attributed to clustering of particles and poor interfacial bonding.

Reactivity of PPh3 towards Ru2Cl(O2CR)4 (R = Me, Ph) in alcoholic medium: a novel decarbonylation process mediated by a diruthenium compound

Abstract is not available.

The nature of hydrogen induced amorphization of SmNi2 laves compound

Abstract is not available.

A study on the nature of the compound layer formed during the ion nitriding of En40B steel

Commercial-grade En40B steel has been ion nitrided in the temperature range 475–550°C in a 25%N2–75%H2 gas mixture. The nature of the compound layer formed was studied by the X-ray diffraction technique and optical metallography. It was observed that the structure of the compound layer gradually transforms from a predominantly epsilon (Porson) nitride to a predominantly γ′ nitride structure with increasing treatment time. Optical metallography studies on sections orthogonal to the nitrided surface showed that, after about 5 h of treatment, the thickness of the compound layer decreases with further increase in treatment time.

A concise synthesis of the bioactive meroterpenoid natural product (+/-)-liphagal, a potent PI3K inhibitor

A short, diversity-oriented synthesis that follows a biomimetic route to the marine natural product liphagal, from a commercially available building block, is delineated.

Evidence for a new metastable crystalline compound in Ge---Te system

Pressure dependence of the electrical resistivity of bulk, melt quenched GexTe100−x glasses (15 less-than-or-equals, slant x less-than-or-equals, slant 28) has been studied up to 8GPa pressure. All the glasses exhibit a sharp, discontinuous glass to crystal transition under pressure. The high pressure crystalline phases are identified to have a face centered cubic structure. The value of the cell constant is 0.779nm for 15 less-than-or-equals, slant x less-than-or-equals, slant 17, 0.642nm for x=20 and 0.55lnm for 22 ≤ x ≤ 28 samples respectively. The cell constants of the high pressure crystalline phases suggest the possible existance of a new metastable crystalline compound in the Ge---Te system with F.C.C. structure and cell constant equal to 1.109nm as reported by Moore et al.

Synthetic studies towards bioactive frondosins: rapid framework access and diversity creation

A very concise and diversity-oriented approach to rapidly access frondosin-related frameworks from commercially available building blocks is outlined.

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.