The identification of 14 alpha,17 beta-dihydroxyandrost-4-en-3-one monohydrate and 14 alpha,17 beta-dihydroxyandrosta-1,4-dien-3-one monohydrate, metabolites of androstenedione in Mucor piriformis

The microorganism Mucor piriformis transforms androst-4-ene-3,17-dione into a major and several minor metabolites. X-ray crystallographic analysis of two of these metabolites was undertaken to determine unambiguously their composition and chirality. Crystals belong to the orthorhombic space-group P2(1)2(1)2(1), with a = 7.199(4) angstrom and a = 6.023(3) angstrom, b = 11.719(3) angstrom and b = 13.455(4) angstrom, c = 20.409(3) angstrom and c = 20.702(4) angstrom for the two title compounds, respectively. The structures have been refined to final R values of 0.060 and 0.040, respectively.

Nuclear-quadrupole resonance in coordination chemistry- identification of bridiging and therminal chlorines in the mercuric chloride-4-picoline n-oxide complex

The temperature dependence of the chlorine-35 n.q.r. in the mercuric chloride-4-picoline N-oxide complex has been studied from 77 K to room temperature, and the results are used to assign the observed frequencies to terminal and bridging chlorines.

Coexistence of para and ferromagnetic phases of Fe3+ in undoped CdZnTe (Zn similar to 4%) crystals

The signatures of the coexistence of para and ferromagnetic phases for the Fe3+ charge state of iron have been identified in the low temperature electron spin resonance (ESR) spectra in undoped CdZnTe (Zn similar to 4%) crystals and independently verified by superconducting quantum interference device (SQUID) and AC susceptibility measurements. In the paramagnetic phase the inverse of AC susceptibility follows the Curie-Weiss law. In the ferromagnetic phase the thermal evolution of magnetization follows the well-known Bloch T-3/2 law. This is further supported by the appearance of hysteresis in the SQUID measurements at 2 K below T-c which is expected to lie in between 2 and 2.5 K. (C) 2010 Elsevier Ltd. All rights reserved.

Synthesis and Identification of a new class of antileukemic agents containing 2-(arylcarboxamide)-(S)-6-amino-4,5,6,7-tetrahydrobenzod]thiazole

Recently we have reported the effect of (S)-6-aryl urea/thiourea substituted-2-amino-4,5,6,7-tetrahydrobenzod]thiazole derivatives as potent anti-leukemic agents. To elucidate further the Structure Activity Relationship (SAR) studies on the anti-leukemic activity of (S)-2,6-diamino-4,5,6,7 tetrahydrobenzod]thiazole moiety, a series of 2-arlycarboxamide substituted-(S)-6-amino-4,5,6,7-tetrahydrobenzod]thiazole were designed, synthesized and evaluated for their anti-leukemic activity by trypan blue exclusion, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), lactate dehydrogenase (LDH) assays and cell cycle analysis. Results suggest that the position, number and bulkiness of the substituent on the phenyl ring of aryl carboxamide moiety at 2nd position of 6-amino-4,5,6,7-tetrhydrobenzod]thiazole play a key role in inhibiting the proliferation of leukemia cells. Compounds with ortho substitution showed poor activity and with meta and para substitution showed good activity. (C) 2010 Elsevier Masson SAS. All rights reserved.

Metsän rakenteen muutokset ja liito-oravan esiintyminen Tampereen kaupunkialueella vuosina 1966–2004

Liito-orava (Pteromys volans) on havumetsävyöhykkeen varttuneissa sekametsissä esiintyvä pieni yöaktiivinen nisäkäs. Suomen liito-oravakannan on arvioitu taantuneen viimeisten vuosikymmenien aikana ja laji on luokiteltu Suomessa vaarantuneeksi. EU:n luontodirektiivissä liito-orava on mainittu erityistä suojelua vaativana lajina, jonka lisääntymis- tai levähdyspaikkoja ei saa hävittää. Liito-oravan suosimat varttuneet kuusivaltaiset sekametsät ovat yleisiä useiden suomalaisten kaupunkien taajama-asutusten tuntumissa. Näihin metsiin kohdistuu suuri kaavoituspaine. Tutkimuksen tarkoituksena on selvittää metsämaiseman rakenteen muutoksen vaikutusta liito-oravaan ja arvioida eroavatko kaupunki- ja metsätalousalueet liito-oravan elinympäristönä. Selvitin Tampereen kaupungin ja Kangasalan kunnan alueella sijaitsevan tutkimusalueen metsärakenteen muutokset vuosina 1966—2004 ja liito-oravaesiintymät vuonna 2004. Tarkoituksena on selvittää miten metsärakenteen muutos on vaikuttanut alueen liito-oravakantaan ja liito-oravien esiintymiseen. Ilmakuvatulkinnalla rajasin 52 km2 kokoisen tutkimusalueen metsät niiden rakenteen perusteella metsäkuvioihin. Keväällä 2004 kartoitettiin tutkimusalueen liito-oravaesiintymiä ja kirjasin metsäkuvioiden tärkeimmät puustotiedot. Luokittelin kaikki metsäkuviot neljään, liito-oravalle soveltuvuuteen perustuvaan luokkaan. Paikkatieto-ohjelmassa annoin kullekin kuvioluokalle eri värin ja lopputuloksena oli monivärinen kartta josta pystyy helposti havaitsemaan liito-oravalle soveltuvat, sopimattomat sekä liikkumiseen soveltuvat alueet. Ilmakuvatulkinnalla tein vastaavia karttoja myös vuosille 1966, 1979, 1987 ja 1995. Metsäkuviotietojen perusteella laskin eri vuosille pirstoutumista kuvaavan läheisyysindeksin. Aiemmin Etelä-Suomesta saatuja liito-orava radiopantatutkimustuloksia ja monivuotisia kartoitustuloksia vertailuaineistona käyttäen tein arvion liito-oravaesiintymien määrän kehityksestä vuosina 1966–2004. Tutkimusalueen liito-oravakartoituksessa löysin 318 papanahavaintopaikkaa. Papanahavainnoista 78 % olivat enintään 500 m päässä lähimmästä ihmisasutuksesta. Tampereen kaupungin alueen havainnoista 73 % sijaitsevat Tampereen kaupungin omistamilla alueilla. Liito-oravalle sopivien metsien pinta-ala on vuosina 1966–2004 laskenut 48,8 %. ja liito-oravalle sopimattomien alueiden pinta-ala on kasvanut 22 %. Liikkumiselle soveltuva metsäpinta-ala on kasvanut 46,3 %. Liito-oravalle sopivien laikkujen keskikoko on laskenut 13,1 hehtaarista 4,7 hehtaariin ja alue on voimakkaasti pirstoutunut. Arvion mukaan Tampereen tutkimusalueen asuttujen liito-orava elinpiirien määrä on laskenut vuosina 1966–2004 yli 59 %. Tutkimusalueen metsiköiden kehitys on ollut vastaava kuin muilla metsätalousalueilla eteläisessä Suomessa. Kaupungin läheisyys ei ole merkittävästi vaikuttanut kehitykseen. Metsänhakkuiden ja asutuksen pirstomassa maisemassa viherkäytävien merkitys korostuu. Kuitenkin suuri osa liito-oravaesiintymistä sijaitsee kaupungin mailla ja jäljellä oleva soveltuvan metsän määrä on niin pieni ja pirstoutunut, että tulevaisuuden kaavoitustoimilla ja metsänkäsittelyllä tulee olemaan suuri vaikutus paikalliseen liito-oravakantaan.

Mesoporous Carbon and Poly(3,4-ethylenedioxythiophene) Composite as Catalyst Support for Polymer Electrolyte Fuel Cells

In situ polymerization of 3,4-ethylenedioxythiophene with sol-gel-derived mesoporous carbon (MC) leading to a new composite and its subsequent impregnation with Pt nanoparticles for application in polymer electrolyte fuel cells (PEFCs) is reported. The composite exhibits good dispersion and utilization of platinum nanoparticles akin to other commonly used microporous carbon materials, such as carbon black. Pt-supported MC-poly(3,4-ethylenedioxythiophene) (PEDOT) composite also exhibits promising electrocatalytic activity toward oxygen reduction reaction, which is central to PEFCs. The PEFC with Pt-loaded MC-PEDOT support exhibits 75% of enhancement in its power density in relation to the PEFC with Pt-loaded pristine MC support while operating under identical conditions. It is conjectured that Pt-supported MC-PEDOT composite ameliorates PEFC performance/durability on repetitive potential cycling. (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3486172] All rights reserved.

A Vicarious One-Pot Transformation of a Fluorocyclitol to a Polycyclitol: Observation of a Formal 4-Fold Axial-Equatorial Epimerization on a Conformationally Locked Scaffold

A conformationally locked fluoropentol undergoes an interesting transformation to (trans,anti,trans,anti,trans)-perhydro-2,3,4a,6,7,8a-naphthalenehexol essentially under conditions of base-induced transesterification. The proposed rationale for the observed metamorphosis involves a nucleophilic displacement of fluoride, and subsequent stereo- and regioselective anti-Furst-Plattner-type ring-opening of the epoxide thus formed.

Three different co-ordination geometries in the pentacopper(II) unit of [Cu5(OH)2(H2O)(O2CMe)6(Him)4][ClO4]2(Him = imidazole)

The reaction of imidazole (Him) with [Cu2(µ-O2CMe)4(H2O)2] in water–NaClO4 led to the formation of a polynuclear copper(II) complex, [Cu5(OH)2(H2O)(O2CMe)6(Him)4][ClO4]21, in which the pentanuclear units, showing four, five and six co-ordination geometries for the copper(II) centres and Cu Cu distances of 3.043(1), 3.178(1) and 3.578(1)Å, were linked by aqua bridges to give an intra-chain inter-unit Cu Cu separation of 4.507(1)Å.

Lanthanide perchlorate complexes of o,o' diisopropyl, n(-4-antipyryl) phosphoramidate

Five new complexes of lanthanide perchlorates with a new ligand O,O' diisopropyl N(-4-antipyryl) phosphoramidate (DIAP) of the general formula Ln(DIAP)4(ClO4)3 where Ln = La, Pr, Nd, Sm and Gd, have been synthesised and characterized by chemical analysis, IR(200–4000cm−1) and electronic spectra and electrical conductance data. Infrared spectral data indicate the coordination of the ligand to the metal ions in a bidentate fashion, through the C=O oxygen of the antipyrine group and the P=O group. IR and conductance values show that the three perchlorate groups are ionic. Electronic spectrum of the Nd3+ complex in the visible region, indicates reasonable covalency in the metal-ligand bond. The available data point to an eight coordinate geometry around the metal ions, with each ligand behaving in a bidentate ‘00’ fashion.

4-Nitro 2-picoline-l-oxide complexes of lanthanide perchlorates

4-Nitro 2-picoline-l-oxide (NPicO) complexes of the formulae La (NPicO)5 (CIO4)3, Ln2 (NPicO)9 (C1O4)6 (Ln = Pr, Nd, and Gd) and Ln (NPicO)4 (CIO4)3 (Ln == Tb, Dy, Ho and Yb) have been synthesised and characterised by analysis, electrolytic conductance, infrared, proton NMR and electronic spectral data. A tentative coordination number of 6 for all the complexes have been assigned

2(4)-SEMA as a sensitive and offset compensated SLF sequence

Separated Local Field (SLF) spectroscopy is a powerful tool for the determination of structure and dynamics of oriented systems such as membrane proteins oriented in lipid bilayers and liquid crystals. Of many SLF techniques available, Polarization Inversion Spin Exchange at Magic Angle (PISEMA) has found wide application due to its many favorable characteristics. However the pulse sequence suffers from its sensitivity to proton resonance frequency offset. Recently we have proposed a new sequence named 2(4)-SEMA (J. Chem. Phys. 132 (2010) 134301) that overcomes this problem of PISEMA. The present work demonstrates the advantage of 2(4)-SEMA as a highly sensitive SLF technique even for very large proton offset. 2(4)-SEMA has been designed for obtaining reliable dipolar couplings by switching the magic-angle spin-lock for protons over four quadrants as against the use of only two quadrants in PISEMA. It is observed that for on-resonance condition, 2(4)-SEMA gives rise to signal intensity comparable to or slightly higher than that from PISEMA. But under off-resonance conditions, intensities from 2(4)-SEMA are several fold higher than those from PISEMA. Comparison with another offset compensated pulse sequence, SAMPI4, also indicates a better intensity profile for 2(4)-SEMA. Experiments carried out on a single crystal of N-15 labeled N-acetyl-DL-valine and simulations have been used to study the relative performance of the pulse sequences considered. (C) 2010 Elsevier Inc. All rights reserved.

Synthesis and electrical properties of the (PVA)(0.7)(Kl)(0.3)center dot xH(2)SO(4) (0 <= x <= 5) polymer electrolytes and their performance in a primary Zn/MnO2 battery

Solid acid polymer electrolytes (SAPE) were synthesised using polyvinyl alcohol, potassium iodide and sulphuric acid in different molar ratios by solution cast technique. The temperature dependent nature of electrical conductivity and the impedance of the polymer electrolytes were determined along with the associated activation energy. The electrical conductivity at room temperature was found to be strongly depended on the amorphous nature of the polymers and H2SO4 concentration. The ac (100 Hz to 10 MHz) and dc conductivities of the polymer electrolytes with different H2SO4 concentrations were analyzed. A maximum dc conductivity of 1.05 x 10(-3) S cm(-1) has been achieved at ambient temperature for electrolytes containing 5 M H2SO4. The frequency and temperature dependent dielectric and electrical modulus properties of the SAPE were studied. The charge transport in the present polymer electrolyte was obtained using Wagner's polarization technique, which demonstrated the charge transport to be mainly due to ions. Using these solid acid polymer electrolytes novel Zn/SAPE/MnO2 solid state batteries were fabricated and their discharge capacity was calculated. An open circuit voltage of 1.758V was obtained for 5 M H2SO4 based Zn/SAPE/MnO2 battery. (C) 2010 Elsevier Ltd. All rights reserved.