Vinyl radical induced Michael additions: Total synthesis of (±)-seychellene

A new strategy for the total synthesis of (±)-seychellene which involves (i) a regiospecific construction of a bicyclo(2.2.2)octene moiety having a methyl group at the bridgehead and (ii) a vinyl radical induced intramolecular Michael addition is described.

Aqueous channels within apolar peptide aggregates. Solvated helix of Boc-Aib-Ala-Leu-Aib-Ala-Leu-Aib- -Ala-Leu-Aib-OMe. H2O.CH3OH

Although the peptide Boc-Aibl-Ala2-Leu3- Aib4-Alas Leu'-Aib7-Ala8-Leu9-Aib'0-OMe [with a t-butoxycarbonyl(Boc) blocking group at the amino terminus, a methyl ester (OMe) at the carboxyl terminus, and four a-aminoisobutyric (Aib) residues] has a 3-fold repeat of residues, the helix formed by the peptide backbone is irregular. The carboxyl-terminal half assumes an at-helical form with torsion angles ) and r of approximately -60° and -45°, respectively, whereas the amino-terminal half is distorted by an insertion of a water molecule between the amide nitrogen of Ala5 [N(5)] and the carbonyl oxygen of Ala2 [0(2)]. The water molecule W(1) acts as a bridge by forming hydrogen bonds N(5).W(1) (2.93 A) and W(1)---0(2) (2.86 A). The distortion of the helix exposes the carbonyl oxygens of Aib' and Aib4 to the outside environment, with the consequence that the helix assumes an amphiphilic character despite having all apolar residues. Neighboring helices in the crystal run in antiparallel directions. On one side of a helix there are only hydrophobic contacts with efficient interdigitation of leucine side chains with those from the neighboring helix. On the other side of the helix there are hydrogen bonds between protruding carbonyl oxygens and four water molecules that separate two neighboring helices. Along the helix axis the helices bind head-to-tail with a direct hydrogen bond N(2)-0(9) (3.00 A). Crystals grown from methanol/water solution are in space group P2, with a = 15.778 ± 0.004 A, b = 11.228 ± 0.002 A, c = 18.415 ± 0.003 A, = 102.10 ± 0.02ur and two formula units per cell for C49HON1003 2H2OCH3OH. The overall agreement factorR is 7.5% for 3394 reflections observed with intensities >3a(F), and the resolution is 0.90 A.

Synthesis and characterization of flexible epoxy nanocomposites reinforced with amine functionalized alumina nanoparticles: a potential encapsulant for organic devices

Research on conducting polymers, organic light emitting diodes and organic solar cells has been an exciting field for the past decade. The challenge with these organic devices is the long term stability of the active material. Organic materials are susceptible to chemical degradation in the presence of oxygen and moisture. The sensitivity of these materials towards oxygen and moisture makes it imperative to protect them by encapsulation. Polymer nanocomposites can be used as encapsulation materials in order to prevent material degradation. In the present work, amine functionalized alumina was used as a cross-linking and reinforcing material for the polymer matrix in order to fabricate the composites to be used for encapsulation of devices. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy were used to elucidate the surface chemistry. Thermogravimetric analysis techniques and CHN analysis were used to quantify grafting density of amine groups over the surface of the nanoparticles. Mechanical characterizations of the composites with various loadings were carried out with dynamic mechanical analyzer. It was observed that the composites have good thermal stability and mechanical flexibility, which are important for an encapsulant. The morphology of the composites was evaluated using scanning electron microscopy and atomic force microscopy.

Effect of altering endogenous gonadotrophin concentrations on the kinetics of testicular germ cell turnover in the bonnet monkey (Macaca radiata)

The role of FSH and diurnal testosterone rhythms in specific germ cell transformations during spermatogenesis were investigated using DNA flow cytometry and morphometry of the seminiferous epithelium of the adult male bonnet monkey (Macaca radiata), the endogenous hormone levels of which were altered by two different protocols. (1) Active immunization of five monkeys for 290 days using ovine FSH adsorbed on Alhydrogel resulted in the neutralization of endogenous FSH, leaving the LH and diurnal testosterone rhythms normal. (2) Desensitization of the pituitary gonadotrophs of ten monkeys by chronically infusing gonadotrophin-releasing hormone analogue, buserelin (50 micrograms/day release rate), via an Alzet pump implant (s.c.) led to a 60-80% reduction in LH and FSH as well as total abolition of testosterone rhythms. The basal testosterone level (3.3 +/- 2.0 micrograms/l), however, was maintained in this group by way of an s.c. testosterone silicone elastomer implant. Both of the treatments caused significant (P < 0.01) nearly identical reduction in testicular biopsy scores, mitotic indices and daily sperm production rates compared with respective controls. The germ cell DNA flow cytometric profiles of the two treatment groups, however, were fundamentally different from each other. The pituitary-desensitized group exhibited a significant (P < 0.001) increase in 2C (spermatogonial) and decrease in 1C (round spermatid) populations while S-phase (preleptotene spermatocytes) and 4C (primary spermatocytes) populations were normal, indicating an arrest in meiosis caused presumably by the lack of increment in nocturnal serum testosterone. In contrast, in the FSH-immunized group, at day 80 when the FSH deprivation was total, the primary block appeared to be at the conversion of spermatogonia (2C) to cells in S-phase and primary spermatocytes (4C reduced by > 90%). In addition, at this time, although the round spermatid (1C) population was reduced by 65% (P < 0.01) the elongate spermatid (HC) population showed an increase of 52% (P < 0.05). This, taken together with the fact that sperm output in the ejaculate is reduced by 80%, suggests a blockade in spermiogenesis and spermiation. Administration of booster injections of oFSH at time-points at which the antibody titre was markedly low (at days 84 and 180) resulted in a transient resurgence in spermatogenesis (at day 180 and 228), and this again was blocked by day 290 when the FSH antibody titre increased.

Breast cancer and human papillomavirus infection: No evidence of HPV etiology of breast cancer in Indian women

Background: Two clinically relevant high-risk HPV (HR-HPV) types 16 and 18 are etiologically associated with the development of cervical carcinoma and are also reported to be present in many other carcinomas in extra-genital organ sites. Presence of HPV has been reported in breast carcinoma which is the second most common cancer in India and is showing a fast rising trend in urban population. The two early genes E6 and E7 of HPV type 16 have been shown to immortalize breast epithelial cells in vitro, but the role of HPV infection in breast carcinogenesis is highly controversial. Present study has therefore been undertaken to analyze the prevalence of HPV infection in both breast cancer tissues and blood samples from a large number of Indian women with breast cancer from different geographic regions. Methods: The presence of all mucosal HPVs and the most common high-risk HPV types 16 and 18 DNA was detected by two different PCR methods - (i) conventional PCR assays using consensus primers (MY09/11, or GP5 +/GP6+) or HPV16 E6/E7 primers and (ii) highly sensitive Real-Time PCR. A total of 228 biopsies and corresponding 142 blood samples collected prospectively from 252 patients from four different regions of India with significant socio-cultural, ethnic and demographic variations were tested. Results: All biopsies and blood samples of breast cancer patients tested by PCR methods did not show positivity for HPV DNA sequences in conventional PCRs either by MY09/11 or by GP5+/GP6+/HPV16 E6/E7 primers. Further testing of these samples by real time PCR also failed to detect HPV DNA sequences. Conclusions: Lack of detection of HPV DNA either in the tumor or in the blood DNA of breast cancer patients by both conventional and real time PCR does not support a role of genital HPV in the pathogenesis of breast cancer in Indian women.

Non-Fermi liquid behavior in a mean-field study of the t-J model: Role of zero-point spin fluctuations

We present analytic results to show that the Schwinger-boson hole-fermion mean-field state exhibits non-Fermi liquid behavior due to spin-charge separation. The physical electron Green's function consists of three additive components. (a) A Fermi-liquid component associated with the bose condensate. (b) A non-Fermi liquid component which has a logarithmic peak and a long tail that gives rise to a linear density of states that is symmetric about the Fermi level and a momentum distribution function with a logarithmic discontinuity at the Fermi surface. (c) A second non-Fermi liquid component associated with the thermal bosons which leads to a constant density of states. It is shown that zero-point fluctuations associated with the spin-degrees of freedom are responsible for the logarithmic instabilities and the restoration of particle-hole symmetry close to the Fermi surface.

Purification and partial characterization of acyl carrier proteins from developing oil seeds of pisa (Actinodaphne hookeri) and ground nut (Arachis hypogaea)

Acyl carrier proteins (ACP) were purified to homogeneity in the active form from developing seeds of pisa (Actinodaphne hookeri) which synthesizes exclusively trilaurin and from ground nut (Arachis hypogaea) which synthesizes triacylglycerols containing long chain fatty acids. Two major isoforms of ACPs were purified from developing pisa seeds using DEAE-cellulose, Superose-6 FPLC and C-4 reversed phase HPLC chromatographic methods. In contrast, only a single form of ACP was present in ground nut seeds which was purified by anion-exchange and activated thiol-Sepharose 4B affinity chromatography. The two isoforms of ACPs from pisa showed nearly the same specific activity of 6,706 and 7,175 pmol per min per mg protein while ground nut ACP showed a specific activity of 3,893 pmol per min per mg protein when assayed using E. coli acyl-ACP synthetase and [1-C-14]palmitic acid. When compared with E. coli ACP, the purified ACPs from both the seeds showed considerable difference in their mobility in native PAGE, but showed similar mobility in SDS-PAGE under reducing conditions. In the absence of reducing agents formation of dimers was quite prominent. The ACPs from both the seed sources were acid- and heat-stable. The major isoform of pisa seed ACP and the ground nut ACP contain 91 amino acids with M(r) 11,616 and 1,228 respectively. However, there is significant variation in their amino acid composition. A comparision of the amino acid sequence in the N-terminal region of pisa and ground nut seed ACPs showed considerable homology between themselves and with other plant ACPs but not with E. coli ACP.

Crystal structure of nonadentate tricompartmental ligand derived from pyridine-2,6-dicarboxylic acid: Spectroscopic, electrochemical and thermal investigations of its transition metal(II) complexes

The coordinating behavior of a new dihydrazone ligand, 2,6-bis(3-methoxysalicylidene) hydrazinocarbonyl]pyridine towards manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) has been described. The metal complexes were characterized by magnetic moments, conductivity measurements, spectral (IR, NMR, UV-Vis, FAB-Mass and EPR) and thermal studies. The ligand crystallizes in triclinic system, space group P-1, with alpha=98.491(10)degrees, beta=110.820(10)degrees and gamma=92.228(10)degrees. The cell dimensions are a=10.196(7)angstrom, b=10.814(7)angstrom, c=10.017(7)angstrom, Z=2 and V=1117.4(12). IR spectral studies reveal the nonadentate behavior of the ligand. All the complexes are neutral in nature and possess six-coordinate geometry around each metal center. The X-band EPR spectra of copper(II) complex at both room temperature and liquid nitrogen temperature showed unresolved broad signals with g(iso) = 2.106. Cyclic voltametric studies of copper(II) complex at different scan rates reveal that all the reaction occurring are irreversible. (C) 2011 Elsevier B.V. All rights reserved.

278. Studies on ass's milk: Composition

The total solids of samples of ass's milk ranged from 7·80 to 9·10, the solids-not-fat from 7·14 to 8·50, and the fat from 0·54 to 0·71%. The nitrogen distribution in ass's milk is: casein 39·5, albumin 35·0, globulin 2·7 and non-protein nitrogen 22·8% of the total nitrogen. Ass's milk contains: casein 0·70, albumin 0·62 and globulin 0·07%. The total protein content is 1·39%. Ass's milk is therefore characterized by a low casein, a low globulin and a high albumin content. The non-protein nitrogen consists of amino nitrogen 8·1, urea nitrogen 24·3 and uric acid 0·7 mg./100 ml. of milk. The urea content is twice that present in cow's milk. The mean chloride and lactose contents of the milk samples are 0·037 and 6·1% respectively. The average calcium and phosphorus content of ass's milk are 0·081 and 0·059% respectively. Half the calcium is ionic, and half is in colloidal form. The phosphorus distribution is: total acid soluble 84·0, acid soluble organic 38·5, easily hydrolysable ester 27·4, inorganic 46·0, and colloidal inorganic 23·0 % of the total phosphorus. The ratio of CaO: P2O5 is 1:1. 46 % of the total phosphorus is in ester form; this is high when compared with only 12 % in cow's milk; most of the phosphoric ester forms soluble barium salts, which is a distinguishing feature of ass's milk. The total sulphur content is 15·8 mg./100 ml. The fat has a penetrating odour and is coloured orange-yellow. It has an iodine value of about 86, which is much higher than that for human milk fat. The Reichert (9·5) and Kirschner values (5·7) are low. In general, the composition of ass's milk resembles that of human rather than of cow's milk.

The electrical switching and thermal behavior of bulk Ge(15)Te(85-x)Sn(x) and Ge(17)Te(83-x)Sn(x) glasses

Bulk Ge(15)Te(85 - x)Sn(x) and Ge(17)Te(83 - x)Sn(x) glasses, are found to exhibit memory type electrical switching. The switching voltages (V(t)) and thermal stability of Ge(15)Te(85 - x)Sn(x) and Ge(17)Te(83 - x)Sn(x) glasses are found to decrease with Sn content. The composition dependence of v, has been understood on the basis of the decrease in the OFF state resistance and thermal stability of these glasses with tin addition. X-ray diffraction studies reveal that no elemental Sn or Sn compounds with Te or Ge are present in thermally crystallized Ge-Te-Sn samples. This indicates that Sn atoms do not interact with the host matrix and form a phase separated network of its own, which remains in the parent glass matrix as an inclusion. Consequently, there is no enhancement of network connectivity and rigidity. The thickness dependence of switching voltages of Ge(15)Te(85 - x)Sn(x) and Ge(17)Te(83 - x)Sn(x) glasses is found to be linear, in agreement with the memory switching behavior shown by these glasses. (C) 2011 Elsevier B.V. All rights reserved.

Thermoluminescence and EPR studies of nanocrystalline Nd2O3:Ni2+ phosphor

Nanocrystalline Nd2O3:Ni2+ (2 mol%) phosphor has been prepared by a low temperature (similar to 400 degrees C) solution combustion method, in a very short time (<5 min). Powder X-ray diffraction results confirm the single hexagonal phase of nanopowders. Scanning electron micrographs show that nanophosphor has porous nature and the particles are agglomerated. Transmission electron microscopy confirms the nanosize (20-25 nm) of the crystallites. The electron paramagnetic resonance (EPR) spectrum exhibits a symmetric absorption at g approximate to 2.77 which suggests that the site symmetry around Ni2+ ions is predominantly octahedral. The number of spins participating in resonance (N) and the paramagnetic susceptibility (chi) has been evaluated. Raman study show major peaks, which are assigned to F-g and combination of A(g) + E-g modes. Thermoluminescence (TL) studies reveal well resolved glow peaks at 169 degrees C along with shoulder peak at around 236 degrees C. The activation energy (E in eV), order of kinetics (b) and frequency factor (s) were estimated using glow peak shape method. It is observed that the glow peak intensity at 169 degrees C increases linearly with gamma-dose which suggest that Nd2O3:Ni2+ is suitable for radiation dosimetry applications. (C) 2012 Elsevier B.V. All rights reserved.

Further evidence for room temperature, indentation-induced nanocrystallization in a bulk metallic glass

Room temperature nanoindentation experiments, employing two different pyramidal (Berkovich and cube-corner) indenters, were performed on a Zr-based bulk metallic glass (BMG) to critically examine the possibility of indentation-induced nanocrystallization in BMGs. Cross-sectional transmission electron microscopy images obtained from high angle annular dark field ( HAADF) and high resolution (HR) modes clearly indicate to the occurrence of nanocrystallization. Pronounced nanocrystallite formation in the case of sharper cube-corner indenter suggests that the structural transformation is favored by the high strains introduced during nanoindentation. (c) 2012 Elsevier B.V. All rights reserved.

Under-representation of intrinsic terminators across bacterial genomic islands: Rho as a principal regulator of xenogenic DNA expression

Two transcription termination mechanisms - intrinsic and Rho-dependent - have evolved in bacteria. The Rho factor occurs in most bacterial lineages, and has been hypothesized to play a global regulatory role. Genome-wide studies using microarray, 2D-gel electrophoresis and ChIP-chip provided evidence that Rho serves to silence transcription from horizontally acquired genes and prophages in Escherichia coli K-12, implicating the factor to be a part of the ``cellular immune mechanism'' protecting against deleterious phages and aberrant gene expression from acquired xenogenic DNA. We have investigated this model by adopting an alternate in silico approach and have extended the study to other species. Our analysis shows that several genomic islands across diverse phyla have under-representation of intrinsic terminators, similar to that experimentally observed in E. coli K-12. This implies that Rho-dependent termination is the predominant process operational in these islands and that silencing of foreign DNA is a conserved function of Rho. From the present analysis, it is evident that horizontally acquired islands have lost intrinsic terminators to facilitate Rho-dependent termination. These results underscore the importance of Rho as a conserved, genome-wide sentinel that regulates potentially toxic xenogenic DNA. (C) 2012 Elsevier B.V. All rights reserved.

Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods and Na0.33V2O5 center dot 1.5H(2)O/RGO composite fabricated by a facile one pot synthesis and its lithium storage behavior

In this work, Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods and Na0.33V2O5 center dot 1.5H(2)O/reduced graphene oxide (RGO) composites have been prepared through a facile hydrothermal route in acidic medium at 200 degrees C for 2 days. The hydrothermally derived products have been characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, UV-Visible spectroscopy, Thermogravimetric analysis (TGA), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM) and electrochemical discharge-charge cycling in lithium ion battery. XRD pattern exhibits the layered structure of Na0.33V2O5 center dot 1.5H(2)O and the composite shows the presence of RGO at 2 theta = 25.8 degrees. FTIR spectrum shows that the band at 760 cm(-1) could be assigned to a V-OH2 stretching mode due to coordinated water. Raman spectrum shows that the band at 264 cm(-1) is due to the presence of water molecules between the layers. FESEM/TEM micrographs reveal that the products consist of nanorings of inner diameter 5 mu m and thickness of the ring is found to be 200-300 nm. Addition of exfoliated graphene oxide (EGO) destroys the formation of rings. The reduction of EGO sheets into RGO is also evidenced by the red shift of the absorbance peak from 228 nm to 264 nm. In this composite Na0.33V2O5 center dot 1.5H(2)O nanorods may adhere to the surface of RGO and/or embedded in the RGO nanosheets. As a result, an effective three-dimensional conducting network was formed by bridging RGO nanosheets, which can facilitate electron transport effectively and thus improve the kinetics and rate performance of Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods. The Na0.33V2O5 center dot 1.5H(2)O/RGO composites exhibited a discharge capacity of 340 mAh g(-1) at a current density of 0.1 mA g(-1) and also an improved cyclic stability. RGO plays a `flexible confinement' function to enwrap Na0.33V2O5 center dot 1.5H(2)O nanorods, which can compensate for the volume change and prevent the detachment and agglomeration of pulverized Na0.33V2O5 center dot 1.5H(2)O, thus extending the cycling life of the electrode. A probable reaction mechanism for the formation of Na0.33V2O5 center dot 1.5H(2)O nanorings is also discussed. (C) 2012 Elsevier B.V. All rights reserved.