102 resultados para fragmentation


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Seizure resistance of several cast aluminium base alloys has been examined using a standard Hohman Wear Tester. Disks of aluminium base alloys were run against a standard aluminium 12% silicon base alloy. The seizure resistance of the alloys (as measured by the lowest bearing parameter reached before seizure) increased with hardness, yield and tensile strength. In Al-Si-Ni alloys where silicon and nickel have little solid solubility in α-aluminium and Si and Ni Al3 hard phases are formed, the minimum bearing parameter decreased with the parameter V (The product of vol. % of hard phases in the disk and the shoe). Apparently the silicon and NiAl3 particles provided discontinuities in the matrix and reduced the probability (1 − V) of the α-aluminium phase in the disk coming into contact with the α-aluminium phase in the shoe. The copper and magnesium containing Al-Si-Ni alloys with lesser volumes of hard phases exhibit considerably better seizure resistance indicating that a slight increase in the solute content or the hardness of the primary α-phase leads to a considerable increase in seizure resistance. Deformation during wear and seizure leads to fragmentation of the original hard particles into considerably smaller particles uniformly dispersed in the deformed α-aluminium matrix.

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Aluminum-Nickel alloys ranging from 0.06 pct to 6.1 pct (by wt) Ni have been developed for high strength-high conductivity applications. These alloys were produced by solidification in a permanent mold followed by homogenization, hot extrusion or hot rolling and cold drawing to wire form. This sequence of fabrication a) led to the production of fine fibrous dispersoids of NiAl3 as part of the Al-NiAl3 eutectic during the initial casting operation, b) permitted the retention of fine fibrous dispersiods of NiAl3 produced during casting without any significant coarsening during processing and c) led to uniform dispersion and general alignment of these fibrous dispersoids along a given direction in the product without any measurable fiber-matrix separation, extensive fiber-fragmentation or crack production in the matrix. These alloys can be processed to wire form as easily as aluminum and when processed by the above sequence, possess very attractive combination of high strength-high electrical conductivity. Tensile strengths range from 173 N/mm2 (at 0.6 pct Ni) to 241 N/mm2 (at 6.1 pct Ni) in combination with corresponding conductivity values between 62 pct IACS and 55.5 pct IACS. The wires also possess attractive yield strength; for instance, the 0.2 pct off-set strength of Al-6.1 pct Ni wire is 213 N/mm2. Using simple composite rules, the estimated strength and the conductivity of NiAl3 fibers were found to be 1380 N/mm2 and 18 pct IACS respectively, in these wires.

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Jacalin [Artocarpus integrifolia (jack fruit) agglutinin] is made up of two types of chains, heavy and light, with M(r) values of 16,200 +/- 1200 and 2090 +/- 300 respectively (on the basis of gel-permeation chromatography under denaturing conditions). Its complete amino acid sequence was determined by manual degradation using a 4-dimethylaminoazobenzene 4'-isothiocyanate double-coupling method. Peptide fragments for sequence analysis were obtained by chemical cleavages of the heavy chain with CNBr, hydroxylamine hydrochloride and iodosobenzoic acid and enzymic cleavage with Staphylococcus aureus proteinase. The peptides were purified by a combination gel-permeation and reverse-phase chromatography. The light chains, being only 20 residues long, could be sequenced without fragmentation. Amino acid analyses and carboxypeptidase-Y-digestion C-terminal analyses of the subunits provided supportive evidence for their sequence. Computer-assisted alignment of the jacalin heavy-chain sequence failed to show sequence similarity to that of any lectin for which the complete sequence is known. Analyses of the sequence showed the presence of an internal repeat spanning residues 7-64 and 76-130. The internal repeat was found to be statistically significant.

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Although requirement for follicle stimulating hormone (FSH) in the initiation of spermatogenesis is well documented, its role in adult spermatogenesis is still debated. In the present communication, we have investigated the effect of specific immunoneutralization of FSH on apoptotic cell death in the testicular germ cells both in immature and adult rats. The germ cells of control animals showed predominantly high molecular weight DNA while the antiserum (a/s) treated group showed DNA fragmentation characteristic of apoptosis. The pattern could be detected within 24 hours of a/s treatment, and became more pronounced after 48 hours. The germ cells were purified from FSH a/s treated rats by centrifugal elutriation and vulnerability of each cell type to undergo apoptosis on FSH neutralization was investigated. The pachytene spermatocytes were found to be most sensitive to absence of FSH, even in the adult animals suggesting the involvement of FSH in spermatogenesis. The in situ analysis of DNA strand breakage following FSH a/s treatment showed fragmentation of the DNA of the pachytene spermatocytes confirming this observation. The in situ analysis also showed that the spermatogonia undergo apoptosis in addition to the pachytene spermatocytes. These data clearly demonstrate the role of FSH in the adult rat spermatogenesis.

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The present work deals with the anticancer effect of benzimidazole derivatives associated with the pyridine framework. By varying the functional group at N-terminal of the benzimidazole by different L-amino acids, several 2-(4-(2,2,2-trifluoroethoxy)-3-methylpyridin-2-ylthio)-1H-benzo[d]imid azole derivatives 9(a-j) were synthesized. Their chemical structures were confirmed by H-1 NMR, IR and mass spectroscopic techniques. The synthesized compounds were examined for their antiproliferative effects against human leukemia cell lines, K562 and CEM. The preliminary results showed most of the derivatives had moderate antitumor activity. Compound 9j containing cysteine residue exhibited good inhibition compared to other amino acid resides. In addition DNA fragmentation results suggest that 9j is more cytotoxic and able to induce apoptosis.

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Natural peptide libraries often contain cyclodepsipeptides containing alpha or beta hydroxy residues. Extracts of fungal hyphae of Isaria yield a microheterogenous cyclodepsipeptide mixture in which two classes of molecules can be identified by mass spectral fragmentation of negative ions. In the case of isaridins, which contain an alpha-hydroxy residue and a beta-amino acid residue, a characteristic product ion corresponding to a neutral loss of 72 Da is obtained. hi addition, neutral loss of water followed by a 72 Da loss is also observed. Two distinct modes of fragmentation rationalize the observed product ion distribution. The neutral loss of 72 Da has also been obtained for a roseotoxin component, which is also an alpha-hydroxy residue containing cyclodepsipeptide. In the case of isariins, which contain a beta-hydroxy acid residue, ring opening and subsequent loss of the terminal residue as an unsaturated ketene fragment, rationalizes the observed product ion formation. Fragmentation of negative ions provide characteristic neutral losses, which are diagnostic of the presence of alpha-hydroxy or beta-hydroxy residues.

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DNA intercalators are one of the most commonly used chemotherapeutic agents. Novel intercalating compounds of pyrimido[4',5':4,5]selenolo(2,3-b)quinoline series having a butylamino or piperazino group at fourth position (BPSQ and PPSQ, respectively) are studied. Our results showed that BPSQ induced cytotoxicity whereas PPSQ was cytostatic. The cytotoxicity induced by BPSQ was concentration- and time-dependent. Cell cycle analysis and tritiated thymidine assay revealed that BPSQ affects the cell cycle progression by arresting at S phase. The absence of p-histone H3 and reduction in the levels of PCNA in the cells treated with BPSQ further confirmed the cell cycle arrest. Further, annexin V staining, DNA fragmentation, nuclear condensation and changes in the expression levels of BCL2/BAD confirmed the activation of apoptosis. Activation of caspase 8 and lack of cleavage of caspase 9, caspase 3 and PARP suggest the possibility of BPSQ triggering extrinsic pathway for induction of apoptosis, which is discussed. Hence, we have identified a novel compound which would have clinical relevance in cancer chemotherapeutics.

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We compute the throughput obtained by a TCP connection in a UMTS environment. For downloading data at a mobile terminal, the packets of each TCP connection are stored in separate queues at the base station (node B). Also due to fragmentation of the TCP packets into Protocol Data Units (PDU) and link layer retransmissions of PDUs there can be significant delays at the queue of the node B. In such a scenario the existing models of TCP may not be sufficient. Thus, we provide a new approximate TCP model and also obtain new closed-form expressions of mean window size. Using these we obtain the throughput of a TCP connection which matches with simulations quite well.

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Carbon nanotubes (CNTs) have emerged as promising candidates for biomedical x-ray devices and other applications of field emission. CNTs grown/deposited in a thin film are used as cathodes for field emission. In spite of the good performance of such cathodes, the procedure to estimate the device current is not straightforward and the required insight towards design optimization is not well developed. In this paper, we report an analysis aided by a computational model and experiments by which the process of evolution and self-assembly (reorientation) of CNTs is characterized and the device current is estimated. The modeling approach involves two steps: (i) a phenomenological description of the degradation and fragmentation of CNTs and (ii) a mechanics based modeling of electromechanical interaction among CNTs during field emission. A computational scheme is developed by which the states of CNTs are updated in a time incremental manner. Finally, the device current is obtained by using the Fowler–Nordheim equation for field emission and by integrating the current density over computational cells. A detailed analysis of the results reveals the deflected shapes of the CNTs in an ensemble and the extent to which the initial state of geometry and orientation angles affect the device current. Experimental results confirm these effects.

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Enantiospecific synthesis of thaps-8-en-5-ol, comprising of the carbon framework of a small group of sesquiterpenes containing three contiguous quaternary carbon atoms has been described. (R)-Carvone has been employed as the chiral starting material and a combination of intramolecular alkyation and Criegec fragmentation have been employed for intramolecular stereospecific transfer of the chirality. An intramolecular diazoketone cyclopropanation and regioselective cyclopropane ring cleavage reactions have been employed for the creation of the three requisite contiguous quaternary carbon atoms.

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In the present work, a numerical study is performed to predict the effect of process parameters on transport phenomena during solidification of aluminium alloy A356 in the presence of electromagnetic stirring. A set of single-phase governing equations of mass, momentum, energy and species conservation is used to represent the solidification process and the associated fluid flow, heat and mass transfer. In the model, the electromagnetic forces are incorporated using an analytical solution of Maxwell equation in the momentum conservation equations and the slurry rheology during solidification is represented using an experimentally determined variable viscosity function. Finally, the set of governing equations is solved for various process conditions using a pressure based finite volume technique, along with an enthalpy based phase change algorithm. In present work, the effect of stirring intensity and cooling rate are considered. It is found that increasing stirring intensity results in increase of slurry velocity and corresponding increase in the fraction of solid in the slurry. In addition, the increasing stirring intensity results uniform distribution of species and fraction of solid in the slurry. It is also found from the simulation that the distribution of solid fraction and species is dependent on cooling rate conditions. At low cooling rate, the fragmentation of dendrites from the solid/liquid interface is more.

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A stereoselective synthesis of the C1-C18 region of marine natural product palmerolide A from chiral pool tartaric acid is presented. The key synthetic sequence includes the elaboration of a gamma-oxo-amide derived from tartaric acid and alkene formation involving Boord type fragmentation.

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Ten new cyclic hexadepsipeptides, six isariins and four isaridins, from the fungus Isaria have been identified and characterized by high-performance liquid chromatography, coupled to tandem electrospray ionization mass spectrometry (LC-ESIMS/MS). The isariins possess a beta-hydroxy acid residue and five alpha-amino acids, while isaridins contain a beta-amino acid, an alpha-hydroxy acid, and four alpha-amino acids. One- and two-dimensional NMR spectroscopy confirmed the chemical identity of some of the isariin fractions. Mass spectral fragmentation patterns of [M + H](+) ions reveal clear diagnostic fragment ions for the isariins and isaridins. Previously described cyclic depsipeptides, isarfelins from Isaria felina (Guo, Y. X.; Liu, Q. H.; Ng, T. B.; Wang H. X. Peptides 2005, 26, 2384), are now reassigned as members of the isaridin family. Examination of isaridin sequences revealed significant similarities with cyclic hexadepsipeptides such as destruxins and roseotoxins. The structure of an isariin (isariin A) investigated by NMR spectroscopy indicated the presence of a hybrid alpha beta C-11 turn, formed by the beta-hydroxy acid and glycine residues and a (D)Leu-(L)Ala type II' beta-turn. Additionally, the inhibitory effect of isariins and an isaridin on the intra-erythrocytic growth of Plasmodium falciparum is presented.

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Peptide disulfides are unstable under alkaline conditions, resulting in the formation of products containing lanthionine and polysulfied linkages. Electrospray ionization mass spectrometry has been used to characterize major species obtained when cyclic and acyclic peptide disulfides are exposed to alkaline media. Studies on a model cyclic peptide disulfide (Boc - Cys - Pro - Leu - Cys - NHMe) and an acyclic peptide, oxidized glutathione, bis ((gamma)Glu Cys - Gly - COOH), are described. Disulfide cleavage reactions are initiated by the abstraction of (CH)-H-alpha or (CH)-H-beta protons of Cys residues, with Subsequent elimination of H2S or H2S2. The buildup of reactive thiol species which act on intermediates containing dehydroalanine residues, rationalizes the formation of lanthionine and polysulfide products. In the case of the cyclic peptide disulfide, the formation of cyclic products is facilitated by the intramolecular nature of the Michael addition reaction of thiols to the dehydroalanine residue. Mass spectral evidence for the intermediate species is presented by using alkylation of thiol groups as a trapping method. Mass spectral fragmentation in the negative ion mode of the peptides derived from trisulfides and tetrasulfides results in elimination of S-2. (J Am Soc Mass Spectrom 2009, 20, 783-791) (C) 2009 American Society for Mass Spectrometry.

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Peptide disulfides are unstable under alkaline conditions, resulting in the formation of products containing lanthionine and polysulfied linkages. Electrospray ionization mass spectrometry has been used to characterize major species obtained when cyclic and acyclic peptide disulfides are exposed to alkaline media. Studies on a model cyclic peptide disulfide (Boc - Cys - Pro - Leu - Cys - NHMe) and an acyclic peptide, oxidized glutathione, bis ((gamma)Glu Cys - Gly - COOH), are described. Disulfide cleavage reactions are initiated by the abstraction of (CH)-H-alpha or (CH)-H-beta protons of Cys residues, with Subsequent elimination of H2S or H2S2. The buildup of reactive thiol species which act on intermediates containing dehydroalanine residues, rationalizes the formation of lanthionine and polysulfide products. In the case of the cyclic peptide disulfide, the formation of cyclic products is facilitated by the intramolecular nature of the Michael addition reaction of thiols to the dehydroalanine residue. Mass spectral evidence for the intermediate species is presented by using alkylation of thiol groups as a trapping method. Mass spectral fragmentation in the negative ion mode of the peptides derived from trisulfides and tetrasulfides results in elimination of S-2. (J Am Soc Mass Spectrom 2009, 20, 783-791) (C) 2009 American Society for Mass Spectrometry.