DNA Condensation by the Rat Spermatidal Protein TP2 Shows GC-Rich Sequence Preference and Is Zinc Dependent

Transition protein-2 (TP2), isolated from rat testes, was recently shown to be a zinc metalloprotein. We have now carried out a detailed analysis of the DNA condensing properties of TP2 with various polynucleotides using circular dichroism spectroscopy. The condensation of the alternating copolymers by TP2 (incubated with 10 mu M ZnSO4), namely, poly(dG-dC). poly(dG-dC) and poly(dA-dT). poly(dA-dT), was severalfold higher than condensation of either of the homoduplexes poly(dG). poly-(dC) and poly(dA). poly(dT) or rat oligonucleosomal DNA. Between the two alternating copolymers, poly(dG-dC). poly(dG-dC) was condensed 3.2-fold more effectively than poly(dA-dT). poly(dA-dT). Preincubation of TP2 with 5 mM EDTA significantly reduced its DNA-condensing property. Interestingly, condensation of the alternating copolymer poly(dI-dC). poly(dI-dC) by TP2 was much less as compared to that of poly(dG-dC). poly(dG-dC). The V8 protease-derived N-terminal fragment (88 aa) condensed poly(dA-dT). poly(dA-dT) to a very small extent but did not have any effect on poly(dG-dC). poly-(dG-dC). The C-terminal fragment (28 aa) was able to condense poly(dA-dT) . poly(dA-dT) more effectively than poly(dG-dC). poly(dG-dC). These results suggest that TP2 in its zinc-coordinated form condenses GC-rich polynucleotides much more effectively than other types of polynucleotides. Neither the N-terminal two-thirds of TP2 which is the zinc-binding domain nor the C-terminal basic domain are as effective as intact TP2 in bringing about condensation of DNA.

Metamorphic-metasomatic fluids and Al, Si order/disorder of K-rich alkali feldspars from southern Indian high grade terrain

The structural state of K-feldspars in the quartzofeldspathic gneisses, charnockites, metapelites and pegmatites from the southern Kamataka, northern Tamil Nadu and southern Kerala high-grade regions of southern India has been characterized using petrographic and powder X-ray diffraction methods. The observed distribution pattern of structural state with a preponderance of disordered K-feldspar polymorphs in granulites compared to the ordered microclines in the amphibolite facies rocks is interpreted to reflect principally the varying H2O contents in the metamorphic-metasomatic fluids across metamorphic grade. The K-feldspars in the pegmatites of granitic derivation and in a pegmatite of inferred metamorphic origin also point to the important role of aqueous fluids in their structural state.

Fluorescence and visual sensing of nitroaromatic explosives using electron rich discrete fluorophores

Several pi-electron rich fluorescent aromatic compounds containing trimethylsilylethynyl functionality have been synthesized by employing Sonogashira coupling reaction and they were characterized fully by NMR (H-1, C-13)/IR spectroscopy. Incorporation of bulky trimethylsilylethynyl groups on the peripheral of the fluorophores prevents self-quenching of the initial intensity through pi-pi interaction and thereby maintains the spectroscopic stability in solution. These compounds showed fluorescence behavior in chloroform solution and were used as selective fluorescence sensors for the detection of electron deficient nitroaromatics. All these fluorophores showed the largest quenching response with high selectivity for nitroaromatics among the various electron deficient aromatic compounds tested. Quantitative analysis of the fluorescence titration profile of 9,10-bis(trimethylsilylethynyl) anthracene with picric acid provided evidence that this particular fluorophore detects picric acid even at ppb level. A sharp visual detection of 2,4,6-trinitrotoluene was observed upon subjecting 1,3,6,8-tetrakis (trimethylsilylethynyl) pyrene fluorophore to increasing quantities of 2,4,6-trinitrotoluene in chloroform. Furthermore, thin film of the fluorophores was made by spin coating of a solution of 1.0 x 10(-3) M in chloroform or dichloromethane on a quartz plate and was used for the detection of vapors of nitroaromatics at room temperature. The vapor-phase sensing experiments suggested that the sensing process is reproducible and quite selective for nitroaromatic compounds. Selective fluorescence quenching response including a sharp visual color change for nitroaromatics makes these fluorophores as promising fluorescence sensory materials for nitroaromatic compounds (NAC) with a detection limit of even ppb level as judged with picric acid.

The production of AlN-rich matrix composites by the reactive infiltration of Al alloys in nitrogen

Aluminium nitride (AlN)-Al matrices reinforced with Al2O3 particulate have been fabricated by reactive infiltration of Al-2% Mg alloy into Al2O3 preforms in N-2 in the temperature range of 900-1075 degreesC. The growth of composites of useful thickness was facilitated by the presence of a Mg-rich external getter, in the absence of which composite growth is self-limiting and terminates prematurely. Successful growth of composites has been attributed to the reduction in residual oxygen partial pressure brought about by the reaction with oxygen of highly volatile Mg in the getter alloy. The microstructure of the matrix consists of AlN-rich regions contiguous with the particulate with metal-rich channels in-between, thereby suggesting that nitridation initiates by preferential wicking of alloy along the particle surfaces. The increase in nitride content of the matrix with temperature is consistent with hardness values that vary between similar to3 and 10 GPa. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Stress Evolution With Temperature in Titanium-Rich NiTi Shape Memory Alloy Films

The effect of deposition temperature on residual stress evolution with temperature in Ti-rich NiTi films deposited on silicon substrates was studied. Ti-rich NiTi films were deposited on 3? Si (100) substrates by DC magnetron sputtering at three deposition temperatures (300, 350 and 400 degrees C) with subsequent annealing in vacuum at their respective deposition temperatures for 4 h. The initial value of residual stress was found to be the highest for the film deposited and annealed at 400 degrees C and the lowest for the film deposited and annealed at 300 degrees C. All the three films were found to be amorphous in the as-deposited and annealed conditions. The nature of the stress response with temperature on heating in the first cycle (room temperature to 450 degrees C) was similar for all three films although the spike in tensile stress, which occurs at similar to 330 degrees C, was significantly higher in the film deposited and annealed at 300 degrees C. All the films were also found to undergo partial crystallisation on heating up to 450 degrees C and this resulted in decrease in the stress values around 5560 degrees C in the cooling cycle. The stress response with temperature in the second thermal cycle (room temperature to 450 degrees C and back), which is reflective of the intrinsic film behaviour, was found to be similar in all cases and the elastic modulus determined from the stress response was also more or less identical. The three deposition temperatures were also not found to have a significant effect on the transformation characteristics of these films such as transformation start and finish temperatures, recovery stress and hysteresis.

(Dimethylamino)borylene and Related Complexes of Electron-Rich Metal Fragments: Generation of Nucleophile-Resistant Cations by Spontaneous Halide Ejection

Spontaneous halide ejection from a three-coordinate Lewis acid has been shown to offer a remarkable new route to cationic metal complexes featuring a linear, multiply bonded boron-donor Ligand. The exploitation of electron-rich [CpM(PR3)(2)] fragments within boryl systems of the type LnMB(hal)NR2 leads to the spontaneous formation in polar solvents of chemically robust borylene complexes, [LnM(BNR2)](+), with exceptionally low electrophilicity and short M-B bonds. This is reflected by M-B distances (ca. 1.80 angstrom for FeB systems) which are more akin to alkyl-/aryl-substituted borylene complexes and, perhaps most strikingly, by the very low exothermicity associated with the binding of pyridine to the two-coordinate boron center (Delta H = -7.4 kcal mol(-1), cf. -40.7 kcal mol(-1) for BCl3). Despite the strong pi electron release from the metal fragment implied by this suppressed reactivity and by such short M-B bonds, the barrier to rotation about the Fe=B bond in the unsymmetrical variant [CpFe(dmpe)(BN{C6H4OMe-4}Me)](+) is found to be very small (ca. 2.9 kcal mol(-1)). This apparent contradiction is rationalized by the orthogonal orientations of the HOMO and HOMO-2 orbitals of the [CpML2](+) fragment, which mean that the M-B pi interaction does not fall to zero even in the highest energy conformation.

Interrelation of grain boundary microstructure and texture in a hot rolled Ni-rich NiTi alloy

This investigation deals with the evolution of grain boundary microstructure and crystallographic texture during hot rolling of a Ni-rich NiTi alloy. Electron backscattered diffraction studies revealed the occurrence of several coincidence site lattice (CSL) boundaries. The origin of these boundaries has been identified. The crystallographic texture of the deformed sample consists mainly of (1 1 1)parallel to normal direction fiber. The texture components on the fiber exhibit some correlation with the type of CSL boundary. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Peraluminous sapphirine-cordierite pods in Mg-rich orthopyroxene granulite from southern India: Implications for lower crustal processes

Sapphirine-cordierite intergrowths occur as pods within garnet-absent, high-Mg orthopyroxene-granulite xenoliths in the Kambam valley, Madurai Block, southern India. Whereas the cores of the pods are composed of sapphirine (X-Mg = 0.871-0.897) - cordierite (X-Mg = 0.892-0.931) intergrowth along with rutile, zircon and monazite, the rims are characterized by cordierite, apatite, plagioclase, K-feldspar, quartz and minor calcite. The surrounding matrix comprises orthopyroxene (maximum Al2O3 4.1 wt.%, X-Mg 0.848-0.850), plagioclase, biotite and quartz, similar to the assemblage in the surrounding charnockites. Sapphirine in the Kambam rocks is characterized by high Al contents with an end-member composition in the range of 7:9:3 and 3:5:1. The occurrence of peraluminous sapphirine in association with cordierite and in the absence of phases such as sillimanite and garnet is distinct from ultrahigh-temperature assemblages in other localities within the Madurai Block. The peraluminous composition of the pods suggests that these domains could represent cryptic pathways through which aluminous melts migrated. The reaction of such peraluminous melts with Mg-rich orthopyroxene in the host granulite at temperatures of 1025 degrees C and pressures around 8 kbar as computed from phase equilibria modeling followed by an isobaric cooling is inferred to have generated the sapphirine-cordierite pods. The unusual high-Mg orthopyroxene granulite suggests interaction of supracrustal rocks with mafic magmas, which probably acted as the heat source for the partial melting of lower crust and UHT metamorphism.

Caryophyllene-Rich Essential Oil of Didymocarpus tomentosa: Chemical Composition and Cytotoxic Activity

The essential oil from the leaves of Didymocarpus tomentosa was extracted by hydrodistillation and analyzed by GC/FID and GC/MS. Twenty five constituents amounting to 81.6% of the oil were identified. The leaf oil contained 78.7% sesquiterpenes and 2.9% monoterpenes. The leaf essential oil of D. tomentosa is a unique caryophyllene-rich natural source containing beta-caryophyllene, caryophyllene oxide, alpha-humulene and humulene oxide. The cytotoxic activity of the oil was determined by the BSLT using shrimp larva and the MTT assay using HeLa tumor cell line. The oil showed significant cytotoxic activity with LC50 and IC50 values of 12.26 and 11.4 mu g/mL, respectively. This is the first report on the chemical composition and cytotoxic activity of the essential oil of D. tomentosa.

Lacrimal Proline Rich 4 (LPRR4) Protein in the Tear Fluid Is a Potential Biomarker of Dry Eye Syndrome

Dry eye syndrome (DES) is a complex, multifactorial, immune-associated disorder of the tear and ocular surface. DES with a high prevalence world over needs identification of potential biomarkers so as to understand not only the disease mechanism but also to identify drug targets. In this study we looked for differentially expressed proteins in tear samples of DES to arrive at characteristic biomarkers. As part of a prospective case-control study, tear specimen were collected using Schirmer strips from 129 dry eye cases and 73 age matched controls. 2D electrophoresis (2DE) and Differential gel electrophoresis (DIGE) was done to identify differentially expressed proteins. One of the differentially expressed protein in DES is lacrimal proline rich 4 protein (LPRR4). LPRR4 protein expression was quantified by enzyme immune sorbent assay (ELISA). LPRR4 was down regulated significantly in all types of dry eye cases, correlating with the disease severity as measured by clinical investigations. Further characterization of the protein is required to assess its therapeutic potential in DES.

Electron rich supramolecular polymers as fluorescent sensors for nitroaromatics

Three pi-electron rich fluorescent supramolecular polymers (1-3) have been synthesized incorporating 2-methyl-3-butyn-2-ol groups in reasonable yield by employing Sonagashira coupling. They were characterized by multinuclear NMR (H-1, C-13), ESI-MS and single crystal X-ray diffraction analyses 1 = 1( 2-methyl-3-butyn-2-ol) pyrene; 2 = 9,10-bis(2-methyl-3-butyn-2-ol) anthracene; 3 = 1,3,6,8-tetrakis(2methyl- 3-butyn-2-ol) pyrene]. Single crystal structures of 1-3 indicated that the incorporation of hydroxy (-OH) groups on the peripheral of the fluorophores helps them to self-associate into an infinite supramolecular polymeric network via intermolecular hydrogen bonding interactions between the adjacent discrete fluorophore units. All these compounds showed fluorescence characteristics in chloroform solution due to the extended pi-conjugation and were used as selective fluorescent sensors for the detection of electron deficient nitroaromatics. The changes in photophysical properties of fluorophores (1-3) upon complex formation with electron deficient nitroaromatic explosives were studied in chloroform solution by using fluorescence spectroscopy. All these fluorophores showed the largest quenching response with moderate selectivity for nitroaromatics over various other electron deficient/ rich aromatic compounds tested (Chart 1). Analysis of the fluorescence titration profile of 9,10-bis(2-methyl-3butyn- 2-ol) anthracene fluorophore (2) with 1,3,5-trinitrotoluene/ 2,4-dinitrotoluene provided evidence that this particular fluorophore detects nitroaromatics in the nanomolar range 2.0 ppb for TNT, 13.7 ppb for DNT]. Moreover, sharp visual color change was observed upon mixing nitroaromatic (DNT) with fluorophores (1-3) both in solution as well as in solid phase. Furthermore, the vapor-phase sensing study of thin film of fluorophores (1-3) showed efficient quenching responses for DNT and this sensing process is reproducible. Selective fluorescence quenching response including a sharp visual color change for nitroaromatics make these tested fluorophores (1-3) as potential sensors for nitroaromatic compounds with a detection limit of ppb level.

Evidence of collective relaxation behavior in the reentrant phase of oxygen-rich LaMnO3

The reentrant low temperature phase of the perovskite manganite LaMnO3+delta (delta=0.22) has been investigated with ac susceptibility and dc magnetization studies. A critical examination of the memory effects in ac susceptibility leads us to the conclusion that the slow dynamics in the system is a consequence of collective relaxation processes resulting from interactions between ferromagnetic clusters, whose presence was indicated in earlier studies. Here, we postulate that the collective behavior is due to the existence of long-range (dipolar) interactions between the large ferromagnetic `superspins'. This is also confirmed by an abnormally large microscopic spin-flip time (similar to 10(-9) s) compared to a canonical spin glass. (C) 2013 Elsevier B.V. All rights reserved.

Isothermal transformation of beta-phase in Cu-rich Cu-Al-Sn alloys

Microstructural changes resulting from isothermal decomposition of the beta-phase have been studied in Cu-rich binary Cu-Al and ternary Cu-Al-Sn alloys containing up to 3 at.% Sn at temperatures from 873 to 673 K. Results are presented as TTT diagrams. The decomposition occurs in several stages, each of which involves the establishment of metastable equilibrium between beta and one or more of the product phases alpha, beta(1) and gamma(2). Addition of Sn has been shown to increase the stability of the ordered beta(1)-phase in relation to beta. In alloys containing more than 2 at.% Sn, the beta(1) emerges as a stable phase. At low Sn concentrations beta(1) is metastable. An important new finding is the existence of three-phase equilibrium microstructure containing alpha, beta(1) and gamma(2). Increasing addition of Sn alters the morphology of beta(1) from rosettes to dendrites and finally to Widmanstatten needles.

Effect of thermal and thermo-mechanical cycling on the microstructure of Ni-rich NiTi shape memory alloys

Microstructural changes of Ni-rich NiTi shape memory alloy during thermal and thermo-mechanical cycling have been investigated using Electron Back Scattered Diffraction. A strong dependence of the orientation of the prior austenite grain on the misorientation development has been observed during thermal cycling and thermo-mechanical cycling. This effect is more pronounced at the grain boundaries compared to grain interior. At a larger applied strain, the volume fraction of stabilized martensite phase increases with increase in the number of cycling. Deformation within the martensite leads to stabilization of martensitic phase even at temperatures slightly above the austenite finish temperature. Modulus variation with respect to temperature has been explained on the basis of martensitic transformation.

Electron microscopy of microstructural transformation in electrodeposited Ni-rich, Ag-Ni film

Ag-Ni films were electrodeposited over a Cu substrate. Structural characterization revealed a fibrous microstructure with an amorphous structure for the as-deposited film. Isothermal annealing at 400 degrees C of the film inside transmission electron microscope led to amorphous-to-crystalline transition along with the evolution of nano-sized particles in the microstructure. The crystalline phase was Ni-Ag solid solution. The relative volume fraction of the nano-sized particles increased gradually with time. There was however no detectable decomposition of solid solution phase till about 4 h of annealing. Beyond 4 h phase separation initiated and pure Ag and Ni phases formed in the film. This study provides a methodology by which microstructural engineering of as-electrodeposited amorphous Ag-Ni films can be conducted to isolate a particular microstructure in order to tap specific potentially usable functionalities. (C) 2013 Elsevier B.V. All rights reserved.