Synthesis, Structure, Negative Thermal Expansion, and Photocatalytic Property of Mo Doped ZrV(2)O(7)

A new series of compounds identified in the phase diagram of ZrO(2)-V(2)O(8)-MoO(3) have been synthesized via the solution combustion method. Single crystals of one of the compounds in the series, ZrV(1.50)Mo(0.50)O(7.25), were grown by the melt-cool technique from the starting materials with double the MoO(3) quantity. The room temperature average crystal structure of the grown crystals was solved using the single crystal X-ray diffraction technique. The crystals belong to the cubic crystal system, space group Pa (3) over bar (No. 205) with a = 8.8969 (4) angstrom, V = 704.24 (6) angstrom(3), and Z = 4. The final R(1) value of 0.0213 was achieved for 288 independent reflections during the structure refinement. The Zr(4+) occupies the special position (4a) whereas V(5+) and Mo(6+) occupy two unique (8c) Wyckoff positions. Two fully occupied O atoms, (24d) and (4b), one partially occupied 0 atom (8c) have been identified for this molybdovanadate, which is a unique feature for these crystals. The structure is related to both ZrV(2)O(7) and cubic ZrMo(2)O(8). The temperature dependent single crystal studies show negative thermal expansion above 370 K. The compounds have been characterized by powder X-ray diffraction, solid-state UV-vis diffuse reflectance spectra, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The photocatalytic activity of these compounds has been investigated for the degradation of various dyes, and these compounds show specificity toward the degradation of non-azoic dyes.

Anomalous temperature dependence of phonons and photoluminescence bands in pyrochlore Er(2)Ti(2)O(7): signatures of structural deformation at 130 K

We report a Raman study of single crystal pyrochlore Er(2)Ti(2)O(7) as a function of temperature from 12 to 300 K. In addition to the phonons, various photoluminescence (PL) lines of Er(3+) in the visible range are also observed. Our Raman data show an anomalous red-shift of two phonons (one at similar to 200 cm(-1) and another at similar to 520 cm(-1)) upon cooling from room temperature which is attributed to phonon-phonon anharmonic interactions. However, the phonons at similar to 310, 330, and 690 cm(-1) initially show a blue-shift upon cooling from room temperature down to about 130 K, followed by a red-shift, indicating a structural deformation at similar to 130 K. The intensities of the PL bands associated with the transitions between the various levels of the ground state manifold ((4)I(15/2)) and the (2)H(11/2) as well as (4)S(3/2) excited state manifolds of Er(3+) show a change at similar to 130 K. Moreover, the temperature dependence of the peak position of the two PL bands shows a change in their slope (d(omega)/d(T)) at similar to 130 K, thus further strengthening the proposal of a structural deformation. The temperature dependence of the peak positions of the PL bands has been analyzed using the theory of optical dephasing in crystals.

Total and inelastic cross sections at LHC at root s=7 TeV and beyond

We discuss expectations for the total and inelastic cross sections at LHC CM energies root s = 7 TeV and 14 TeV obtained in an eikonal minijet model augmented by soft gluon k(t)-resummation, which we describe in some detail. We present a band of predictions which encompass recent LHC data and suggest that the inelastic cross section described by two-channel eikonal models include only uncorrelated processes. We show that this interpretation of the model is supported by the LHC data.

Toll-Like Receptors 7, 8, and 9 Expression and Function in Primary Human Cervical Cancer Langerhans Cells Evidence of Anergy

Objective: Human papillomavirus oncoproteins E6 and E7 down modulate Toll-like receptor (TLR) 9 expression in infected keratinocytes. We explored the status of expression and function of TLR7, TLR8, and TLR9 in primary human Langerhans cells (LCs) isolated from cervical tumors. Methodology: Single-cell suspensions were made from fresh tissues of squamous cell carcinoma (International Federation of Gynecology and Obstetrics stage IB2); myeloid dendritic cells were purified using CD1c magnetic activated cell separation kits. Langerhans cells were further flow sorted into CD1a(+)CD207(+) cells. Acute monocytic leukemia cell line THP-1-derived LCs (moLCs) formed the controls. mRNA from flow-sorted LCs was reverse transcribed to cDNA and TLR7, TLR8, and TLR9 amplified. Monocyte-derived Langerhans cells and cervical tumor LCs were stimulated with TLR7, TLR8, and TLR9 ligands. Culture supernatants were assayed for interleukin (IL) 1 beta, IL-6, IL-10, IL-12p70, interferon (IFN) alpha, interferon gamma, and tumor necrosis factor (TNF) alpha by Luminex multiplex bead array. Human papillomavirus was genotyped. Results: We have for the first time demonstrated that the acute monocytic leukemia cell line THP-1 can be differentiated into LCs in vitro. Although these moLCs. expressed all the 3 TLRs, tumor LCs expressed TLR7 and TLR8, but uniformly lacked TLR9. Also, moLCs secreted IL-6, IL-1 beta, and tumor necrosis factor alpha to TLR8 ligand and interferon alpha in response to TLR9 ligand; in contrast, tumor LCs did not express any cytokine to any of the 3 TLR ligands. Human papillomavirus type 16 was one of the common human papillomavirus types in all cases. Conclusions: Cervical tumor LCs lacked TLR9 expression and were functionally anergic to all the 3: TLR7, TLR8, and TLR9 ligands, which may play a crucial role in immune tolerance. The exact location of block(s) in TLR7 and TLR8 signaling needs to be investigated, which would have important immunotherapeutic implications.

Multicomponent self-sorting of a Pd-7 molecular boat and its use in catalytic Knoevenagel condensation

Unique three-component self-assembly of a cis-blocked 90 degrees Pd(II) acceptor with amixture of tri- and tetra-imidazole donors led to the self-sorting of a Pd-7 molecular boat with an internal nanocavity, which catalyses the Knoevenagel condensation of a series of aromatic aldehydes with 1,3-dimethylbarbituric acid and Meldrum's acid in aqueous media.

Conformational Diversity in Contryphans from Conus Venom: cis-trans Isomerisation and Aromatic/Proline Interactions in the 23-Membered Ring of a 7-Residue Peptide Disulfide Loop

Conformational diversity or shapeshifting in cyclic peptide natural products can, in principle, confer a single molecular entity with the property of binding to multiple receptors. Conformational equilibria have been probed in the contryphans, which are peptides derived from Conus venom possessing a 23-membered cyclic disulfide moiety. The natural sequences derived from Conus inscriptus, GCV(D)LYPWC* (In936) and Conus loroisii, GCP(D)WDPWC* (Lo959) differ in the number of proline residues within the macrocyclic ring. Structural characterisation of distinct conformational states arising from cis-trans equilibria about Xxx-Pro bonds is reported. Isomerisation about the C2-P3 bond is observed in the case of Lo959 and about the Y5-P6 bond in In936. Evidence is presented for as many as four distinct species in the case of the synthetic analogue V3P In936. The Tyr-Pro-Trp segment in In936 is characterised by distinct sidechain orientations as a consequence of aromatic/proline interactions as evidenced by specific sidechain-sidechain nuclear Overhauser effects and ring current shifted proton chemical shifts. Molecular dynamics simulations suggest that Tyr5 and Trp7 sidechain conformations are correlated and depend on the geometry of the Xxx-Pro bond. Thermodynamic parameters are derived for the cis trans equilibrium for In936. Studies on synthetic analogues provide insights into the role of sequence effects in modulating isomerisation about Xxx-Pro bonds.

Dielectric Function of Undoped and Doped Poly2-methoxy-5-(3 `,7 `-dimethyloctyloxy)-1,4-phenylene-vinylene] by Ellipsometry in a Wide Spectral Range

Ellipsometric measurements in a wide spectral range (from 0.05 to 6.5 eV) have been carried out on the organic semiconducting polymer, poly2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene-vinylene] (MDMO-PPV), in both undoped and doped states. The real and imaginary parts of the dielectric function and the refractive index are determined accurately, provided that the layer thickness is measured independently. After doping, the optical properties show the presence of new peaks, which could be well-resolved by spectroscopic ellipsometry. Also for the doped material, the complex refractive index, with respect to the dielectric function, has been determined. The broadening of the optical transitions is due to the delocalization of polarons at higher doping level. The detailed information about the dielectric function as well as refractive index function obtained by spectroscopic ellipsometry allows not only qualitative but also quantitative description of the optical properties of the undoped/doped polymer. For the direct characterization of the optical properties of MDMO-PPV, ellipsometry turns out to be advantageous compared to conventional reflection and transmission measurements.

Solid state structure of p-bromo phenyl 4,5,7-tri-O-benzyl-beta-D-glycero-D-talo-septanoside and an analysis of non-covalent interactions

The solid state structure of a new seven-membered sugar oxepane derivative, namely, p-bromo phenyl 4,5,7-tri-O-benzyl-beta-D-glycero-D-talo-septanoside is discussed, as determined through single crystal X-ray structural determination and in relation to their conformational features. The molecule adopts twist-chair as the preferred conformation, with conformational descriptor (TC2,3)-T-0,1. The solid state packing of molecules is governed by a rich network of non-covalent bonding originating from O-H center dot center dot center dot O, C-H center dot center dot center dot pi, C-H center dot center dot center dot Br and aromatic pi center dot center dot center dot pi interactions that stabilize the packing of molecules in the crystal. (C) 2015 Elsevier Ltd. All rights reserved.

Micro-scale composite compliant mechanisms for evaluating the bulk stiffness of MCF-7 cells

Biomechanical assays offer a good alternative to biochemical assays in diagnosing disease states and assessing the efficacy of drugs. In view of this, we have developed a miniature compliant tool to estimate the bulk stiffness of cells, particularly MCF-7 (Michigan Cancer Foundation) cells whose diameter is 12-15 mu m in suspension. The compliant tool comprises a gripper and a displacement-amplifying compliant mechanism (DaCM), where the former helps in grasping the cell and the latter enables vision-based force-sensing. A DaCM is necessary because the microscope's field of view at the required magnification is not sufficient to simultaneously observe the cell and the movement of a point on the gripper, in order to estimate the force. Therefore, a DaCMis strategically embedded within an existing gripper design leading to a composite compliant mechanism. The DaCM is designed using the kinetoelastostatic map technique to achieve a 42 nN resolution of the force. The gripper, microfabricated with SU-8 using photolithography, is within the footprint of about 10 mm by 10 mm with the smallest feature size of about 5 mu m. The experiments with MCF-7 cells suggest that the bulk stiffness of these is in the range of 8090 mN/m. The details of design, prototyping and testing comprise the paper. (C) 2015 Elsevier Ltd. All rights reserved.

Stable isotope evidence for ca. 2.7-Ga-old Archean cap carbonates from the Dharwar Supergroup, southern India

Carbon isotope compositions of carbonate rocks from similar to 2.7-Ga-old Neoarchean Vanivilas Formation of the Dharwar Supergroup presented earlier by us are re-evaluated in this study, besides oxygen isotope compositions of a few silica dolomite pairs. The purpose of such a revisit assumes significance in view of recent field evidences that suggest a glaciomarine origin for the matrix-supported conglomerate member, the Talya conglomerate, which underlies the carbonate rocks of the Vanivilas Formation. An in-depth analysis of carbon isotope data reveals preservation of their pristine character despite the rocks having been subjected to metamorphism to different degrees (from lower greenschist to lower amphibolite facies). The dolomitic member of Vanivilas Formation of Marikanive area is characterized by highly depleted delta C-13 value (up to -5 parts per thousand VPDB) and merits as the Indian example of ca. 2.7-Ga-old cap carbonate. This inference is further supported by estimated low temperature of equilibration documented by a few silica dolomite pairs from the Vanivilas Formation collected near Kalche area. These pairs show evidence for oxygen isotopic equilibrium at low temperatures (similar to 0-20 degrees C) with depleted water (delta O-18 = -21 parts per thousand to -15 parts per thousand VSMOW) of glacial origin. We propose that the mineral pairs were deposited during the deglaciation period when the ocean temperature was in its gradual restoration phase. The dolomite of Marikanive area is the first record of cap carbonates from the Indian subcontinent with Neoarchean antiquity.

Halogen Bonding and Chalcogen Bonding in 4,7-Dibromo-5, 6-dinitro-2,1,3-benzothiadiazole

An organic solid, 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole, has been designed to serve as an illustrative example to quantitatively evaluate the relative merits of halogen and chalcogen bonding in terms of charge density features. The compound displays two polymorphic modifications, one crystallizing in a non-centrosymmetric space group (Z' = 1) and the other in a centrosymmetric space group with two molecules in the asymmetric unit (Z' = 2). Topological analysis based on QTAIM clearly brings out the dominance of the chalcogen bond over the halogen bond along with an indication that halogen bonds are more directional compared to chalcogen bonds. The cohesive energies calculated with the absence of both strong and weak hydrogen bonds as well as stacking interaction are indicative of the stabilities associated with the polymorphic forms.

In Vitro Production of Echioidinin, 7-O-Methywogonin from Callus Cultures of Andrographis lineata and Their Cytotoxicity on Cancer Cells

Andrographis lineata is an herbal medicinal plant used in traditional medicine as a substitute for Andrographis paniculata. Here, using mature leaf explants of A. lineata we demonstrate for the first time the callus induction established on MS medium containing 1.0 mg l(-1) IAA. Dried callus was subjected to solvent extraction with acetone. Further the acetone residue was separated by silica gel column chromatography, crystallized and characterized on the basis of nuclear magnetic resonance (proton and c13) and liquid chromatographic mass spectroscopy. This analysis revealed the occurrence of two known flavones namely, 7-O-methylwogonin (MW) and Echioidinin (ED). Furthermore, these compounds were tested for their cytotoxicity against leukemic cell line, CEM. We identify that ED and MW induced cytotoxicity in a time-and concentration-dependent manner. Further increase in the LDH release upon treatment with ED and MW further confirmed our cytotoxicity results against leukemic cell line. Strikingly, MW was more potent than ED when compared by trypan blue and MTT assays. Our results recapitulate the utility of callus cultures for the production of plant specific bioactive secondary metabolites instead of using wild plants. Together, our in vitro studies provide new insights of A. lineata callus cultures serving as a source for cancer chemotherapeutic agents.