Evolution of confined ice nano structures at different levels of pore filling: a synchrotron based X-ray diffraction study.

We have thoroughly investigated the crystal structure of ice evolved from super cooled water confined in MCM-41 cylindrical nano pores through a synchrotron-based X-ray diffraction (XRD) technique for two different levels of pore filling. A rigorous analysis of XRD data shows that the nucleation dynamics and the structure of nucleated ice highly depend on the level of pore filling. In the nearly fully hydrated pores, ice crystallites start nucleating inside the pores below 240 K and creep out of the pores to form bulk crystals having crystalline structure of a mixed phase of hexagonal and cubic forms. In the partially hydrated pores, on the other hand, ice crystals cannot creep out of the pore crossing the energy barrier. The crystalline ice particles remaining inside the cylindrical pore show a short range "cubic rich" structure. The "pure cubic" phase has not been identified at either of the pore fillings in these 2.5 nm average size pores. A large fraction of water inside the pores remains in the super cooled liquid phase even at 180 K. This observation is relevant for understanding the ice nucleation through the pore condensation and freezing mechanism, which is a major pathway for the formation of cirrus clouds in the upper atmosphere.

Phase Transformation, Vibrational and Electronic Properties of K2Ce(PO4)2: A Combined Experimental and Theoretical Study.

Herein we report the high-temperature crystal chemistry of K2Ce(PO4)2 as observed from a joint in situ variable-temperature X-ray diffraction (XRD) and Raman spectroscopy as well as ab initio density functional theory (DFT) calculations. These studies revealed that the ambient-temperature monoclinic (P21/n) phase reversibly transforms to a tetragonal (I41/amd) structure at higher temperature. Also, from the experimental and theoretical calculations, a possible existence of an orthorhombic (Imma) structure with almost zero orthorhombicity is predicted which is closely related to tetragonal K2Ce(PO4)2. The high-temperature tetragonal phase reverts back to ambient monoclinic phase at much lower temperature in the cooling cycle compared to that observed at the heating cycle. XRD studies revealed the transition is accompanied by volume expansion of about 14.4%. The lower packing density of the high-temperature phase is reflected in its significantly lower thermal expansion coefficient (αV = 3.83 × 10-6 K-1) compared to that in ambient monoclinic phase (αV = 41.30 × 10-6 K-1). The coexistences of low- and high-temperature phases, large volume discontinuity in transition, and large hysteresis of transition temperature in heating and cooling cycles, as well as drastically different structural arrangement are in accordance with the first-order reconstructive nature of the transition. Temperature-dependent Raman spectra indicate significant changes around 783 K attributable to the phase transition. In situ low-temperature XRD, neutron diffraction, and Raman spectroscopic studies revealed no structural transition below ambient temperature. Raman mode frequencies, temperature coefficients, and reduced temperature coefficients for both monoclinic and tetragonal phases of K2Ce(PO4)2 have been obtained. Several lattice and external modes of rigid PO4 units are found to be strongly anharmonic. The observed phase transition and structures as well as vibrational properties of both ambient- and high-temperature phases were complimented by DFT calculations. The optical absorption studies on monoclinic phase indicated a band gap of about 2.46 eV. The electronic structure calculations on ambient-temperature monoclinic and high-temperature phases were also carried out.

Temperature dependent structural, vibrational and magnetic properties of K3Gd5(PO4)6.

Herein we report the evolution of the crystal structure of K3Gd5(PO4)6 in the temperature range from 20 K to 1073 K, as observed from variable temperature X-ray diffraction and Raman spectroscopic studies. K3Gd5(PO4)6 has an open tunnel containing a three dimensional structure built by [Gd5(PO4)6]3- ions which in turn are formed of PO4 tetrahedra and GdOn (n = 8 and 9) polyhedra. The empty tunnels in the structure are occupied by K+ ions and maintain charge neutrality in the lattice. Evolution of unit cell parameters with temperature shows a systematic increase with temperature. The average axial thermal expansion coefficients between 20 K and 1073 K are: αa = 10.6 × 10-6 K-1, αb = 5.5 × 10-6 K-1 and αc = 16.4 × 10-6 K-1. The evolution of distortion indices of the various coordination polyhedra with temperature indicates a gradual decrease with increasing temperature, while those of Gd2O9 and K2O8 polyhedra show opposite trends. The overall anisotropy of the lattice thermal expansion is found to be controlled largely by the effect of temperature on GdOn polyhedra and their linkages. Temperature dependent Raman spectroscopic studies indicated that the intensities and wavenumbers of most of the Raman modes decrease continuously with increasing temperature. Anharmonic analyses of Raman modes indicated that the lattice, rigid translation and librational modes have larger contributions towards thermal expansion of K3Gd5(PO4)6 compared to high frequency internal modes. The temperature and field dependent magnetic measurements indicated no long range ordering down to 2 K and the observed effective magnetic moment per Gd3+ ion and the Weiss constant are 7.91 µB and 0.38 K, respectively.

Structural Stability and Anharmonicity of Pr2Ti2O7: Raman Spectroscopic and XRD Studies.

Herein we report results of pressure- and temperature-dependent Raman scattering studies on Pr2Ti2O7. Pressure-dependent studies performed up to 23 GPa suggest a reversible phase transition above 15 GPa with subtle changes. Temperature-dependent investigations performed in the range of 77-1073 K showed anomalous temperature dependence of some of the Raman modes. Temperature-dependent X-ray diffraction data indicated no structural transition but nonlinear expansion of unit-cell parameters with increasing temperature. With increasing temperature, the structure dilates anisotropically, and volume of coordination polyhedra around all the atoms expands. Also with increasing temperature the distortions in coordination polyhedra around all the atoms decrease, and appreciable decrease is observed in Pr(1)O10 and Pr(3)O9 units. The pressure evolution of Raman-mode frequencies was analyzed for both ambient as well as high-pressure phases, and mode Grüneisen parameters for ambient pressure phase were obtained. The temperature evolution of Raman-mode frequencies was analyzed to obtain the explicit and implicit anharmonic components, and it was found that some of the modes attributable to TiO6 octahedra and PrOn polyhedra have dominating explicit anharmonic component. Comparison of the structural data with the temperature dependence of Raman modes suggests that the anomalous behavior in Raman modes is due to phonon-phonon interaction.

Structural and Thermal Properties of BaTe2O6: Combined Variable-Temperature Synchrotron X-ray Diffraction, Raman Spectroscopy, and ab Initio Calculations.

Variable-temperature Raman spectroscopic and synchrotron X-ray diffraction studies were performed on BaTe2O6 (orthorhombic, space group: Cmcm), a mixed-valence tellurium compound with a layered structure, to understand structural stability and anharmonicity of phonons. The structural and vibrational studies indicate no phase transition in it over a wider range of temperature (20 to 853 K). The structure shows anisotropic expansion with coefficients of thermal expansion in the order αb ≫ αa > αc, which was attributed to the anisotropy in bonding and structure of BaTe2O6. Temperature evolution of Raman modes of BaTe2O6 indicated a smooth decreasing trend in mode frequencies with increasing temperature, while the full width at half-maximum (fwhm) of all modes systematically increases due to a rise in phonon scattering processes. With the use of our earlier reported isothermal mode Grüneisen parameters, thermal properties such as thermal expansion coefficient and molar specific heat are calculated. The pure anharmonic (explicit) and quasiharmonic (implicit) contribution to the total anharmonicity is delineated and compared. The temperature dependence of phonon mode frequencies and their fwhm values are analyzed by anharmonicity models, and the dominating anharmonic phonon scattering mechanism is concluded in BaTe2O6. In addition to the lattice modes, several external modes of TeOn (n = 5, 6) are found to be strongly anharmonic. The ab initio electronic structure calculations indicated BaTe2O6 is a direct band gap semiconductor with gap energy of ∼2.1 eV. Oxygen orbitals, namely, O-2p states in the valence band maximum and the sp-hybridized states in the conduction band minimum, are mainly involved in the electronic transitions. In addition a number of electronic transitions are predicted by the electronic structure calculations. Experimental photoluminescence results are adequately explained by the ab initio calculations. Further details of the structural and vibrational properties are explained in the manuscript.

Effect of COVID-19 pandemic on blood transfusion service: an experience from a regional blood transfusion center.

The unforeseen and uncertain life-threatening situation of the COVID-19 pandemic dramatically affected all areas of the human daily work schedule. This study was designed to assess the impact of the COVID-19 pandemic on blood transfusion services and discuss the adopted confrontation measures for uninterrupted blood supply during the pandemic situation. The data on blood donation, blood component preparation, and issue from January 2019 to December 2022 were collected from the inventory registers of the RBTC, Delhi, India. Compared to the non-pandemic year 2019, during the year 2020, all variables decreased gradually. The observed maximum decrease in variables such as blood collection (-79.16%) in the month of October, blood issue (-71.61%) in the month of August, random donor platelets (RDP) preparation (-98.09%) in the month of October, RDP issue (-86.08%) in the month of September, fresh frozen plasma (FFP) preparation (-100%) in the month of October, and FFP issue (-96.08%) in the month of July with an annual decrease of -45.52%, -42.87%, -33.00%, -59.79%, -40.98%, and -54.48%, respectively, as compared to year 2019. Compared to year 2020, in year 2021, the annual increase in blood collection, blood issue, FFP preparation, FFP issue, RDP preparation, and RDP issue was +50.20%, +21.68%, +65.31%, +78.52%, +116.23%, and +213.30%, respectively. Our study results show that the COVID-19 pandemic has significantly affected blood transfusion services at our blood bank. The adopted coping strategies to maintain the safe and uninterrupted blood transfusion chain at our blood bank gave us lessons for future preparedness if faced with a similar situation.

Reactivity of allyl methyl sulphide, the in-vitro metabolite of garlic, with some amino acids and with phospholipid involved in viral infections.

Garlic, as well as several natural food ingredients such as basil, ginger, turmeric, cinnamon, clove, pepper etc., has long been traditionally used as routine anti-viral and anti-bacterial remedy. Allyl methyl sulfide (AMS) is reportedly a persistent main active metabolite component of allicin after garlic ingestion accounting for at least 90% of the allicin consumed. Several studies have reported the presence of AMS in organs such as lung, kidney etc. and body fluids such as mucous, and blood-plasma. Glycoproteins of enveloped viruses are actively involved in viral pathogenesis. N-acetylneuraminic acid (sialic acid) and N-Acetylglucosamine, are some of the vital amino acids involved in several viral infections using glycoproteins via glycosylation. Simulations studies based on First-principles density functional theory show that these amino acids attach with AMS, and the reactions are thermodynamically spontaneous (ΔG and ΔS negative are at 310.15 K as well as lower and higher temperatures). Further, phospholipid phosphatidylethanolamine (a component of some viral envelops) also attaches readily with AMS and the reaction is spontaneous. AMS molecules attachment with viral phospholipids and amino-acids involved in viral infection would denature the virus and prevent its attachment to the host cell.Communicated by Ramaswamy H. Sarma.

New organic-inorganic hybrid microporous organosilica having high metal ion adsorption capacity.

A new microporous organic-inorganic hybrid organosilica LHMM-2 containing a bis(propyliminomethyl)benzene moiety inside the framework has been synthesized hydrothermally without using any template or structure-directing agent. Powder XRD and TEM image analyses suggest a new disordered microporous structure with pores of dimension ca. 0.54 nm, and (13)C and (29)Si MAS NMR and spectroscopic results indicate the presence of bridging organic bis(propyliminomethyl)benzene moiety in this framework. TPD-NH(3) results suggested that nearly 5 times as much bis(propyliminomethyl)benzene moiety is located inside the micropore walls (matrix) than in the surface of the pores. LHMM-2 shows very high adsorption capacity for metal cations like Fe(3+), Cu(2+) and Zn(2+).

Preparation and crystal structure of K2Ce(PO4)2: a new complex phosphate of Ce(iv) having structure with one-dimensional channels.

In this manuscript we report crystal structure of a new complex binary phosphate K2Ce(4+)(PO4)2 in K2O-P2O5-CeO2 system prepared by solid state reaction at moderate temperature conditions. The prepared material was characterized by powder X-ray diffraction using lab source and synchrotron radiation as well as thermal analyses, Raman scattering, FTIR, and X-ray photoelectron spectroscopic studies. The crystal structure of the compound has been determined from powder XRD data by ab initio structure solution in direct space followed by Rietveld refinements. K2Ce(PO4)2 crystallizes in a monoclinic (P21/n) lattice with unit cell parameters: a = 9.1060(4), b = 10.8160(5), c = 7.6263(4) Å, ß = 111.155(2)°, V = 700.50(6) Å(3). The unit cell contains two distinguishable PO4 tetrahedra and one CeO8 distorted square anti-prism. Raman spectroscopy confirmed the presence of isolated PO4(3-) groups in the structure. These PO4 tetrahedra are connected to one CeO8 polyhedra by sharing one edge and three other CeO8 polyhedra by sharing corners to form the three dimensional structure and empty channels parallel to a-axis. The channels are occupied by two crystallographically distinguishable K(+) ions which maintain the charge neutrality. Contrast to the earlier reported composition K4Ce2P4O15, this study revealed the composition in actual is K4Ce2P4O16 with Ce in 4+ oxidation state and is also supported by X-ray photoelectron spectroscopic and X-ray absorption near edge structure studies. Differential scanning calorimetric studies revealed a structural transition around 525 °C which reverts on cooling with a large thermal hysteresis. At higher temperature it undergoes a loss of oxygen atom and subsequently loss of phosphorus as P2O5. These thermal effects are also supported by in situ high temperature XRD studies. Finally the crystal chemistry of complex phosphates with tetravalent cations is also discussed.

Preparation and characterization of novel mesoporous ceria-titania.

Synthesis of a novel thermally stable mesoporous ceria-titania phase using a neutral templating route is reported. The as-made inorganic-template hybrid mesostructured matrix showed a broad low-angle XRD peak characteristic of mesoporous materials. Careful thermal treatment of the matrix allowed the subsequent densification (of the pore walls) of the inorganic component and removal of the organic component so that a high-quality mesoporous ceria-titania was formed as observed by TEM analysis. The calcined material showed the formation of fluorite type structure of CeO(2) but no crystalline titania phase was observed. The mesoporous structure remained even after high-temperature treatment. The material had high surface area after calcination up to the temperature of 973 K, with well-dispersed ceria and titania components and negligible bulk oxide formation (from XRD, UV-vis, and XPS analysis). These novel mesoporous ceria-titania materials showed high performance for the removal of volatile organic compound (toluene). The toluene removal performance was further enhanced for Pt impregnated mesoporous ceria-titania.

Structural investigations in BaFe(2-x)Ru(x)As2 as a function of Ru and temperature.

We present the results of synchrotron X-ray diffraction (XRD) measurements on powdered single-crystal samples of BaFe(2-x)Ru(x)As2, as a function of Ru content, and as a function of temperature, across the spin-density wave transition in BaFe(1.9)Ru(0.1)As2. The Rietveld refinements reveal that with Ru substitution, while the a-axis increases, the c-axis decreases. In addition, the variation of positional coordinates of As (z(As)), the Fe-As bond length and the As-Fe-As bond angles have also been determined. In the sample with x = 0.1, temperature-dependent XRD measurements indicate that the orthorhombicity shows the characteristic increase with a decrease in temperature, below the magnetic transition. It is seen that the c-axis, the As-Fe-As bond angles, Fe-As bond length and positional coordinates of the As show definite anomalies close to the structural transition. The observed anomalies in structural parameters are analysed in conjunction with restricted geometric optimization of the structure using ab initio electronic structure calculations.

Iron Nanoparticles Supported on Graphene Oxide: A Robust, Magnetically Separable Heterogeneous Catalyst for the Oxidative Cyanation of Tertiary Amines.

Well-dispersed iron nanoparticles supported on chemically derived graphene oxide containing uniform distribution of iron nanoparticles (FeNPs) throughout the surface was synthesized and was used as a heterogeneous catalyst for oxidative cyanation of tertiary amines to the corresponding α-aminonitriles in high to excellent yields using hydrogen peroxide with sodium cyanide in acetic acid. After the reaction the catalyst could easily be separated by the influence of an external magnet and reused for several runs without any significant change in the catalytic activity and without leaching of the metal during the reaction.

Temperature-dependent reaction pathways for the anomalous hydrocracking of triglycerides in the presence of sulfided Co-Mo-catalyst.

Kinetic studies and product profiling was done to understand the anomalous cracking of jathropha oil triglycerides in the presence of sulfided Co-Mo/Al(2)O(3) catalyst. At temperatures between 320 and 340 °C, only deoxygenation and oligomerization reactions took place whereas at temperatures above 340 °C, internal conversions between the products and direct conversion to lighter and middle distillates were favored High pressures (80 bar) and H(2)/feed ratios (>1500) were necessary to minimize oligomerization of the products and to increase the lifespan of the catalyst. Lumped kinetic models were validated with experimental results. Activation energies for the formation of lighter (83 kJ/mol) and middle fractions (126 kJ/mol) were higher than those for the heavy (47 kJ/mol) and deoxygenated (47 kJ/mol) products. Jatropha oil triglycerides hydroconversion pathways were dependent on temperature and the triglycerides could be hydrocracked to lower range hydrocarbons (C5-C14) by increasing the reaction temperatures.

Cyclotriphosphazene grafted silica: a novel support for immobilizing the oxo-vanadium Schiff base moieties for hydroxylation of benzene.

The first report on the use of chlorotriphosphazenyl anchored mesoporous silica as a novel support for the immobilization of oxo-vanadium Schiff base moieties is described. The resulting heterogeneous material showed better catalytic activity than homogeneous as well as silica immobilized oxo-vanadium Schiff base for the hydroxylation of benzene with hydrogen peroxide.

Click on silica: systematic immobilization of Co(II) Schiff bases to the mesoporous silica via click reaction and their catalytic activity for aerobic oxidation of alcohols.

The systematic immobilization of cobalt(II) Schiff base complexes on SBA-15 mesoporous silica via copper catalyzed [3 + 2] azide-alkyne cycloaddition (CuAAC) "click reaction" involving either step-wise synthesis of silica-bound Schiff base ligand followed by its subsequent complexation with cobalt ions, or by the direct immobilization of preformed Co(II) Schiff base complex to the silica support is described. The catalytic activity of the prepared complexes was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were recycled for several runs without loss in catalytic activity and no leaching was observed during this course.

Dynamics of supercooled water in various mesopore sizes.

Double-quantum-filtered NMR and T(1) inversion-recovery spectroscopy were employed to exploit the temperature-dependent dynamics of D(2)O confined in MCM-41. Samples with three pore sizes of 1.58, 2.03, and 2.34 nm and two D(2)O contents were investigated. The reorientation correlation times of confined D(2)O in variously sized pores exhibit different temperature dependencies. The results reveal that the D(2)O molecules at fast motion site remain mobile below approximately 225 K and a liquid-liquid phase transition occurs around this temperature for all samples studied. This temperature is thought to be unreachable for supercooled D(2)O. Particularly, in 20 wt % D(2)O loaded samples with pore diameters of 1.58 and 2.03 nm, the reorientational correlation times of D(2)O at fast motion site exhibit Arrhenius behavior between 225 and 290 K, while other samples show power law dependency. Thus, a liquid phase of the fragile type in bigger pores changes to the strong type in samples with smaller pores.