Dynamical Transition of Water in the Grooves of DNA Duplex at Low Temperature

At low temperature (below its freezing/melting temperature), liquid water under confinement is known to exhibit anomalous dynamical features. Here we study structure and dynamics of water in the grooves of a long DNA duplex using molecular dynamics simulations with TIP5P potential at low temperature. We find signatures of a dynamical transition in both translational and orientational dynamics of water molecules in both the major and the minor grooves of a DNA duplex. The transition occurs at a slightly higher temperature (TGL ≈ 255 K) than the temperature at which the bulk water is found to undergo a dynamical transition, which for the TIP5P potential is at 247 K. Groove water, however, exhibits markedly different temperature dependence of its properties from the bulk. Entropy calculations reveal that the minor groove water is ordered even at room temperature, and the transition at T ≈ 255 K can be characterized as a strong-to-strong dynamical transition. Confinement of water in the grooves of DNA favors the formation of a low density four-coordinated state (as a consequence of enthalpy−entropy balance) that makes the liquid−liquid transition stronger. The low temperature water is characterized by pronounced tetrahedral order, as manifested in the sharp rise near 109° in the O−O−O angle distribution. We find that the Adams−Gibbs relation between configurational entropy and translational diffusion holds quite well when the two quantities are plotted together in a master plot for different region of aqueous DNA duplex (bulk, major, and minor grooves) at different temperatures. The activation energy for the transfer of water molecules between different regions of DNA is found to be weakly dependent on temperature.

Temperature dependence of 35Cl NQR in 2,6-dichloropyridine

Chlorine NQR in 2,6-dichloropyridine has been investigated in the temperature range 77 K to room temperature and a single resonance line has been observed throughout. Using this data, torsional frequencies of the molecule have been evaluated on the basis of both the Bayer theory and the modified Bayer theory incorporating Tatsuzaki correction.

1H NMR and a study of the anomalous temperature dependence of the 35Cl NQR frequencies in 2-chloro-3-pyridinol

A 35Cl NQR study of 2-chloro-3-pyridinol showed the presence of four NQR signals at 77 K. One of the lines showed a positive temperature coefficient of the NQR frequency. 1H NMR studies showed the presence of intramolecular hydrogen bonding, and the anomalous NQR temperature dependence has been explained in terms of Bayer and hydrogen bond effects. The room temperature x-ray structure and the low-temperature NQR data suggest the presence of a phase transition.

In Situ Phase Separation Following Dehydration in Bimetallic Sulfates: A Variable-Temperature X-Ray Diffraction Study

Phase separation resulting in a single-crystal-single-crystal transition accompanied by a polycrystalline phase following the dehydration of hydrated bimetallic sulfates [Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O and K4Cd3-(SO4)(5)center dot 3H(2)O] has been investigated by in situ variable-temperature single-crystal X-ray diffraction. With two examples, we illustrate the possibility of generating structural frameworks following dehydration in bimetallic sulfates, which refer to the possible precursor phases at that temperature leading to the mineral formation. The room-temperature structure of Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O is trigonal, space group R (3) over bar. On heating the crystal in situ on the diffractometer, the diffraction images display spherical spots and concentric rings suggesting phase separation, with the spherical spots getting indexed in a monoclinic space group, C2/c. The structure determination based on this data suggests the formation of Na2Mn(SO4)(2). However, the diffraction images from concentric rings could not be indexed. In the second example, the room-temperature structure is determined to be K4Cd3(SO4)(5)center dot 3H(2)O, crystallizing in a monoclinic space group, P2(1)/n. On heating the crystal in situ, the diffraction images collected also have both spherical spots and diffuse rings. The spherical spots could be indexed to a cubic crystal system, space group P2(1)3, and the structure is K4Cd3(SO4)(3). The possible mechanism for the phase transition in the dehydration regime resulting in this remarkable single-crystal to single-crystal transition with the appearance of a surrogate polycrystalline phase is proposed.

Temperature dependence of 35Cl NQR in 3,4-Dichlorophenol

NQR frequencies in 3,4-dichlorophenol are investigated in the temperature range 77 K to room temperature. Two resonances have been observed throughout the temperature range, corresponding to the two chemically inequivalent chlorine sites. Using Bayer's theory and Brown's method torsional frequencies and their temperature dependence in this range are estimated.

Temperature-dependence of 35Cl N.Q.R. in sodium chloroacetate

N.q.r. in sodium chloroacetate has been investigated at temperatures from 77 K to room temperature (c.300 K). A single line has been observed throughout this temperature range. Torsional frequencies of the molecule have been calculated in the above temperature range from Bayer's theory. Also the temperature coefficient of the torsional frequencies has been calculated by Brown's method.

Temperature dependence of chlorine NQR in 2-chloro 5-nitrobenzoic acid and 4-chloro 3-nitrobenzoic acid

Temperature dependence of chlorine nuclear quadrupole resonance in 2-chloro 5-nitrobenzoic acid and 4-chloro 3-nitrobenzoic acid has been investigated in the region 77° K to room temperature. No phase transition has been observed. The results are analysed to obtain the torsional frequencies and their temperature dependence. A nonlinear temperature dependence is obtained for the torsional frequencies.

Towards a temperature-guided molecular switch: an unusual reversible low-temperature polymorphic phase transition in a conformational locked environment

A conformationally locked tetraacetate undergoes, quite akin to a temperature-guided molecular switch, a reversible thermal switching between two polymorphic modifications; the room-temperature alpha-form converted at -4 degrees C to a low-temperature denser beta-form, which displayed an unusual kinetic stability till 67 degrees C and transformed back to the alpha-form beyond this temperature.

High pressure clamp for electrical measurements up to 8 GPa and temperature down to 77 K

A compact clamp-type high pressure cell for carrying out electrical conductivity measurements on small solid samples of size 1 mm or less at pressures upto 8 GPa (i.e., 80 kbar) and for use down to 77 K has been designed and fabricated. The pressure generated in the sample region has been calibrated at room temperature against the polymorphic phase transitions of Bismuth and Ytterbium. The pressure relaxation of the clamp at low temperatures has been estimated by monitoring the electrical conductivity behavior of lead. Review of Scientific Instruments is copyrighted by The American Institute of Physics.

Low temperature molten-salt synthesis of nanocrystalline cubic Sr2SbMnO6

Sr2SbMnO6 (SSM) powders were successfully synthesized at reasonably low temperatures via molten-salt synthesis (MSS) method using eutectic composition of 0.635 Li2SO4-0.365 Na2SO4 (flux). High-temperature cubic phase SSM was stabilized at room temperature by calcining the as-synthesized powders at 900 degrees C/10 h. The phase formation and morphology of these powders were characterized via X-ray powder diffraction and scanning electron microscopy, respectively. The SSM phase formation associated with similar to 60 nm sized crystallites was also confirmed by transmission electron microscopy. The activation energy associated with the particle growth was found to be 95 +/- 5 kJ mol(-1). The dielectric constant of the tetragonal phase of the ceramic (fabricated using this cubic phase powder) with and without the flux (sulphates) has been monitored as a function of frequency (100 Hz-1 MHz) at room temperature. Internal barrier layer capacitance (IBLC) model was invoked to rationalize the dielectric properties.

High-temperature heat capacity and heat content of CaCu3Ti4O12 (CCTO)

The isobaric heat capacity of CaCu3Ti4O12 (CCTO) was measured from 300 to 1100 K using differential scanning calorimetry (DSC). The results were verified using drop calorimetric measurement of enthalpy increment (H-T - H-298.15) at T= 973 and 1073 K. The samples were dropped from room temperature into a calorimeter maintained at high temperature. The results show small negative deviation from Neumann-Kopp rule. The enthalpy and entropy increments are computed as a function of temperature and compared with values available in the literature. The results obtained in this study are consistent with available information on enthalpy and Gibbs energy of formation of CCTO.

Apparent shortening of the Csp(3)-Csp(3) bond analysed via a variable-temperature X-ray diffraction study in racemic 1,1 '-binaphthalene-2,2 '-diyl diethyl bis(carbonate)

Crystal structure determination at room temperature [292 (2) K] of racemic 1,1'-binaphthalene-2,2'-diyl diethyl bis(carbonate), C26H22O6, showed that one of the terminal carbon-carbon bond lengths is very short [Csp(3)-Csp(3) = 1.327 (6) angstrom]. The reason for such a short bond length has been analysed by collecting data sets on the same crystal at 393, 150 and 90 K. The values of the corrected bond lengths clearly suggest that the shortening is mainly due to positional disorder at two sites, with minor perturbations arising as a result of thermal vibrations. The positional disorder has been resolved in the analysis of the 90 K data following the changes in the unit-cell parameters for the data sets at 150 and 90 K, which appear to be an artifact of a near centre of symmetry relationship between the two independent molecules in the space group P (1) over bar at these temperatures. Indeed, the unit cell at low temperature (150 and 90 K) is a supercell of the room-temperature unit cell.

Possible application of carbon nanotube bundles for low temperature sensing

We report on the R-T measurement of carbon nanotube bundles from room temperature down to 1 K. The resistance at a particular temperature depends on the diameter of the bundle. The larger the bundle diameter is, the lower the value of the resistance. The resistance increases with the decrease in temperature as in the case of carbon, carbon glass resistance thermometer, and carbon nanotubes reported in the literature. The rate of the variation of resistance depends on the resistance of the bundle at room temperature which can be explored for the low temperature thermometry. Overall, the resistance and the sensitivity of the bundle depend on the bundle diameter which can be monitored easily.

ESR study of dibarium copper formate tetrahydrate Part II. Optical absorption and temperature dependence of spin-hamiltonian parameters

The variations in certain spin-Hamiltonian parameters of the Cu++ ion in dibarium copper formate tetrahydrate with temperature have been studied. Optical absorption investigations on single crystals of the salt at room temperature and 90° K. are reported. The results are discussed in terms of a model in which vibronic mixing of certain electron levels of the Cu++ ion play an important role.

Mechanism of low-temperature deformation in quenched aluminium-magnesium alloys

The dislocation mechanisms for plastic flow in quenched AlMg alloys with 0.45, 0.9, 2.7 and 6.4 at. % Mg were investigated using tensile tests and change-in-stress creep experiments in the temperaturhttp://eprints.iisc.ernet.in/cgi/users/home?screen=EPrint::Edit&eprintid=28109&stage=core#te range 87° -473° K. The higher the magnesium content in the alloy, the higher was the temperature dependence of flow stress. The alloys showed no perceptible creep in the vicinity of room temperature, while they crept at lower as well as higher temperatures. The most probable cause of hardening at temperatures below ∼ 200° K was found to be the pinning of dislocations by randomly distributed solute atoms, while athermal locking of dislocations by dynamic strain ageing during creep was responsible for the negligibly small creep rate in the room temperature range.