NQR, NMR and Crystal Structure Studies of [C(NH2)3]2HgX4 (X = Br, I)

The crystal structure of [C(NH₂)₃]₂HgBr₄ has been determined at room temperature: monoclinic, space group C2/c, with a = 10.035(2), b = 11.164(2), c = 13.358(3) Å, β = 111.67(3)°, and Z = 4. The crystal consists of planar [C(NH₂)₃]⁺ and distorted tetrahedral [HgBr₄]^2? ions. The Hg atom is located on a two-fold axis such that two sets of inequivalent Br atoms exist in an [HgBr₄]^2? ion. In accordance with the crystal structure, two ⁸¹Br NQR lines widely separated in frequency were observed between 77 and ca. 380 K. [C(NH₂)₃]₂HgI₄ yielded four ¹²⁷I NQR lines ascribable to m = ±1/2 ? ±3/2 transitions, indicating that its crystal structure is different from the bromide complex. The ¹H NMR T ₁ measurements showed a single minimum for the bromide but two minima for the iodide. The analyses based on the C₃ reorientations of the planar [C(NH₂)₃]⁺ ions gave the activation energies of 29.8 kJ mol^?1 for the bromide, and 30.2 and 40.0 kJ mol^?1 for the iodide.     

Influence of Nitrogen Supply and Temperature on Stable Carbon Isotope Ratios in Plants of Different Photosynthetic Pathways (C3, C4, CAM)

Abstract

One representative species of each of the three photosynthetic pathways (C₃, C₄, CAM) were cultivated in growth chambers with high and low nitrogen nutrition level respectively once at 20°C day/13°C night temperature, once at 30°C day/13°C night. Leaf conductances and δ¹³C values of the leaves of each plant were determined. At 20°C day temperature the C₃ species showed higher leaf conductance with low nitrogen nutrition level than with high nitrogen level, which is also reflected in a more negative δ¹³C value, whereas both C₄ and CAM plants did not respond in this manner to nitrogen supply. An increase of day temperature to 30°C diminished the significant response of the C₃ plant, while the response of C₄ and CAM representatives to nitrogen nutrition did not change markedly.     

Über die Anreicherung des Stabilen Isotops 34S im System Hydrogensulfit/Schwefeldioxid, 2. Mitt.: Das System NH4HSO3/SO2

Es wurde im System NH₄HSO₃/SO₂ die Abhängigkeit des Gesamttrennfaktors für die ³¹S-Anreicherung von der NH₄HSO₃-Konzentration und bei Temperaturen von 20 °C und 80 °C untersucht. Für den elementaren Trennfaktor wurde bei 20 °C eine Abhängigkeit von der NH₄HSO₃-Konzentration festgestellt, während er bei 80 °C für 3…10 Mol NH₄HSO₃/l ～ = 1,007 beträgt. Die Trennstufenhöhen lagen bei 20 °C zwischen 1,23 cm und 5,55 cm und bei 80 °C zwischen 0,93 cm und 2,12 cm.     

Lattice thermal expansion of cesium plumbo chloride

The temperature variation of the lattice parameter of CsPbCl₃ in the cubic phase has been studied by x-ray method, from a determination of the precision lattice parameter at various temperatures, ranging from 50°C to 400°C. The coefficient of thermal expansion of CsPbCl₃ can be expressed by the quadratic equation,α _T = 21.6 × 10⁻⁶ + 2.44 × 10⁻⁹ T + 5.90 × 10⁻¹¹ T ².     

Improved Estimation of Protein Rotational Correlation Times fromN Relaxation Measurements

In the study of protein backbone dynamics by¹⁵N relaxation measurements, an initial estimation of the isotropic global correlation time, τ_m, is usually obtained from the averageT₁/T₂ratio of nuclear spins that do not exhibit slow internal motion and withT₂values not significantly shortened by chemical or conformational exchange processes. Different methods have been used for identification of the rates of internal motion. However, the number of nuclear spins included in the τ_mestimation is often larger than the number that ultimately can be fitted to a single-order parameter,S², implying that some nuclear spins involved in the initial τ_mestimation actually have an effective internal correlation time, τ_e, not as fast as assumed. As a consequence, τ_mis underestimated, since internal motion reduces theT₁/T₂ratio. This situation becomes more obvious if the molecule has a large τ_mvalue because the reduction inT₁/T₂ratio arising from internal motion is more significant than for molecules with smaller τ_mand the same degree of internal motion. This Communication describes a more reliable method for identifying nuclear spins which should be excluded from the τ_mestimation because of insufficiently rapid internal motion. This results in an improved τ_mvalue, giving a much better agreement between the number of nuclear spins fitted successfully to a single-order parameter,S², and those used in the τ_mestimation.     

Novel Peak Assignments of in VivoC MRS in Human Brain at 1.5 T

¹³C MRS studies at natural abundance and after intravenous 1-¹³C glucose infusion were performed on a 1.5-T clinical scanner in four subjects. Localization to the occipital cortex was achieved by a surface coil. In natural abundance spectra glucose C_3β,5β, myo-inositol, glutamate C_1,2,5, glutamine C_1,2,5, N-acetyl-aspartate C_1-4,C=O, creatine CH₂, CH₃, and C_C=N, taurine C_2,3, bicarbonate HCO⁻₃ were identified. After glucose infusion ¹³C enrichment of glucose C_1α,1β, glutamate C_1-4, glutamine C_1-4, aspartate C_2,3, N-acetyl-aspartate C_2,3, lactate C₃, alanine C₃, and HCO⁻₃ were observed. The observation of ¹³C enrichment of resonances resonating at >150 ppm is an extension of previously published studies and will provide a more precise determination of metabolic rates and substrate decarboxylation in human brain.     

P−T phase diagram for ferromagnetic semiconductor CdCr2Se42

The P?T phase diagram associated with the ferromagnetic semiconductor CdCr₂Se₄ was determined between 600 and 964°C for the first time from the P_{Se2(or Cd)} ? T diagram for the stability of the compound disclosed by annealing experiments under controlled Se₂ and Cd vapor pressures, and from the phase equilibria in the CdSeCrSeSe system examined by usual annealing experiments. The following characteristic features are also clarified. (1) The maximum temperature for the stability of CdCr₂Se₄ is about 900°C. (2) CdCr₂Se₄ dissolves into Se melt and is in equilibrium with the Se-rich melt which has a CdSe content in excess of CdSe·Cr₂Se₃. The solubility decreases rapidly as temperature falls from 900 to 860°C. (3) Cr₂Se₃ is the only compound in the CrSe system in equilibrium with CdCr₂Se₄ above about 860°C. Both Cr₃Se₄ and Cr₂Se₃ exist below this temperature. (4) The P_Se2 range for the stability of CdCr₂Se₄ is estimated as a measure of the concentration ranges of native defects due to nonstoichiometry. It increases as temperature decreases and is about 5 × 10⁹ at 600°C.     

Structure and properties of the anions MF4−, MCl4− and MBr4− (M = C,Si, Ge)

Density functional theory (DFT), Møller–Plesset (MP2) and coupled cluster with single and double substitutions including non-iterative triple excitations (CCSD(T)) calculations on the anions MX₄^?, with M = C, Si, Ge and X = F, Cl, Br, show that GeF₄^?, SiCl₄^?, GeCl₄^? and SiBr₄^? prefer a C_2v conformation, but CCl₄^? is an elongated C_3v structure. CBr₄^? has T_d symmetry in MP2, but is slightly more stable in elongated C_3v form with DFT and CCSD(T). GeBr₄^? has T_d symmetry. CF₄^? and SiF₄^? are unstable with respect to loss of an electron. Vertical electron affinities (EAs) are negative also for CCl₄ and SiCl₄, and close to zero for GeF₄ and SiBr₄. Adiabatic EAs range from 0.47 eV for SiCl₄ to 1.78 eV for GeBr₄. The lowest excited states at T_d symmetry are ²T₂ resonances with energies of 2.1–3.5 eV, resulting from excitation of the a₁ singly occupied molecular orbital to vacant t₂ orbitals. Vertical excitation energies (VEEs) and vibrational frequencies are given for the most stable anionic geometries. Comparison with experimental VEEs for CCl₄^? is made. From dissociation energies of MX₄, MX₄^?, MX₃ and MX₃^?, appearance energies of X^?, MX₃^?, X₂^? and MX₂^? were calculated. Most were found to be in reasonable agreement with experimental values. Theoretical spin densities and g-factors have been compared with experimental results available for CCl₄^?, SiCl₄^? and GeCl₄^?.     

Polarizing Microscopic and 31P NMR Studies of Decylammonium Chloride/Potassium Chloride/Water System. Containing Phosphoric Acid Monodecyl Ester and H3PO4

The decylammonium chloride (DACl), KCl and D₂O system forms two phases(N_c+N_d) in the nematic range. The N_d phase was ca. 15% by volume and exhibited extinct appearance. From conoscopic measurements it was inferred that the optical axis of the N_d phase was tilted. The lamellar phase of the DACl-KCl-D₂O system as well as the lamellar phase obtained by adding phosphoric acid decylester/phosphoric acid (PDE/H₃PO₄) showed the following phase sequence: L_α + N_d 35°C H_α + N_d 40°C N_c + N_d 45°C N_c 50°C isotropic The line shapes of ³¹P NMR of PDE/H₃PO₄ were found to be sensitive to micelle size and dynamics occuring in the lyotropic system, but they do not differentiate between different micelle shapes.     

3D dependence of the dielectric dispersion in a BaTiO3 single crystal

The 3D dependences ?′(log f, T) and tanδ(logf, T) of a perfect BaTiO₃ single crystal grown by the Remeika method have been studied in the ranges f = 1–2 × 10⁷ Hz and T = ?80–130°C. These dependences characterize a transition from the paraelectric phase (121.5°C) as a near-antiferroelectric transition followed by the transition to the tetragonal phase at ～79.5°C. According to a number of signs, the range 121.5–79.5°C corresponds to a metastable phase typical of first-order phase transitions. The unexpected result of this work has been discussed with invoking the hypothesis on the BaTiO₃ structure in the paraelectric phase, according to which it consists of three antiferroelectric states oriented along the crystallographic axes. Using the dielectric properties of BaTiO₃ as an example, the method of direct correct determination of the temperatures of the structural transformations from the anomaly of tanδ(logf, T) has also been demonstrated.     

Anomalous acid proton self-diffusion in N(CH3)4HSO4 — A candidate for proton superionic conductivity

The appearance of a “liquid-like” proton T₂ component above 100°C and the relatively high value of the proton self-diffusion coefficient D = (5–8) × 10^-7cm²sec^-1 between 175°C and 200°C demonstrate the onset of a super-ionic state in N(CH₃)₄HSO₄. The ratio between the “liquid” and “solid” like components shows that acid protons are responsible for the high ionic conductivity.     

The effects of irradiation temperature and preinjected gases on voids in aluminum

Voids in high purity aluminum irradiated to a fast (E>1 MeV) fluence of 4 × 10²⁰ n/cm² at 125 (0.43T _m) and 150°C (0.45T _m) are fewer in number but very much larger in size than those in material irradiated at 55°C (0.35T _m). Additionally, at 125 and 150°C, the voids adopt a variety of shapes including plates, ribbons, cylinders and more equiaxed polyhedra, and are frequently associated with particles of transmutation-produced silicon. At the higher temperatures voids are larger near grain boundaries than in grain interiors. Injection of hydrogen or helium prior to irradiation causes an increase in the number of voids and a corresponding decrease in size in specimens irradiated at 150°C; 3 at. ppm He is more effective than either 3 or 9 at. ppm H. The gases do not appear to influence swelling.

A commercial purity (99 per cent) aluminum subjected to the same irradiation treatments did not develop voids whether preinjected with gases or not; the visible radiation damage consisted solely of small loops on or near grown-in dislocations.     

Thermoluminescence of Al2O3:Cr3+ films synthesized by the nonaqueous sol–gel method

The thermoluminescence (TL) properties of Al₂O₃:Cr³⁺ thin films prepared by the nonaqueous sol–gel method were evaluated. The obtained thin films were characterized by scanning electron microscope and energy dispersive spectrometry. They were irradiated with ⁶⁰Co gamma rays of the different doses. TL glow curves exhibited two peaks centered at 197°C and 322°C.The heights of peaks were found to be sensitive to exposures of ionizing irradiation and the integral area of the TL signals had a linear response in the dose range of 5–60 Gy.This remarkable result suggests that Al₂O₃:Cr³⁺ films might potentially be used for radiation dosimetry.     

TSC study of electric dipole relaxations in chlorapatite

Electric dipole relaxations in chlorapatite, Ca₅(PO₄)₃Cl, have been studied with the fractional polarization mode of the thermally stimulated currents (TSC) method. Fifty-one of the fifty-seven sets of data obtained in the range 10–443°K fell naturally into four groups yielding compensation temperatures T_C of T_C1, = 202°C, T_C2: = 202°C, T_C3 = 420°C and T_C4= 644°C, with estimated error < 10°C, and characteristic relaxation times τ_C of τ_C1 = 1.3 × 10^?7s, τ_C2 = 3.2 × 10^?6s, τ_C3 = 8.8 × 10^?5s and τ_C4 = 2.3 × 10^?4s. Atomic-scale physical models involving Cl^? ion motion are offered for the 202°C compensation at the temperature of the reported monoclinic-to-hexagonal phase transition and for the 420°C compensation, at which temperature the Cl^? ions individually are thought to have enough thermal energy to maintain the hexagonal form dynamically.     

Dependence of Tg and T ll on tacticity of PMMA by differential scanning calorimetry

A differential scanning calorimeter (DSC) investigation (heating rate 10 K/min) is presented on the multiple transition (relaxation) spectra of PMMA: T_β < T_g; T_g, T_ll > T_g; and T_lρ > T_ll, as a function of tacticity. Specimens are characterized by fractional triad content: isotactic (it-), Xii; syndiotactic (st-), Xss; and atactic (at-), Xis. Values for the seven specimens are it-, 1.0;, at-, 0.495 to 0.750; st-, 0.958. Results on T_β were inconclusive. Our T_g results clarify some discrepancies in the prior literature.

Linear least squares regression analyses give: T_g (°C) = 56.6 + 76.6 Xss (our data) T_g (°C) = 49.1 + 87.3 Xss (our data plus selected literature data)

Extrapolated T_g 's for Xss = 1 are 133.2°C and 136.1°C, respectively, in contrast to Thompson's extrapolated value of 160°C. Similarly T_g(°C) = 99.5 + 71.6 (1?Xii) for our DSC data. The extrapolated T_ll for Xss = 1 is 171.1°C. The intensity of T_ll is high for st-and it-, with a broad minimum over the at-region. A second liquid state process, T_lρ > T_ll, occurs at 149°C for it-, but is above the measured range for at-and st-. T_ll (at-) from DSC compares favorably with reported literature values by a variety of techniques. T_ll and T_lρ at all tacticities agree well with those from a companion study by the thermally stimulated current (TSC) technique on the same group of specimens, as reported elsewhere. This includes the influence of tacticity on intensity. These cross-comparisons by a variety of methods indicate that neither T_ll nor T_lρ is an artifact of our DSC technique. The Frenkel segment-segment contact hypothesis is favored to explain the molecular origin of T_ll Sequences longer than triads may be needed for improved correlations of T_g and T_lρ with tacticity.     

NQR, NMR and Crystal Structure Studies of [C(NH2)3]3Sb2Br9

The crystal structure of [C(NH₂)₃]₃Sb₂Br₉ was determined at 143 K: monoclinic, space group C2/c, Z = 4, a = 15.695 (3), b = 9.039(2), c = 18.364(3) Å, β = 96.94(1)°. The structure consists of two crystallographically independent guanidinium ions and two-dimensional corrugated sheets of (Sb₂Br₉ ^3?) _n , in which SbBr₆ octahedra are connected through three bridging Br atoms each other. One of the cations situates in a cavity of the (Sb₂Br₉ ^3?) _n layer with statistical disorder, while the other situates between the layers without disorder. Three ⁸¹Br NQR resonance lines were assignable to terminal Br atoms, while only one line was found for two inequivalent bridging Br atoms. All the ⁸¹Br NQR resonance lines were subjected to fade-out at low temperatures. The temperature dependence curve of ¹H NMR T ₁ showed well defined two minima, which were explained by postulating the C₃ reorientations of two types of cations with very different activation energies. The DTA (DSC) measurement revealed a phase transition of a first-order type at 444 K.     

Non-invasive temperature mapping using MRI: comparison of two methods based on chemical shift and T1-relaxation

Purpose: To implement and evaluate the accuracy of non-invasive temperature mapping using MRI methods based on the chemical shift (CS) and T₁ relaxation in media of various heterogeneity during focal (laser) and external thermal energy deposition.Materials and Methods: All measurements were performed on a 1.5 T superconducting clinical scanner using the temperature dependence of the water proton chemical shift and the T₁ relaxation time. Homogeneous gel and heterogeneous muscle phantoms were heated focally with a fiberoptic laser probe and externally of varying degree ex vivo by water circulating in a temperature range of 20–50°C. Magnetic resonance imaging data were compared to simultaneously recorded fiberoptic temperature readings.Results: Both methods provided accurate results in homogeneous media (turkey) with better accuracy for the chemical shift method (CS: ±1.5°C, T₁: ±2.0°C). In gel, the accuracy with the CS method was ±0.6°C. The accuracy decreased in heterogeneous media containing fat (T₁: ±3.5°C, CS: +5°C). In focal heating of turkey muscle, the accuracy was within 1.5°C with the T₁ method.Conclusion: Temperature monitoring with the chemical shift provides better results in homogeneous media containing no fat. In fat tissue, the temperature calculation proved to be difficult.     

35Cl NQR study of the low temperature transition in ferroelectric (CH3NH3)HgCl3

In addition to the paraelectric-ferroelectric phase transition at T_c = + 62°C there is another low T phase transition in the −152 to −165°C range associated with a sudden change in the NQR spectra.The three ³⁵Cl NQR lines observed in the P3₂ ferroelectric phase of (CH₃NH₃)HgCl₃ below T_c = 62°C suddenly disappear on cooling below −152°C. No lines could be observed between 152 and −165°C. Below this temperature five ³⁵Cl NQR lines appear and remain down to liquid nitrogen temperature.     

Theory studies of the local lattice distortions and the EPR parameters for Cu2+, Mn2+ and Fe3+ centres in ZnWO4

The local lattice distortions and the electron paramagnetic resonance (EPR) parameters (g factors, hyperfine structure constants and zero-field splittings) for Cu²⁺, Mn²⁺ and Fe³⁺ in ZnWO₄ are theoretically studied based on the perturbation calculations for rhombically elongated octahedral 3d⁹ and 3d⁵ complexes. The impurity centres on Zn²⁺ sites undergo the local elongations of 0.01, 0.002 and 0.013 Å along the C₂ axis and the planar bond angle variations of 8.1°, 8.0° and 8.6° for Cu²⁺, Mn²⁺ and Fe³⁺, respectively, due to the Jahn–Teller effect and size and charge mismatch. In contrast to the host Zn²⁺ site with obvious axial elongation (～0.31 Å) and perpendicular (angular) rhombic distortion, all the impurity centres demonstrate more regular octahedral due to the above local lattice distortions. The copper centre exhibits significant Jahn–Teller reductions for the spin-orbit coupling and orbital angular momentum interactions, characterised by the Jahn–Teller reduction factor J (≈0.29 ? 1). The calculated EPR parameters agree well with the experimental results. The local structures of the impurity centres are analysed in view of the corresponding lattice distortions.     

Optically stimulated heating using Nd3+ doped NaYF4 colloidal near infrared nanophosphors

Although efficient in heat generation, gold nanoparticles dedicated for photostimulated localized hyperthermia treatment (LHT) lack luminescent properties suitable for detection in heterogeneous and autofluorescent tissue. Here, we study and report the use of bifunctional luminescent neodymium (Nd³⁺) ions doped ??-NaYF₄ colloidal nanoparticles as potential nanoheaters suitable for LHT. Up to 35°C (0.8°C/mW@514.5?nm) temperature rise in ??0.5?ml colloidal 25%Nd³⁺:NaYF₄ solution was achieved in comparison to around a 4°C rise for the undoped colloidal NaYF₄. The maximum temperature (T _max?) was linearly proportional to the concentration of Nd³⁺ dopant. The time required to elevate temperature to 1/e×T _max? varied from 100 to 135 seconds. The proposed approach gives premises to the construction of multi-functional therapeutic agents detectable by means of fluorescence molecular imaging.