The study for the incipient solvation process of NaCl in water: the observation of the NaCl-(H2O)n (n = 1, 2, and 3) complexes using Fourier-transform microwave spectroscopy

Pure rotational spectra of the sodium chloride-water complexes, NaCl-(H(2)O)(n) (n = 1, 2, and 3), in the vibronic ground state have been observed by a Fourier- transform microwave spectrometer coupled with a laser ablation source. The (37)Cl-isotopic species and a few deuterated species have also been observed. From the analyses of the spectra, the rotational constants, the centrifugal distortion constants, and the nuclear quadrupole coupling constants of the Na and Cl nuclei were determined precisely for all the species. The molecular structures of NaCl-(H(2)O)(n) were determined using the rotational constants and the molecular symmetry. The charge distributions around Na and Cl nuclei in NaCl are dramatically changed by the complex formation with H(2)O. Prominent dependences of the bond lengths r(Na-Cl) on the number of H(2)O were also observed. By a comparison with results of theoretical studies, it is shown that the structure of NaCl-(H(2)O)(3) is approaching to that of the contact ion-pair, which is considered to be an intermediate species in the incipient solvation process.     

The oldest mid-oceanic carbonate buildup complex: Setting and lithofacies of the Vendian (Late Neoproterozoic) Baratal limestone in the Gorny Altai Mountains,Siberia

The Baratal limestone in the Gorny Altai Mountains, southern Siberia, occurs as large allochthonous blocks within a Cambrian accretionary complex that developed around the Siberia craton. Before the final accretion to Siberia in the Cambrian, the terrigenous clastic-free Baratal limestone was deposited directly upon a basaltic basement with a geochemical signature identical to that of modern oceanic plateau. The Baratal limestone with 598 ± 25 Ma (Early Vendian) Pb-Pb isochron age consists of three distinct facies; 1) massive lime mudstone with ooids and stromatolites, 2) bedded lime mudstone, and 3) limestone conglomerate/breccia dominated by ooid-bearing lime mudstone clasts. The first represents a shallow marine environment on top of an ancient oceanic plateau, while the latter two represent the deeper slope to bottom-of-slope facies of a plateau. The Vendian Baratal limestone provides the oldest example of a reconstructed shallow marine carbonate buildup complex developed on a plateau/seamount in a mid-ocean.     

Biospecific thermal analyzer coupled with a flowthrough immobilized enzyme column

A thermal analyzer consisting of a pair of glass thermistors was coupled with a flowthrough immobilized enzyme reactor for the determination of ATP concentration. Hexokinase was covalently bound to poly(chloromethyl-styrene-divinyl benzene) beads and packed in the reactor. The thermal analyzer was designed so as to respond to heat generation in the reactor. A maximum temperature change was exhibited within 1.5 min after the injection of a sample solution containing ATP together with glucose. Thermal decay occurred within 1 min. The thermal analyzer responded reproducibly to ATP at a constant concentration. Assays could be repeated at 3-min intervals. The effects of sample volume and flow rate on the response were examined with regard to an empirical equation. Concentration of ATP was determined with the thermal analyzer in the range of 0-10 mM. The thermal analyzer may be a simple device for the rapid determination of ATP concentration.     

Microwave spectroscopy of the CCl radical

The CCl radical was generated by a dc glow discharge in CCl₄, and rotational transitions of C³⁵Cl in both ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ were observed in the mm-wave region by using a source modulation microwave spectrometer. From an analysis of the observed spectra the magnetic and electric quadrupole hyperfine coupling constants of the ³⁵Cl nucleus were determined precisely. The Λ-doubling constant p₀ was determined to be positive, indicating that unknown ²Σ^? excited electronic states are making dominant contributions to the Λ doubling in the ground state. The previous diode-laser result [J. Mol. Spectrosc.85, 416–426 (1981)] was reanalyzed by using improved wavelength standards and by fixing the ground-state parameters to the present microwave values including the B₀ rotational constant 20 797.1725(38) MHz. The vibration-rotation constant α^B and the equilibrium bond length r_e were thus determined to be 0.006 768 2(48) cm^?1 and 1.645 218(16) Å, respectively, with 2.5 times standard deviations in parentheses. The spin density on the chlorine atom was estimated to be about 0.20 from the observed hyperfine coupling constants.     

Microwave spectroscopic study of the SiF radical

The microwave spectrum of the SiF radical was observed in both ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ of the ground vibronic state. The SiF radical was produced by a dc discharge either in a $\text{SiF}{}_4\text{SiH}{}_4$ mixture or in a transient molecule SiF₂ generated by the reaction of SiF₄ with heated solid silicon. The latter gave twice as intense a spectrum. A least-squares fit to the observed spectrum showed the rotational constant and the centrifugal distortion constant to be 17 350.2752(63) and 0.03188(13) MHz, respectively, with three standard errors in parentheses applying to the last digits of the constants. The lambda-doubling parameter p₀ was found to be negative, ?87.67 MHz, indicating that the ²Σ⁺ excited state contributions dominate over those of ²Σ^?. All four hyperfine coupling constants a, b, c, and d were determined and were employed to discuss the unpaired-electron spin and orbital distributions in the SiF radical.     

Analysis of the nuclear quadrupole interaction of Disulfur Dichloride, S2Cl2

Pure rotational spectra of S₂³⁵Cl₂ and S₂³⁵Cl³⁷Cl have been observed using a Fourier-transform microwave spectrometer. An analysis of the hyperfine structure made by considering the nuclear spin statistics showed that S₂Cl₂ has C₂symmetry, where the hyperfine splittings due to the two Cl nuclei were analyzed precisely. The nuclear quadrupole coupling constants including the off-diagonal (χ_ab, χ_ac, χ_bc) components and the nuclear spin–rotation interaction constants associated with the two Cl nuclei have been determined for the first time. We have shown that the nuclear quadrupole interaction plays an important role in the ortho–para mixing.     

Rapid sea-level change in the Late Guadalupian (Permian) on the Tethyan side of South China: litho- and biostratigraphy of the Chaotian section in Sichuan

The Capitanian (Late Guadalupian) Maokou Formation at Chaotian in northern Sichuan, South China, is composed mainly of shallow marine shelf carbonates deposited on the Tethyan side of South China. By detailed field mapping and scientific drilling, we newly found out unique fossil assemblages and a sharp lithologic change in the upper part of the Maokou Formation. The main part of the Maokou Formation (over 130 m thick) is composed of algal packstone with Wordian-Capitanian large-tested fusulines, rugose corals and other sessile benthos, whereas the Uppermost Member (13 m thick) is composed of black limy mudstone/chert with Capitanian offshore biota (ammonoids, radiolarians, and conodonts). The topmost Capitanian conodont zones are missing; however, the Maokou Formation is disconformably overlain by 260+/-4 Ma volcanic ash (Wangpo bed) and the Early Lopingian Wujiaping Formation with plant-bearing coaly mudstone and shallow marine carbonates (packstone). The newly identified facies change indicates that northern Sichuan has experienced rapid sea-level changes in the late Guadalupian, i.e., first a transgression in the mid-Capitanian and then a regression across the Guadalupian-Lopingian boundary. As the end-Guadalupian is characterized by a global regression, such a volatile sea-level fluctuation, in particular the sea-level rise, is unique to the Tethyan side of South China. The newly recognized relatively deep-water late Guadalupian sequence adds new paleo-environmental information and further provides a paleotectonic interpretation of the low-latitude eastern Tethyan margin immediately before the end-Guadalupian mass extinction.