Clay Mineral and Geochemical Proxies for Intense Climate Change in the Permian Gondwana Rock Record from Eastern India.

The clay mineral assemblages and geochemical compositions of the Permian Talchir and Barakar mudstones of the Raniganj basin, India, have been used to interpret terrestrial paleoclimate. The Talchir Formation presents unequivocal evidences of the Permian global glacial climate, and the overlying Barakar Formation with braided fluvial deposits immediately follows the glacial amelioration stage to a humid warm climate. Sediments unaffected by burial diagenesis and originated from a similar source under contrasting climates are ideal for developing proxies for substantial climate shift. Illite (28.4-63.8%), illite/smectite (0-58.6%, 40-80% illite), chlorite (0-53.9%), and chlorite/smectite (5.6-29.8%) constitute the clay mineral assemblage in the Talchir Formation whereas illite (5.3-78.2%), illite/smectite (trace-34.1%, mostly 60-90% illite), and kaolinite (36.1-86.8%) dominate the clay mineral assemblage in the Barakar Formation. The Talchir mudrocks are enriched in mobile elements and depleted in alumina w.r.t. PAAS, have relatively higher K2O/Al2O3 ratios (~0.3), high ICV (1.12-1.28), and lower CIA values (52.6-65.1) compared to those of the younger Barakar mudstones. The Barakar mudstones are depleted in mobile elements w.r.t. PAAS, have relatively low ICV (0.33-0.62) and K2O/Al2O3 values (0.11-0.16), and higher CIA values (72.9-88.2). Textural, mineralogical immaturity, and rock fragments of different components of the basement seen in the Talchir sandstones show these sediments being a first-cycle sedimentary deposit. The distinctive clay mineral assemblage and major oxide composition of the Talchir mudrocks attest to a unique low intensity chemical weathering in cold arid climate. Significant presence of kaolinite as well as distinctive geochemical characters of the Barakar mudrocks marks a shift in the paleoclimate from cold arid to humid. This climatic shift is further supported by the proportion and composition of illite/smectite across the formations. The relative proportion of chlorite and kaolinite and composition of illite/smectite therefore closely corroborate the significant climate shift, and such proxies, therefore, are useful indicators of climate extremes in the geological record.

Tracking the migration of the Indian continent using the carbonate clumped isotope technique on Phanerozoic soil carbonates.

Approximately 140 million years ago, the Indian plate separated from Gondwana and migrated by almost 90° latitude to its current location, forming the Himalayan-Tibetan system. Large discrepancies exist in the rate of migration of Indian plate during Phanerozoic. Here we describe a new approach to paleo-latitudinal reconstruction based on simultaneous determination of carbonate formation temperature and δ(18)O of soil carbonates, constrained by the abundances of (13)C-(18)O bonds in palaeosol carbonates. Assuming that the palaeosol carbonates have a strong relationship with the composition of the meteoric water, δ(18)O carbonate of palaeosol can constrain paleo-latitudinal position. Weighted mean annual rainfall δ(18)O water values measured at several stations across the southern latitudes are used to derive a polynomial equation: δ(18)Ow = -0.006 × (LAT)(2) - 0.294 × (LAT) - 5.29 which is used for latitudinal reconstruction. We use this approach to show the northward migration of the Indian plate from 46.8 ± 5.8°S during the Permian (269 M.y.) to 30 ± 11°S during the Triassic (248 M.y.), 14.7 ± 8.7°S during the early Cretaceous (135 M.y.), and 28 ± 8.8°S during the late Cretaceous (68 M.y.). Soil carbonate δ(18)O provides an alternative method for tracing the latitudinal position of Indian plate in the past and the estimates are consistent with the paleo-magnetic records which document the position of Indian plate prior to 135 ± 3 M.y.

Combination of Cyanine Behaviour and Giant Hyperpolarisability in Novel Merocyanine Dyes: Beyond the Bond Length Alternation (BLA) Paradigm.

Merocyanine dyes that exhibit antithetic cyanine-like behaviour and giant first-order hyperpolarisability (ß) values have been designed. These cyanine-type dyes open up an intriguing route towards molecular-based electro-optic materials as well as new second-harmonic generation dyes for imaging.

Geometry and quadratic nonlinearity of charge transfer complexes in solution using depolarized hyper-Rayleigh scattering.

We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, ß(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D=I(2ω,X,X)/I(2ω,Z,X) and D(')=I(2ω,X,C)/I(2ω,Z,C) in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, ß(HRS), and the value of macroscopic depolarization ratios, D and D('), are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical ß(HRS), D and D(') values as a function of the geometry of the complex. The calculated ß(HRS), D, and D(') values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30° is observed. Thus, we have demonstrated in this paper that the polarization resolved HRS technique along with theoretical calculations can unravel the geometry of CT complexes in solution.

Environmental and excitonic effects on the first hyperpolarizability of polar molecules and related dimers.

We investigate the second-order nonlinear optical properties of a push-pull chromophore in different external and supramolecular environments, through a combined experimental and theoretical approach. In particular, we compare the first hyperpolarizability (beta) of a model dipolar and polarizable chromophore with that of a charged analogue and of a molecular dimer based on the chromophore itself. We find that the beta value of the model chromophore in solutions of low-polarity solvents is strongly affected by association effects, already at concentrations of 10 (-3) M. The presence of a positive charge in close proximity to the chromophore is found to lead to a 100% increase of the beta response of the model push-pull chromophore. This effect is of major importance for biological applications, in particular when chromophores are used as markers in charged anisotropic environments. Finally, excitonic effects, beyond the Frenkel exciton approximation, are discussed for the dimer and found to be more important the higher the order of nonlinearity is.

Quadratic nonlinearity of one- and two-electron oxidized metalloporphyrins and their switching in solution.

We report the quadratic nonlinearity of one- and two-electron oxidation products of the first series of transition metal complexes of meso-tetraphenylporphyrin (TPP). Among many MTPP complexes, only CuTPP and ZnTPP show reversible oxidation/reduction cycles as seen from cyclic voltammetry experiments. While centrosymmetric neutral metalloporphyrins have zero first hyperpolarizability, beta, as expected, the cation radicals and dications of CuTPP and ZnTPP have very high beta values. The one- and two-electron oxidation of the MTPPs leads to symmetry-breaking of the metal-porphyrin core, resulting in a large beta value that is perhaps aided in part by contributions from the two-photon resonance enhancement. The calculated static first hyperpolarizabilities, beta0, which are evaluated in the framework of density functional theory by a coupled perturbed Hartree-Fock method, support the experimental trend. The switching of optical nonlinearity has been achieved between the neutral and the one-electron oxidation products but not between the one- and the two-electron oxidation products since dications that are electrochemically reversible are unstable due to the formation of stable isoporphyrins in the presence of nucleophiles such as halides.

Age trends in anthropometric characteristics among 6-9 years old Bengalee Hindu school girls of Kolkata, India.

A cross-sectional study of 431 6-9 years old urban Bengalee Hindu schoolgirls of Kolkata, India, was undertaken to study age trends in anthropometric characteristics including regional and subcutaneous adiposity. The anthropometric variables measured included height, weight, sitting height (SH), waist (WC), hip (HPC), thigh (TC), mid-upper arm (MUAC) and medial calf (MC) circumferences as well as triceps (TSF), biceps (BSF), subscapular SUBSF), suprailliac (SUPSF) and medial calf (MCASF) skinfolds. The results revealed, that there was a significant increasing age trend for all the anthropometric variables including the two derived variables: body mass index (BMI) and subischial leg length (SLL). For all variables, the lowest and the highest means were observed at the age of 6 and 9 years, respectively. The maximum increase in weight, BMI, all linear measurements, WC and HPC were observed during the period 6-7 years of age. In general, all skinfolds recorded similar yearly increments. More importantly, this study clearly indicated that among Bengalee girls aged 6-9 years, the highest amount of linear growth (height, SH and SLL) was observed at 6 years of age. The overall adiposity (BMI) also recorded the maximum increment during this period. The unique data presented here can be used as reference values for urban Bengalee Hindu girls aged 6-9 years.

Effect of dietary co-administration of sodium selenite on sodium arsenite-induced ovarian and uterine disorders in mature albino rats.

The subchronic treatment of mature female Wistar-strain albino rats in diestrous phase with sodium arsenite at a dose of 0.4 ppm/100 g body weight/rat/day via drinking water for period of 28 days (seven estrous cycles) caused a significant reduction in the plasma levels of leutinizing hormone (LH), follicle-stimulating hormone (FSH), and estradiol along with a significant decrease in ovarian activities of delta five, 3 beta-hydroxysteroid dehydrogenase (Delta5,3beta-HSD), and 17 beta-hydroxysteroid dehydrogenase (17beta-HSD) followed by a reduction in ovarian and uterine peroxidase activities. A significant weight loss of the ovary and uterus was also observed after this treatment, along with a prolonged diestrous phase and a high accumulation of arsenic in the plasma and these organs. Moreover, sodium arsenite was also responsible for ovarian follicular and uterine cell degeneration characterized by a high number of regressing follicles and a reduction in the uterine luminal diameter, respectively, in comparison with the controls. A dietary supplementation of sodium selenite at the dose of 0.6 mg/100 g body weight/rat/day for a period of 28 days along with arsenic treatment minimized the gonadal weight loss significantly and increased the activities of the ovarian steroidogenic enzymes as well as the ovarian and uterine peroxidase at the control level. Selenium was also able to increase the plasma levels of LH, FSH, and estradiol toward the control level. Vaginal smears showed normal estrous cyclicity in sodium selenite-supplemented arsenic-treated rats along with lower arsenic levels in the plasma and gonadal tissue in comparison with arsenic-only-treated rats. Histological sections of ovary and uterine tissues in the control and experimental groups confirmed that sodium selenite supplementation was able to prevent arsenic-induced histopathological changes in the ovary and uterus. Plasma levels of norepinephrine and dopamine in the midbrain and diencephalon decreased significantly, whereas the serotonin level was increased significantly after 28 days of sodium arsenite treatment. All of these parameters were, in most cases, unchanged from the control level when sodium selenite was co-administered with sodium arsenite. Arsenic intoxication was also associated with increased liver weight and elevation in the activities of hepatic and renal acid phosphatase, alkaline phosphatase, and transaminases, but selenium co-administration was not able to change these toxic effects of arsenic. The results of our experiments indicate the significant protective action of sodium selenite on arsenic-induced toxicity in the female reproductive system, while there was no significant protective effect of selenium on arsenic-induced toxicity in other organs.