Structural Crystallography and Crystal Chemistry

CaH406P-.K +, M r = 206.10, is orthorhombic, space group Pbca (from systematic absences), a = 14.538(4), b = 13.364(5), c = 6.880 (6)A, U = 1383.9 A 3, D x = 2.07 Mg m -a, Z = 8, ~.(Mo Ka) = 0.7107/~, p(MO Ka) = 1.015 mm -1. The final R value is 0.042 for a total of 1397 reflections. The high energy P-O(13) and the enolic C(1)-O(13) bonds are 1.612 and 1.374 A respectively. The enolpyruvate moiety is essentially planar. The orientation of the phosphate with respect to the pyruvate group in PEP.K is distinctly different from that in the PEP-cyclohexylammonium salt, the torsion angle C (2)-C (1)-O(13)- P being -209.1 in the former and -90 �� in the latter. The K + ion binds simultaneously to both the phosphate and carboxyl ends of the same PEP molecule. The ester O(13) is also a binding site for the cation. The K + ion is coplanar with the pyruvate moiety and binds to 0(22) and O(13) almost along their lone-pair directions. The carbonyl 0(22) prefers to bind to the K + ion rather than take part in the formation of hydrogen bonds usually observed in carboxylic acid structures.

Conjunctival Melanoma in Finland 1967-2000: a population-based study

Eighty-five new cases of conjunctival melanoma (CM) were diagnosed in Finland between 1967 and 2000. The annual crude incidence of CM was 0.51 per million inhabitants. The average age-adjusted incidence of 0.54 doubled during the study period, analogous to the increase in the incidence of cutaneous malignant melanoma during this period, suggesting a possible role for ultraviolet radiation in its pathogenesis. Nonlimbal tumors were more likely than limbal ones to recur and they were associated with decreased survival. Increasing tumor thickness and recurrence of the primary tumor were other clinical factors related to death from CM. The histopathologic specimens of 85 patients with CM melanoma were studied for cell type, mitotic count, tumor-infiltrating lymphocytes and macrophages, mean vascular density, extravascular matrix loops and networks, and mean diameter of the ten largest nucleoli (MLN). The absence of epithelioid cells, increasing mitotic count and small MLN were associated with shorter time to recurrence according to the Cox univariate regression. None of the histopathologic variables was associated with mortality from CM. Four (5%) patients had a CM limited to the cornea without evidence of a tumor other than primary acquired melanosis of the conjunctiva. Because there are no melanocytes in the cornea, the origin of these melanomas most likely is the limbal conjunctiva. All four corneally displaced CM were limited to the epithelium, and none of the patients developed metastases. An anatomic sub-classification based on my patients and world literature was developed for corneally displaced CM. In 20 patients the metastatic pattern could be determined. Ten patients had initial systemic metastases detected, nine had initial regional metastases, and in one case the two types were detected simultaneously. The patients most likely to develop either type of initial metastases were those with nonlimbal conjunctival melanoma, those with a primary tumor more than 2 mm thick, and those with a recurrent conjunctival melanoma. Approximately two thirds of the patients had limbal CM, a location associated with good prognosis. One third, however, had a primary CM originating outside the limbus. In these patients the chance of developing local recurrences as well as systemic metastases was significantly higher than in patients with limbal CM. Each recurrence accompanies an increased risk of developing metastases, and recurrences contribute to death along with increasing tumor thickness and nonlimbal tumor location. In my data, an equal number of patients with initial locoregional and systemic metastasis existed. Patients with limbal primary tumors less than 2 mm in thickness rarely experienced metastases, unless the tumor recurred. Consequently, the patients most likely to benefit from sentinel lymph node biopsy are those who have nonlimbal tumors, CM that are over 2 mm thick, or recurrent CM. The histopathology of CM differs from that of uveal melanoma. Microvascular factors did not prove to be of prognostic importance, possibly due to the fact that CM at least as often disseminates first to the regional lymph nodes, unlike uveal melanoma that almost always disseminates hematogenously.

Fugacity coefficients. Enthalpy, and second virial coefficients of boron trifluoride

Fugacity coefficients and isothermal changes of enthalpy have been calculated and reported. The calculations cover a temperature range of 0�� to 75��C. up to gas densities of 1.0 gram per cc. The generalized Benedict-Webb-Rubin constants evaluated from generalized PVT relations is found to predict the experimental data with an over-all absolute deviation of 3.1%. Second virial coefficients and potential energy parameters for Lennard-Jones (12-6) potential energy function are reported also.

Diffractive W and Z production at the Fermilab Tevatron

We report on a measurement of the fraction of events with a W or Z boson produced diffractively in antiproton-proton collisions at a center of mass energy of 1.96 TeV, using data from 0.6 inverse femtobarns of integrated luminosity collected with the CDF-II detector equipped with a Roman-pot spectrometer that detects the antiproton (pbar) from pbar+p --> pbar+[X+W/Z]. We find that (0.97 +/- 0.11)% of Ws and (0.85 +/- 0.22)% of Zs are produced diffractively in a region of (anti)proton fractional momentum loss (\xi) of 0.03-1t p+[X+W/Z]+pbar, and on exclusive Z production, pbar+p-->pbar+Z+p. No signal is seen above background for these processes, and comparisons are made with expectations.

Endo-polygalacturonate lyase of Cytophaga johnsonii

An extracellular endopolygalacturonate lyase of Cytophaga johnsonii was purified from the culture filtrate. It appeared to be homogeneous as judged by polyacrylamide gel electrophoresis at pH 8.6 as well as pH 4.3. The purified enzyme had a pH optimum around 9.0 and required Ca++ ions for its maximum activity. The apparent Kmfor polygalacturonic acid was found to be 0.22%. Both paper and column chromatography indicated formation and accumulation of an unsaturated monomer along with unsaturated di-, tri-, tetra- and pentamers from polygalacturonic acid by the enzyme action, indicating that the enzyme cleaved the substrate randomly in a non-hydrolytic manner. The glycosidic linkage next to the non-reducing end of polygalacturonic acid was not resistant to attack by this enzyme unlike in other known polygalacturonate lyases.

Porsastuotannon tuottavuuskehitys sikatilinp����t��stiloilla vuosina 2003���2008

Tutkimuksessa mitataan porsastuotannon tuottavuuden kehityst�� ProAgrian sikatilinp����t��stiloilla vuosina 2003���2008. Tuottavuutta mitataan Fisher-tuottavuusindeksill��, joka dekomponoidaan tekniseen, allokatiiviseen ja skaalatehokkuuteen sek�� teknologiseen kehitykseen ja hintavaikutukseen. Koko aineistosta aggregoidulla tuottavuusindeksill�� mitattuna tuottavuus kasvoi viidess�� vuodessa yhteens�� 14,3 % vuotuisen kasvun ollessa 2,7 %. Tuottajien keskim����r��inen tuottavuusindeksi antaa l��hes saman tuloksen: sen mukaan tuottavuus kasvaa yhteens�� 14,7 %, mik�� tekee 2,8 % vuodessa. Skaalatehokkuuden paraneminen havaitaan merkitt��vimm��ksi tuottavuuskasvun l��hteeksi. Skaalatehokkuus paranee aggregoidusti mitattuna 1,6 % vuodessa ja tiloilla keskim����rin 2,1 % vuodessa. Teknisen tehokkuuden koheneminen on toinen tuottavuuskasvua edist��v�� tekij�� tutkimusjaksolla. Molemmilla mittaustavoilla nousu on keskim����rin 1,4 % vuodessa. Allokatiivinen tehokkuus laskee hieman: aggregoidusti mitattuna 0,1 % ja keskim����rin 0,4 % vuodessa. Teknologinen kehitys tutkimusjaksolla on liev��sti negatiivista, keskim����rin -0,1 % vuodessa. Vuosittaiset vaihtelut ovat kuitenkin voimakkaita. Hintojen muutokset eiv��t juuri ole vaikuttaneet tuottavuuden tasoon, sill�� hintavaikutuksen vuotuiset muutokset j����v��t jokaisena vuonna alle puoleen prosenttiin ja keskim����r��inen vuotuinen muutos on -0,1 %. Keskeinen tuottavuuskasvua edist��nyt tekij�� n��ytt���� olleen tilakoon kasvu, joka on parantanut rakenteellista tehokkuutta. Teknologisen kehityksen j����minen negatiiviseksi kuitenkin tarkoittaa, ett�� paras havaittu tuottavuuden taso ei ole noussut lainkaan.

Characterization of mitochondrial neutral protease activity and the response of lysosomal enzymes to clofibrate feeding in rat liver

The phosphate-inhibitable neutral protease activity of the heavy mitochondrial fraction of rat liver is of lysosomal origin. The activity is essentially due to the thiol proteinases of the lysosomes. Digitonin treatment of the mitochondrial fraction results in the release of about 85 per cent of the neutral protease activity and the residual activity has an alkaline pH optimum and is not inhibited by phosphate. Clofibrate feeding at 0.5 per cent level in the diet results in enhanced levels of lysosomal enzymes. The increase is however restricted to the lysosome-rich fraction such that the activities associated with the heavy mitochondrial fraction show a significant decrease. It is suggested that clofibrate inhibits engulfment of mitochondria by lysosomes and this results in enhanced mitochondrial protein content.

Oxygen content of liquid cobalt in equilibrium with CoO.(1+x)Al2O3 and ���-Al2O3

The oxygen concentration of liquid cobalt in equilibrium with cobalt aluminate and a-alumina has been measured by suction sampling and crucible quenching techniques at temperatures between 1770 and 1975 K. Experiments were made with cobalt of high and low initial oxygen contents, and with and without the addition of cobalt aluminate. The effect of temperature on the equilibrium oxygen content is represented by the equation, log (at.% 0) = -10,4001T(K) + 4.64 (��0.008). The composition of the spinel phase, CoO.(1+x)AI20 3, saturated with alumina, has been determined by electron probe microanalysis. The values of x are 0.22 at 1770 Kand 0.28 at 1975 K. The oxygen potential corresponding to the three-phase equilibrium between cobalt, aluminate and alumina, and the standard Gibbs' energy of formation of nonstoichiometric cobalt aluminate are evaluated by combining the results of this study with recently published data on the activity of oxygen in liquid cobalt. Implications of the present results to aluminium deoxidation of liquid cobalt are discussed.

l-pGlu-(2-propyl)-l-His-l-ProNH2 attenuates 4-aminopyridine-induced epileptiform activity and sodium current: a possible action of new thyrotropin-releasing hormone analog for its anticonvulsant potential

L-PGlu-(2-proPyl)-L-His-L-ProNH(2) (NP-647) is a CNS active thyrotropin-releasing hormone (TRH) analog with potential application in various CNS disorders including seizures. In the present study, mechanism of action for protective effect of NP-647 was explored by studying role of NP-647 on epileptiform activity and sodium channels by using patch-clamp methods. Epileptiform activity was induced in subicular pyramidal neurons of hippocampal slice of rat by perfusing 4-aminopyridine (4-AP) containing Mg(+2)-free normal artificial cerebrospinal fluid (nACSF). Increase in mean firing frequency was observed after perfusion of 4-AP and zero Mg(+2) (2.10+/-0.47 Hz) as compared with nACSF (0.12+/-0.08 Hz). A significant decrease in mean firing frequency (0.61+/-0.22 Hz), mean frequency of epileptiform events (0.03+/-0.02 Hz vs. 0.22+/-0.05 Hz of 4-AP+0 Mg), and average number of action potentials in paroxysmal depolarization shift-burst (2.54+/-1.21 Hz vs. 8.16+/-0.88 Hz of 4-AP +0 Mg) was observed. A significant reduction in peak dV/dt (246+/-19 mV ms(-1) vs. 297 18 mV ms-1 of 4-AP+0 Mg) and increase (1.332+/-0.018 ms vs. 1.292+/-0.019 ms of 4-AP+0 Mg) in time required to reach maximum depolarization were observed indicating role of sodium channels. Concentration-dependent depression of sodium current was observed after exposure to dorsal root ganglion neurons to NP-647. NP-647 at different concentrations (1, 3, and 10 mu M) depressed sodium current (15+/-0.5%, 50+/-2.6%, and 75+/-0.7%, respectively). However, NP-647 did not show change in the peak sodium current in CNa18 cells. Results of present study demonstrated potential of NP-647 in the inhibition of epileptiform activity by inhibiting sodium channels indirectly. (C) 2011 IBRO. Published by Elsevier Ltd. All rights reserved.

Error, Confidence, and Cost in Engineering Computations

The questions that one should answer in engineering computations - deterministic, probabilistic/randomized, as well as heuristic - are (i) how good the computed results/outputs are and (ii) how much the cost in terms of amount of computation and the amount of storage utilized in getting the outputs is. The absolutely errorfree quantities as well as the completely errorless computations done in a natural process can never be captured by any means that we have at our disposal. While the computations including the input real quantities in nature/natural processes are exact, all the computations that we do using a digital computer or are carried out in an embedded form are never exact. The input data for such computations are also never exact because any measuring instrument has inherent error of a fixed order associated with it and this error, as a matter of hypothesis and not as a matter of assumption, is not less than 0.005 per cent. Here by error we imply relative error bounds. The fact that exact error is never known under any circumstances and any context implies that the term error is nothing but error-bounds. Further, in engineering computations, it is the relative error or, equivalently, the relative error-bounds (and not the absolute error) which is supremely important in providing us the information regarding the quality of the results/outputs. Another important fact is that inconsistency and/or near-consistency in nature, i.e., in problems created from nature is completely nonexistent while in our modelling of the natural problems we may introduce inconsistency or near-inconsistency due to human error or due to inherent non-removable error associated with any measuring device or due to assumptions introduced to make the problem solvable or more easily solvable in practice. Thus if we discover any inconsistency or possibly any near-inconsistency in a mathematical model, it is certainly due to any or all of the three foregoing factors. We do, however, go ahead to solve such inconsistent/near-consistent problems and do get results that could be useful in real-world situations. The talk considers several deterministic, probabilistic, and heuristic algorithms in numerical optimisation, other numerical and statistical computations, and in PAC (probably approximately correct) learning models. It highlights the quality of the results/outputs through specifying relative error-bounds along with the associated confidence level, and the cost, viz., amount of computations and that of storage through complexity. It points out the limitation in error-free computations (wherever possible, i.e., where the number of arithmetic operations is finite and is known a priori) as well as in the usage of interval arithmetic. Further, the interdependence among the error, the confidence, and the cost is discussed.

An estimate of equilibrium sensitivity of global terrestrial carbon cycle using NCAR CCSM4

Increasing concentrations of atmospheric CO2 influence climate, terrestrial biosphere productivity and ecosystem carbon storage through its radiative, physiological and fertilization effects. In this paper, we quantify these effects for a doubling of CO2 using a low resolution configuration of the coupled model NCAR CCSM4. In contrast to previous coupled climate-carbon modeling studies, we focus on the near-equilibrium response of the terrestrial carbon cycle. For a doubling of CO2, the radiative effect on the physical climate system causes global mean surface air temperature to increase by 2.14 K, whereas the physiological and fertilization on the land biosphere effects cause a warming of 0.22 K, suggesting that these later effects increase global warming by about 10 % as found in many recent studies. The CO2-fertilization leads to total ecosystem carbon gain of 371 Gt-C (28 %) while the radiative effect causes a loss of 131 Gt-C (10 %) indicating that climate warming damps the fertilization-induced carbon uptake over land. Our model-based estimate for the maximum potential terrestrial carbon uptake resulting from a doubling of atmospheric CO2 concentration (285-570 ppm) is only 242 Gt-C. This highlights the limited storage capacity of the terrestrial carbon reservoir. We also find that the terrestrial carbon storage sensitivity to changes in CO2 and temperature have been estimated to be lower in previous transient simulations because of lags in the climate-carbon system. Our model simulations indicate that the time scale of terrestrial carbon cycle response is greater than 500 years for CO2-fertilization and about 200 years for temperature perturbations. We also find that dynamic changes in vegetation amplify the terrestrial carbon storage sensitivity relative to a static vegetation case: because of changes in tree cover, changes in total ecosystem carbon for CO2-direct and climate effects are amplified by 88 and 72 %, respectively, in simulations with dynamic vegetation when compared to static vegetation simulations.

Evidence of collective relaxation behavior in the reentrant phase of oxygen-rich LaMnO3

The reentrant low temperature phase of the perovskite manganite LaMnO3+delta (delta=0.22) has been investigated with ac susceptibility and dc magnetization studies. A critical examination of the memory effects in ac susceptibility leads us to the conclusion that the slow dynamics in the system is a consequence of collective relaxation processes resulting from interactions between ferromagnetic clusters, whose presence was indicated in earlier studies. Here, we postulate that the collective behavior is due to the existence of long-range (dipolar) interactions between the large ferromagnetic `superspins'. This is also confirmed by an abnormally large microscopic spin-flip time (similar to 10(-9) s) compared to a canonical spin glass. (C) 2013 Elsevier B.V. All rights reserved.

Self-assembled multicomponent Pd-6 aggregates showing low-humidity proton conduction

Two Pd-6 molecular aggregates (1 and 2), self-sorted via a template-free three-component self-assembly process, represent new examples of discrete architectures exhibiting very high proton conductivity 0.78 x 10(-3) S cm(-1) (1) and 0.22 X 10(-3) S cm(-1) (2)] at 300 K at low relative humidity (B46%) with low activation energy comparable to that of currently used Nafion in fuel cells.

Near-infrared photoactive Cu3BiS3 thin films by co-evaporation

Semiconducting Cu3BiS3 (CBS) thin films were deposited by co-evaporation of Cu, Bi elemental metallic precursors, with in situ sulphurisation, using a quartz effusion cell. Cu3BiS3 thin films were structurally characterized by XRD and FE-SEM. The chemical bonding of the ions was examined by XPS. As deposited films were demonstrated for metal-semiconductor-metal near IR photodectection under lamp and laser illuminations. The photo current amplified to three orders and two orders of magnitude upon the IR lamp and 60 m W cm(-2) 1064 nm IR laser illuminations, respectively. Larger grains, made up of nano needle bunches aided the transport of carriers. Transport properties were explained based on the trap assisted space charge conduction mechanism. Steady state detector parameters like responsivity varied from 1.04 AW(-1) at 60 m Wcm(-2) to 0.22 AW(-1) at 20 m Wcm(-2). Detector sensitivity of 295 was found to be promising and further could be tuned for better responsivity and efficiency in utilization of near infra-red photodetector. (C) 2014 AIP Publishing LLC.

Na2.44Mn1.79(SO4)(3): a new member of the alluaudite family of insertion compounds for sodium ion batteries

Sodium-ion batteries have been extensively pursued as economic alternatives to lithium-ion batteries. Investigating the polyanion chemistry, alluaudite structured Na2Fe2II(SO4)(3) has been recently discovered as a 3.8 V positive electrode material (Barpanda et al., Nature Commun., 5: 4358, 2014). Registering the highest ever Fe-III/Fe-II redox potential (vs. Na/Na+) and formidable energy density, it has opened up a new polyanion family for sodium batteries. Exploring the alluaudite family, here we report isotypical Na2+2xMn2-xII(SO4)(3) (x = 0.22) as a novel high-voltage cathode material for the first time. Following low-temperature (ca. 350 degrees C) solid-state synthesis, the structure of this new alluaudite compound has been solved adopting a monoclinic framework (s.g. C2/c) showing antiferromagnetic ordering at 3.4 K. Synergising experimental and ab initio DFT investigation, Na2+2xMn2-xII(SO4)(3) has been found to be a potential high-voltage (ca. 4.4 V) cathode material for sodium batteries.