A motif for heteronuclear C[triple bond, length as m-dash]E (E = Si, Ge, Sn, Pb) bonding: Lewis acid-base pair strategy.

The design and characterization of the heteronuclear group 14 C[triple bond, length as m-dash]E (E = Si, Ge, Sn, Pb) triple bonds have attracted intensive interest in the past few decades. In the current work, utilizing the advantages of N-heterocyclic carbenes (NHCs) and Lewis acid-base pair strategy, we theoretically designed a new class of compounds III-1, i.e., (NHCAR)C[triple bond, length as m-dash]E(Al(C6F5)3). Quantum chemical calculations showed that these singlet compounds possess very favourable isomerization, fragmentation and dimerization stabilities at the B3LYP/def2-TZVPP//B3LYP/def2-SVP level. The calculated bond lengths of CE in III-1 are 1.63 Å for Si, 1.70 Å for Ge, 1.91 Å for Sn and 2.01 Å for Pb, respectively, which are close to or even shorter than the known C[triple bond, length as m-dash]E bond lengths. In addition, the significant Mayer bond order values, two orthogonal π orbitals and one σ orbital between the C and E atoms also indicate the characteristics of triple bonds. Based on several bonding analyses, strong delocalization is found to exist between the C[triple bond, length as m-dash]E core and NHCAR forming a weak C[double bond, length as m-dash]C double bond. Hence, such obtained C[triple bond, length as m-dash]E species also can be described by their resonace structures as cunmulene analogs. In all, III-1 proposed here not only presents a universal C[triple bond, length as m-dash]E motif for all the heavier group 14 elements, but also provides a new strategy for the design and synthesis of heteronuclear group 14 triple bonds in the future.

A sixteen-valence-electron carbon-group 13 family with global penta-atomic planar tetracoordinate carbon: an ionic strategy.

The design of planar tetracoordinate carbon (ptC) has always been a challenge due to its unique bonding mode that necessitates the perfect balance between the carbon center and surrounding ligands both electronically and mechanically. A unique type of 18-valence-electron (18ve) template, i.e., CAl42-, has been found to be very effective in designing various novel 18ve-species upon skeletal substitution. In this work, we showed that though ptC is not the global structure for the parent 16ve-CAl4, suitable skeletal substitution can allow for a series of global minimum ptC species. Theoretical calculations at the level of CCSD(T)/def2-QZVP//B3LYP/def2-QZVP for 35 carbon-group 13 systems with 16-ve, i.e., CXaYbZcKd (X, Y, Z, K = Al/Ga/In/Tl; 0 ≤ a, b, c, d ≤ 4, a + b + c + d = 4), showed that 9 systems (CAl3Tl, CGa3Tl, CGa2Tl2, CAl2GaTl, CAl2InTl, CGa2InTl, CAlGa2Tl, CGa2InTl and CAlGaInTl) possess global minimum ptC and 2 systems (CAl3In and CAl2Tl2) have quasi-GM ptC. Except for CAl3Tl and CAl3In, all the ptCs were predicted for the first time. All these stable ptC structures have the same skeleton and can be described as the same ionic sub-structure, i.e., [A-]B+. This study not only enriches 16ve-ptC, but also directly demonstrates that utilizing an ionic strategy, non-ptC CAl4 also can be used as a template to extend the ptC family.

Mono-silicon isoelectronic replacement in CAl4 : van't hoff/le bel carbon or not?

In cluster studies, the isoelectronic replacement strategy has been successfully used to introduce new elements into a known structure while maintaining the desired topology. The well-known penta-atomic 18 valence electron (ve) species C Al 4 2 - and its Al- /Si or Al/Si+ isoelectronically replaced clusters CAl3 Si- , CAl2 Si2 , C AlSi 3 - , and C Si 4 2 + , all possess the same anti-van't Hoff/Le Bel skeletons, that is, nontraditional planar tetracoordinate carbon (ptC) structure. In this article, however, we found that such isoelectronic replacement between Si and Al does not work for the 16ve-CAl4 with the traditional van't Hoff/Le Bel tetrahedral carbon (thC) and its isoelectronic derivatives CAl3 X (X = Ga/In/Tl). At the level of CCSD(T)/def2-QZVP//B3LYP/def2-QZVP, none of the global minima of the 16ve mono-Si-containing clusters CAl2 SiX+ (X = Al/Ga/In/Tl) maintains thC as the parent CAl4 does. Instead, X = Al/Ga globally favors an unusual ptC structure that has one long C─X distance yet with significant bond index value, and X = In/Tl prefers the planar tricoordinate carbon. The frustrated formation of thC in these clusters is ascribed to the CSi bonding that prefers a planar fashion. Inclusion of chloride ion would further stabilize the ptC of CAl2 SiAl+ and CAl2 SiGa+ . The unexpectedly disclosed CAl2 SiAl+ and CAl2 SiGa+ represent the first type of 16ve-cationic ptCs with multiple bonds. © 2019 Wiley Periodicals, Inc.

Responses of soil active carbon and nitrogen to short-term warming in alpine treeline of west Sichuan, China.

Alpine treeline ecosystem is more sensitive to global warming under low temperature limitation with the aggravation of greenhouse effect, which may directly affect plant growth and soil carbon and nitrogen processes. We expected that climate warming would change soil active carbon and nitrogen content in alpine ecosystems. This experiment was conducted in long-term research station of alpine forest ecosystems, in Lixian County, Sichuan Province. The open top camber (OTC) was used to simulate warming, intact soil core (soil organic layer and mineral soil layer) of OTC and CK were collected in April, July and October 2017. Soil dissolved organic carbon (DOC), soil microbial biomass carbon (MBC), dissolved organic nitrogen (DON) and soil microbial biomass nitrogen (MBN) were measured. The results showed that average temperature increased by 0.88 ℃ for air, 0.48 ℃ for soil organic layer and 0.23 ℃ for mineral soil layer. The simulated warming did not significantly change soil organic matter and water content, but significantly increased pH of mine-ral soil layer, and significantly reduced DOC and DON contents of mineral soil layer in non-growing season. There was significant seasonal variation for the contents of DOC, DON and MBN in the two layers, but not for MBC. The MBC and MBN contents of soil organic layer were significantly higher than that of mineral soil layer. There was a significant positive correlation between active carbon and nitrogen with soil organic matter and water content. There was a significant positive correlation between MBC, MBN and soil pH, whereas MBN was negatively correlated with soil temperature.

A kinetically persistent isomer found for pentazole: a global potential energy surface survey.

Among the N5R family, pentazoles (A1) with a 103-year-old research history remain the only class of kinetically persistent isomers. Aided by the first global isomeric survey and substitution study of N5H at the composite CBS-QB3 level, we predicted a new N5R isomer (C1) with kinetic stability close to pentazoles.

CAl3X (X = B/Al/Ga/In/Tl) with 16 valence electrons: can planar tetracoordinate carbon be stable?

As a perpetual chemical curiosity, planar tetracoordinate carbon (ptC) that violates the traditional tetrahedral carbon (thC) has made enormous achievements. In particular, the 18-valence-electron (18ve) counting rule has been found to be very effective in predicting ptC structures, as in CX42- (X = Al/Ga/In/Tl). By contrast, the corresponding neutral CX4 with 16ve each takes the thC form like methane. Herein, we report a mono-substituted neutral 16ve-CAl3X (X = Al/Ga/In/Tl). Our theoretical results showed that the competition between thC and ptC can be well tuned upon variation of X, and for X = In and Tl, the ptC structure becomes isoenergetic to and even more stable than thC, respectively. Thus, a low-lying ptC can be achieved in the 16ve-CAl3X set without acquiring additional electrons. This unintuitive result can be ascribed to the increased energetic preference of the ionic sub-structure [CAl3-]X+ from X = Al to Tl. We thus predict the first penta-atomic ptC species with 16ve, and the ionic strategy presented in this work is expected to promote novel designs of ptC molecules.

[Application of regression tree in analyzing the effects of climate factors on NDVI in loess hilly area of Shaanxi Province].

Based on the 10-day SPOT VEGETATION NDVI data and the daily meteorological data from 1998 to 2007 in Yan' an City, the main meteorological variables affecting the annual and interannual variations of NDVI were determined by using regression tree. It was found that the effects of test meteorological variables on the variability of NDVI differed with seasons and time lags. Temperature and precipitation were the most important meteorological variables affecting the annual variation of NDVI, and the average highest temperature was the most important meteorological variable affecting the inter-annual variation of NDVI. Regression tree was very powerful in determining the key meteorological variables affecting NDVI variation, but could not build quantitative relations between NDVI and meteorological variables, which limited its further and wider application.

[Nitrate pollution in groundwater for drinking and its affecting factors in Hailun, northeast China].

Nitrate pollution in groundwater has become a worldwide problem. It may affect the water quality for daily use and thus the health of people. The temporal and spatial characteristics of nitrate pollution in the groundwater were addressed by sample analysis of the drinkable water from 157 wells in Hailun, Heilongjiang, northeastern China. It was found that the mean value of nitrate concentration in all wells was 14.01 mg x L(-1). Of all the samples, the nitrate concentrations of 26.11% wells exceeded the standard of drinkable water (10.00 mg x L(-1)). A significant difference was found on the spatial distribution of nitrate pollution in the study area. The pollution degree in term of nitrate pollution was in the order: the central rolling hills and flooding plain > the northeastern mountain area > the southwest rolling hills and plain. Based on the results, the factors causing the pollution we analyzed from the well properties and pollution sources. As for well properties, the type of the pipe material plays a critical role in the groundwater nitrate pollution. It was found that the wells with seamless pipe have less pollution than those with multiple-sections pipe. The concentrations of seamless pipe wells and multiple ones were respectively 5.08 mg x L(-1) and 32.57 mg x L(-1), 12.26% and 82.35% of these two kinds wells exceeded 10.00 mg x L(-1), the state drinking water standard. In the whole Hailun, there is no statistically relationship between nitrate-N levels of wells and the well depth. However, a statistically lower nitrate-N was observed in the deep wells than that in the shallower ones. The mean values of nitrate concentration of the seamless-pipe deep wells, seamless-pipe shallow wells, multiple-section-pipe deep wells and multiple-section-pipe shallow wells were 1.84, 12.02, 25.14 and 45.61 mg x L(-1). Analysis of pollution source shows that the heavily polluted regions are usually associated with large use of nitrogen fertilizer and household livestock or poultry. This indicates a positive correlation between the nitrate-N pollution of groundwater and the nitrogen fertilizer, household livestock, poultry.

Voltage-dependent slowly activating anion current regulated by temperature and extracellular pH in mouse B cells.

Voltage-dependent, outwardly rectifying anion channels have been described in various cells including lymphocytes. In this study, we found that murine B cells express the voltage-dependent slowly activating anion channels (VSACs). Using a whole-cell configuration, I (VSAC) in Bal-17 was induced by a sustained depolarization (>0 mV) which was remarkably facilitated at 35 degrees C (Q (10)=23 at 30 mV of clamp voltage). Substitution of extracellular Cl(-) with gluconate shifted the reversal potential to the right (35.7 mV). Gd(3+) (IC(50)=0.11 microM) significantly attenuated I (VSAC), but DIDS partially blocked I (VSAC). In addition, extracellular acidification suppressed I (VSAC) whereas alkalinization facilitated the channel activation. I (VSAC) was decreased by 90% at pH 6.35 and increased by 180% at pH 8.0. In cell-attached and inside-out patch clamps, depolarization slowly activated the anion channels of large conductance (approximately 270 pS) with multiple levels of subconductances. The single channel currents were also blocked by Gd(3+) and acidic pH. Furthermore, I (VSAC) was also observed in WEHI-231 (an immature B cell line) and freshly isolated splenic B cells of mice. In summary, murine B cells express unique voltage-dependent anion channels that show a strong sensitivity to both temperature and extracellular pH. Further investigation is required to understand the physiological roles of VSAC and its molecular identity.

Flux enhancement during ultrafiltration of produced water using turbulence promoter.

Concentration polarization and membrane fouling remain one of the major hurdles for the implementation of ultrafiltration of produced water. Although many applications for ultrafiltration were already suggested, only few were implemented on an industrial scale. Among those techniques, turbulence promoter can be more simple and effective in overcoming membrane fouling and enhancing membrane flux. As for the result that turbulence promoter increase fluid velocity, wall shear rates and produce secondary flows or instabilities, the influence of turbulence promoter was investigated on permeate flux during produced water ultrafiltration and the potential application of this arrangement for an industrial development. Experimental investigations were performed on 100 KDa molecular weight cut-off PVDF single-channel tubular membrane module using four kinds of turbulence promoters. It is observed that the significant flux enhancement in the range of 83%-164% was achieved while the hydraulic dissipated power per unit volume of permeate decreased from 31%-42%, which indicated that the using of turbulence promoter is more efficient than operation without the turbulence promoter. The effects of transmembrane pressure and cross-flow velocity with and without turbulence promoter were studied as well. Among the four kinds of turbulence promoters, winding inserts with 20.0 mm pitch and 1.0 mm wire diameter showed better performances than the others did.

Role of arachidonic acid in hyposmotic membrane stretch-induced increase in calcium-activated potassium currents in gastric myocytes.

AIM: To study effects of arachidonic acid (AA) and its metabolites on the hyposmotic membrane stretch-induced increase in calcium-activated potassium currents (I(KCa)) in gastric myocytes. METHODS: Membrane currents were recorded by using a conventional whole cell patch-clamp technique in gastric myocytes isolated with collagenase. RESULTS: Hyposmotic membrane stretch and AA increased both I(K(Ca))) and spontaneous transient outward currents significantly. Exogenous AA could potentiate the hyposmotic membrane stretch-induced increase in I(K(Ca)). The hyposmotic membrane stretch-induced increase in I(K(Ca)) was significantly suppressed by dimethyleicosadienoic acid (100 micromol/L in pipette solution), an inhibitor of phospholipase A2. Nordihydroguaiaretic acid, a lipoxygenase inhibitor, significantly suppressed AA and hyposmotic membrane stretch-induced increases in I(K(Ca)). External calcium-free or gadolinium chloride, a blocker of stretch-activated channels, blocked the AA-induced increase in I(K(Ca)) significantly, but it was not blocked by nicardipine, an L-type calcium channel blocker. Ryanodine, a calcium-induced calcium release agonist, completely blocked the AA-induced increase in I(K(Ca)); however, heparin, a potent inhibitor of inositol triphosphate receptor, did not block the AA-induced increase in I(K(Ca)). CONCLUSION: Hyposmotic membrane stretch may activate phospholipase A2, which hydrolyzes membrane phospholipids to ultimately produce AA; AA as a second messenger mediates Ca(2+) influx, which triggers Ca(2+)-induced Ca(2+) release and elicits activation of I(K(Ca)) in gastric antral circular myocytes of the guinea pig.

Effects of unsaturated fatty acids on calcium-activated potassium current in gastric myocytes of guinea pigs.

AIM: To investigate the effects of exogenous unsaturated fatty acids on calcium-activated potassium current (I(K(Ca))) in gastric antral circular myocytes of guinea pigs. METHODS: Gastric myocytes were isolated by collagenase from the antral circular layer of guinea pig stomach. The whole-cell patch clamp technique was used to record I(K(Ca)) in the isolated single smooth muscle cells with or without different concentrations of arachidonic acid (AA), linoleic acid (LA), and oleic acid (OA). RESULTS: AA at concentrations of 2,5 and 10 micromol/L markedly increased I(K(ca)) in a dose-dependent manner. LA at concentrations of 5, 10 and 20 micromol/L also enhanced I(K(Ca)) in a dose-dependent manner. The increasing potency of AA, LA, and oleic acid (OA) on I(K(Ca)) at the same concentration (10 micromol/L) was in the order of AA>LA>OA. AA (10 micromol/L)-induced increase of I(K(ca)) was not blocked by H-7 (10 micromol/L), an inhibitor of protein kinase C (PKC), or indomethacin (10 micromol/L), an inhibitor of the cyclooxygenase pathway, and 17-octadecynoic acid (10 micromol/L), an inhibitor of the cytochrome P450 pathway, but weakened by nordihydroguaiaretic acid (10 micromol/L), an inhibitor of the lipoxygenase pathway. CONCLUSION: Unsaturated fatty acids markedly increase I(K(ca)), and the enhancing potencies are related to the number of double bonds in the fatty acid chain. The lipoxygenase pathway of unsaturated fatty acid metabolism is involved in the unsaturated fatty acid-induced increase of I(K(ca)) in gastric antral circular myocytes of guinea pigs.

Effect of actin microfilament on potassium current in guinea pig gastric myocytes.

AIM: To investigate the effect of actin microfilament on potassium current and hyposmotic membrane stretch-induced increase of potassium current in gastric antral circular myocytes of guinea pig. METHODS: Whole-cell patch clamp technique was used to record potassium current in isolated gastric myocyes. RESULTS: When the membrane potential was clamped at -60 mV, an actin microfilament disruptor, cytochanlasin-B(Cyt-B, 20 micromol/L in pipette) increased calcium-activated potassium current (I(K(Ca))) and delayed rectifier potassium current (I(K(V))) to 138.4+/-14.3% and 142.1+/-13.1% respectively at +60 mV. In the same condition, an actin microfilament stabilizer phalloidin (20 micromol/L in pipette) inhibited I(K(Ca)) and I(K(V)) to 74.2+/-7.1% and 75.4+/-9.9% respectively. At the holding potential of -60 mV, hyposmotic membrane stretch increased I(K(Ca)) and I(K(V)) by 50.6+/-9.7% and 24.9+/-3.3% at +60 mV respectively. In the presence of cytochalasin-B and phalloidin (20 micromol/L, in the pipette) condition, hyposmotic membrane stretch also increased I(K(Ca)) by 44.5+/-7.9% and 55.7+/-9.8% at +60 mV respectively. In the same condition, cytochalasin-B and phalloidin also increased I(K(V)) by 23.0+/-5.5% and 30.3+/-4.5% respectively. However, Cyt-B and phalloidin did not affect the amplitude of hyposmotic membrane stretch-induced increase of I(K(Ca)) and I(K(V)). CONCLUSION: Actin microfilaments regulate the activities of potassium channels, but they are not involved in the process of hyposmotic membrane stretch-induced increase of potassium currents in gastric antral circular myocytes of guinea pig.

Role of calcium-activated potassium currents in CNP-induced relaxation of gastric antral circular smooth muscle in guinea pigs.

AIM: To investigate ion channel mechanism in CNP-induced relaxation of gastric circular smooth muscle in guinea pigs. METHODS: Spontaneous contraction of gastric smooth muscle was recorded by a four -channel physiograph. The whole cell patch-clamp technique was used to record calcium-activated potassium currents and membrane potential in the gastric myocytes isolated by collagenase. RESULTS: C-type natriuretic peptide (CNP) markedly inhibited the spontaneous contraction in a dose-dependent manner in gastric circular smooth muscle in guinea pigs. Ly83583, an inhibitor of guanylate cyclase, weakened CNP-induced inhibition on spontaneous contraction but Zaparinast, an inhibitor of cGMP sensitive phosphoesterase, potentiated CNP-induced inhibition in gastric circular smooth muscles. The inhibitory effects of CNP on spontaneous contraction were blocked by tetrathylammonium (TEA), a nonselective potassium channel blocker. CNP hyperpolarized membrane potential from -60.0 mV+/-2.0 mV to -68.3 mV+/-3.0 mV in a single gastric myocyte. CNP increased calcium-activated potassium currents (I(K(ca))) in a dose-dependent manner in gastric circular myocytes. CNP also increased the spontaneously transient outward currents (STOCs). Ly83583 partly blocked CNP-induced increase of calcium-activated potassium currents, but Zaparinast potented the effect. CONCLUSION: CNP inhibits spontaneous contraction, and potassium channel may be involved in the process in gastric circular smooth muscle of guinea pigs. CNP-induced increase of I(K(ca)) is mediated by a cGMP dependent pathway.