几种生物CaCO3霰石结晶的取向性

CaCO3结晶广泛分布于生物界,其主要结晶形式为方解石、霰石及球霰石。用X－射线衍射法对三角帆蚌及合浦珍珠母贝的珍珠层、墨鱼骨和大黄鱼耳石的CaCO3结晶进行测定,发现各样品均有一定取向性,以三角帆蚌和合浦珍珠母贝珍珠层的取向性为最强,墨鱼骨的取向性次之,大黄鱼耳石的取向性最小,以上材料粉末样的衍射分析表明,各样品对应d值间差异极小,均为X射线衍射卡（5－0453）所表征的CaCO3霰石结构。     

Growth and survival of coral transplants with and without electrochemical deposition of CaCO3

This study aims to investigate experimentally the effect of electrochemical deposition of CaCO₃ on linear and girth growth, survival and skeletal structure of Porites cylindrica Dana. Transplanted coral nubbins were subjected to up to 18 V and 4.16 A of direct current underwater to induce the precipitation of dissolved minerals. Naturally growing colonies showed a significant increase in percentage longitudinal growth over the treated and untreated corals. Survival followed a similar trend as the growth rate. Lowest survival rates were found in the untreated nubbins. Phenotypic alterations were observed in the treated nubbins where the basal corallites decreased in size with a concomitant increase in their number per unit area. This was probably due to increased mineral concentration (such as Ca²⁺, Na⁻, Mg²⁺, CO₃²⁻, Cl⁻, OH⁻ and HCO₃⁻) at the basal region of the nubbins. These alterations were accompanied by a significant increase in girth growth rates of the treated nubbins at their basal regions. The abundance of mineral ions at the basal region thus appeared to be utilized by the numerous small polyps for a lateral increase in size of the nubbins instead of a longitudinal increase.     

Ancient latitudinal gradients of C3/C4 grasses interpreted from stable isotopes of New World Pleistocene horse (Equus) teeth

Carbon and oxygen isotopic data are reported from 116 Pleistocene Equus teeth from sixty-six localities in the New World ranging from 68°N (Alaska, Canada) to 35°S (Argentina). Equus species have been predominantly grazers, and as such, carbon isotopic values of their tooth enamel provide evidence of the Pleistocene distribution of C₃ and C₄ grasses. The carbon data presented here indicate a gradient (δ¹³C range of 10 parts/mil) in the relative proportion of C₃ and C₄ grasses between high latitude and equatorial Equus samples. The largest amount of change from C₃ to C₄ grasses during the Pleistocene occurred in the mid-latitudes between about 30 to 40°. The oxygen data, which vary proportionately with temperature, indicate a latitudinal gradient (δ¹⁸O range of 20 parts/mil) between high-latitude and equatorial Equus samples. The basic pattern of latitudinal gradients of C₃/C₄ grass distribution and temperature as interpreted from these Pleistocene data is similar to the modern-day. The use of stable isotopes of fossil herbivore teeth represents a new means to interpret Pleistocene climates and terrestrial ecology.     

碳酸钙对水稻吸收重金属(Pb、Cd、Zn)和As的影响

选用重金属(Pb、Cd、Zn)和As复合污染土壤进行水稻盆栽试验,结果表明,碳酸钙的添加显著提高了土壤pH值,显著降低了土壤中交换态Pb、Cd、Zn和As的含量,与对照相比,交换态Pb、Cd、Zn和As含量分别最多降低了98.35%,93.72%,98.52%和69.48%。碳酸钙对水稻根、稻谷干重和总生物量没有显著影响,添加量过高时显著降低了水稻分蘖数和茎叶干重,说明过量施用碳酸钙对水稻生长会产生负面作用。因为碳酸钙的添加,水稻植株各部位重金属Zn含量显著降低,糙米中Zn含量最多减少了34.95%;根、谷壳中Pb、Cd含量显著降低,但糙米中含量却未显著降低;水稻各部位As含量均没有显著降低。参照《食品中污染物限量》(GB2762—2012),试验糙米中Pb、Cd、无机As含量均未达到限量标准。显然,碳酸钙的添加降低了Pb、Cd、Zn的生物有效性(水稻根系对Pb、Cd、Zn的吸收累积减少),但并未有效地抑制Pb、Cd向糙米转运;碳酸钙显著降低了土壤的交换态As含量,但并未使土壤中As的生物有效性明显降低(水稻植株各部位的As含量并未显著减少)。     

Syntheses and characterization of the W(II) and W(III) N2 complexes, [WCl2(PMe3)3]2N2 and [WCl3(PMe3)2]2N2

Refluxing WCl₄(PMe₃)₃ under a nitrogen atmosphere in the presence of two equivalents of sodium amalgam leads to a reduction to the W(II) complex [cis,mer-WCl₂(PMe₃)₃]₂N₂ (1), which can be converted to [mer,trans-WCl₃(PMe₃)₂]₂N₂ (2) via appropriate oxidation/chlorination. Structural data have been obtained for both complexes, and demonstrate significantly increased steric crowding in 1 due to PMe₃/PMe₃ interactions. The N-N bond distances in the two compounds are similar, at 1.279(4) and 1.243(18) Å, respectively.     

Fire and the Miocene expansion of C4 grasslands

C₄ photosynthesis had a mid‐Tertiary origin that was tied to declining atmospheric CO₂, but C₄‐dominated grasslands did not appear until late Tertiary. According to the ‘CO₂‐threshold’ model, these C₄ grasslands owe their origin to a further late Miocene decline in CO₂ that gave C₄ grasses a photosynthetic advantage. This model is most appropriate for explaining replacement of C₃ grasslands by C₄ grasslands, however, fossil evidence shows C₄ grasslands replaced woodlands. An additional weakness in the threshold model is that recent estimates do not support a late Miocene drop in pCO₂. We hypothesize that late Miocene climate changes created a fire climate capable of replacing woodlands with C₄ grasslands. Critical elements were seasonality that sustained high biomass production part of year, followed by a dry season that greatly reduced fuel moisture, coupled with a monsoon climate that generated abundant lightning‐igniting fires. As woodlands became more open from burning, the high light conditions favoured C₄ grasses over C₃ grasses, and in a feedback process, the elevated productivity of C₄ grasses increased highly combustible fuel loads that further increased fire activity. This hypothesis is supported by paleosol data that indicate the late Miocene expansion of C₄ grasslands was the result of grassland expansion into more mesic environments and by charcoal sediment profiles that parallel the late Miocene expansion of C₄ grasslands. Many contemporary C₄ grasslands are fire dependent and are invaded by woodlands upon cessation of burning. Thus, we maintain that the factors driving the late Miocene expansion of C₄ were the same as those responsible for maintenance of C₄ grasslands today.     

Using stable isotopes to determine soil carbon input differences under ambient and elevated atmospheric CO2 conditions

Quantitative estimates of soil C input under ambient (35 Pa) and elevated (60 Pa) CO₂-partial pressure (pCO₂) were determined in a Free-Air Carbon dioxide Enrichment (FACE) experiment. To facilitate ¹³C-tracing, Trifolium repens L. was grown in a soil with an initial δ¹³C distinct by at least 5‰ from the δ¹³C of T. repens grown under ambient or elevated pCO₂. A shift in δ¹³C of the soil organic C was detected after one growing season. Calculated new soil C inputs in soil under ambient and elevated pCO₂ were 2 and 3 t ha^–1, respectively. Our findings suggest that under elevated CO₂ conditions, soil C sequestration may be altered by changes in plant biomass production and quality.     

Seasonal variation in pathways of CH4 production and in CH4 oxidation in rice fields determined by stable carbon isotopes and specific inhibitors

Flooded rice fields, which are an important source of the atmospheric methane, have become a model system for the study of interactions between various microbial processes. We used a combination of stable carbon isotope measurements and application of specific inhibitors in order to investigate the importance of various methanogenic pathways and of CH₄ oxidation for controlling CH₄ emission. The fraction of CH₄ produced from acetate and H₂/CO₂ was calculated from the isotopic signatures of acetate, carbon dioxide (CO₂) and methane (CH₄) measured in porewater, gas bubbles, in the aerenchyma of the plants and/or in incubation experiments. The calculated ratio between both pathways reflected well the ratio determined by application of methyl fluoride (CH₃F) as specific inhibitor of acetate‐dependent methanogenesis. Only at the end of the season, the theoretical ratio of acetate: H₂ = 2 : 1 was reached, whereas at the beginning H₂/CO₂‐dependent methanogenesis dominated. The isotope discrimination was different between rooted surface soil and unrooted deep soil. Root‐associated CH₄ production was mainly driven by H₂/CO₂. Porewater CH₄ was found to be a poor proxy for produced CH₄. The fraction of CH₄ oxidised was calculated from the isotopic signature of CH₄ produced in vitro compared to CH₄ emitted in situ, corrected for the fractionation during the passage from the aerenchyma to the atmosphere. Isotope mass balances and in situ inhibition experiments with difluoromethane (CH₂F₂) as specific inhibitor of methanotrophic bacteria agreed that CH₄ oxidation was quantitatively important at the beginning of the season, but decreased later. The seasonal pattern was consistent with the change of potential CH₄ oxidation rates measured in vitro. At the end of the season, isotope techniques detected an increase of oxidation activity that was too small to be measured with the flux‐based inhibitor technique. If porewater CH₄ was used as a proxy of produced CH₄, neither magnitude nor seasonal pattern of in situ CH₄ oxidation could be reproduced. An oxidation signal was also found in the isotopic signature of CH₄ from gas bubbles that were released by natural ebullition. In contrast, bubbles stirred up from the bulk soil had preserved the isotopic signature of the originally produced CH₄.     

Crystal structures of MoCl2(O)(O2)(OPMePh2)2 and mixtures of MoCl2(O2)(OPPh3)2 and MoCl2(O)(O2)(OPPh3)2: allylic alcohol isomerization studies using MoCl2(O)(O2)(OPMePh2)2

Adding one equivalent of H₂O₂ to compounds of stoichiometry MoCl₂(O)₂(OPR₃)₂, OPR₃ = OPMePh₂ or OPPh₃, leads to the formation of oxo-peroxo compounds MoCl₂(O)(O₂)(OPR₃)₂. The compound MoCl₂(O)(O₂)(OPMePh₂)₂ crystallized with an unequal disorder, 63%:37%, between the oxo and peroxo ligands, as verified by single-crystal X-ray diffractometry, and can be isolated in reasonable yields. MoCl₂(O)(O₂)(OPPh₃)₂, was not isolated in pure form, co-crystallized with MoCl₂(O)₂(OPPh₃)₂ in two ratios, 18%:82% and 12%:88%, respectively, and did not contain any disorder in the arrangement of the oxo and peroxo groups. These complexes accomplish the isomerization of various allylic alcohols. A mechanism of this reaction has been constructed based on ¹⁸O isotopic studies and involves exchange between the alcohol and metal bonded O atoms.     

Effect of prostaglandins A1, A2, B1, B2, E2 and F2α on human umbilical cord vessels

The effect of six naturally occurring prostaglandins on isolated umbilical arteries and veins has been studied. All six prostaglandins had a constricting effect on the umbilical vessels. On the umbilical artery preparations the potencies in decreasing order were A₂>B₂>F_2α>B₁>E₂>A₁. Prostaglandin B₂ was more potent than PGA₂ on the umbilical vein. Polyphloretin phosphate (PPP) antagonised the constricting effect of all six prostaglandins without altering responses to 5-hydroxytryptamine.     

Comparative reactivity of triorganosilanes, HSi(OEt)3 and HSiEt3, with IrCl(CO)(PPh3)2. Formation of IrCl(H)2(CO)(PPh3)2 or Ir(H)2(SiEt3)(CO)(PPh3)2 depending on the substituents at Si

Reaction of HSi(OEt)₃ with IrCl(CO)(PPh₃)₂ (5:1 molar ratio) at room temperature for 1 h gives IrCl(H){Si(OEt)₃}(CO)(PPh₃)₂ (1), which is observed by the ¹H and ³¹P{¹H} NMR spectra of the reaction mixture. The same reaction, but in 20:1 molar ratio at 50 °C for 24 h produces IrCl(H)₂(CO)(PPh₃)₂ (2) rather than the expected product Ir(H)₂{Si(OEt)₃}(CO)(PPh₃)₂ (3) that was previously reported to be formed by this reaction. Accompanying formation of Si(OEt)₄, (EtO)₃SiOSi(OEt)₃, and (EtO)₂HSiOSi(OEt)₃ is observed. On the other hand, trialkylhydrosilane HSiEt₃ reacts with IrCl(CO)(PPh₃)₂ (10:1 molar ratio) at 80 °C for 84 h to give Ir(H)₂(SiEt₃)(CO)(PPh₃)₂ (4) in a high yield, accompanying with a release of ClSiEt₃.     

Sn-S and Ru-Ru bonds cleavage reactions between [Ph3SnS(CH2)3SSnPh3] and Ru3(CO)12: X-ray crystal structures of [Ph3SnS(CH2)3SSnPh3] and trans-[Ru(CO)4(SnPh3)2]

The organotin complex [Ph₃SnS(CH₂)₃SSnPh₃] (1) was synthesized by PdCl₂ catalyzed reaction between Ph₃SnCl and disodium-1,3-propanedithiolate which in turn was prepared from 1,2-propanedithiol and sodium in refluxing THF. Reaction of 1 with Ru₃(CO)₁₂ in refluxing THF affords the mononuclear complex trans-[Ru(CO)₄(SnPh₃)₂] (2) and the dinuclear complex [Ru₂(CO)₆(μ-κ²-SCH₂CH₂CH₂S)] (3) in 20 and 11% yields, respectively, formed by cleavage of Sn-S bond of the ligand and Ru-Ru bonds of the cluster. Treatment of pymSSnPPh₃ (pymS = pyrimidine-2-thiolate) with Ru₃(CO)₁₂ at 55-60 °C also gives 2 in 38% yield. Both 1 and 2 have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction analysis.     

Solution-mediated syntheses and characterizations of two new zincophosphites [C6H14N2]0.5[Zn(H2PO3)2] and [C4H12N2]0.5[(CH3)2NH2][Zn2(HPO3)3]

Two new zincophosphites [C₆H₁₄N₂]_0.5[Zn(H₂PO₃)₂] 1 and [C₄H₁₂N₂]_0.5[(CH₃)₂NH₂][Zn₂(HPO₃)₃] 2 have been solvothermally synthesized in mixed solvents of N,N-dimethylformamide (DMF) and 1,4-dioxane (DOA), respectively. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a neutral inorganic chain formed by ZnO₄ and HPO₂(OH) units. Interestingly, the left- and right-handed hydrogen-bonded helical chains are alternately formed via the hydrogen-bonds between two adjacent chains. Compound 2 exhibits a layer structure with 4- and 12-MRs formed by ZnO₄ and HPO₃ units, in which two kinds of organic amine molecules both act as countercations to compensate the overall negative electrostatic charge of the anionic network.     

Synthesis and characterization of SrCu2(O2CR)3(bdmap)3 and Bi2(O2CCH3)4(bdmap)2(H2O) (R = CH3, CF3; bdmap = 1,3-bis(dimethylamino)-2-propanolato)

New mixed metal complexes SrCu₂(O₂CR)₃(bdmap)₃ (R = CF₃ (1a), CH₃ (1b)) and a new dinuclear bismuth complex Bi₂(O₂CCH₃)₄(bdmap)₂(H₂O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF₂ and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi₂O₃ at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm⁻¹. Crystal data for 1a: C₂₇H₅₁N₆O₉F₉Cu₂Sr/THF, monoclinic space group P2₁/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) ų, Z = 2; for 1b: C₂₇H₆₀N₆O₉Cu₂Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) ų, Z = 8; for 2: C₂₂H₄₈O₁₁N₄Bi₂, monoclinic space group P2₁/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) ų, Z = 4.     

C3植物稳定碳同位素组成与盐分的关系

植物在盐生环境中δ13C值的改变可能包含两个成分:一个是盐分对CO2的扩散、传递或光合速率的影响而引起的δ13C值的改变;另一个是光合途径的转换引起的δ13C值的变化,δ13C值的大小与诱导发生CAM或C4代谢的程度有关.植物组织的δ13C值随盐度的变化趋势除了与植物本身固有的耐盐性有关以外,盐度和胁迫时间是影响植物δ13C的重要因素.根据盐生条件下同位素分馏特点可知,盐生植物与非盐生植物的δ13C随盐度的变化趋势有所不同.对非盐生植物而言,在低盐度和短期的盐处理下,随盐度的增加和胁迫时间的延长植物的δ13C值增大,这个阶段限制光合作用的主要因素是气孔导度;但是如果盐度过低,δ13C变化很小,则难以表现出应有的相关性;随着胁迫的加强,当限制光合作用的非气孔因素成为主导因素时,由于光合作用受到强烈抑制(光合结构遭到破坏),δ13C将随之降低.对盐生植物而言,其δ13C与最适盐度有关.最适盐度下,植物的δ13C低于其它盐度条件下的δ13C值.盐生条件下,有些C3植物可能发生光合途径的转换,无论诱导发生的是C4代谢还是CAM代谢,δ13C值均趋于增大.但是,一般情况下,盐处理诱导的光合途径的改变对植物组织整体的δ13C的影响很小.在密闭环境中或郁闭林地,植物和土壤呼吸释放的CO2再次参与光合作用,也会改变植物的δ13C值.为了更加全面地考察植物δ13C与盐度的关系,需要设置较大的盐度范围和进行长期的胁迫处理,才能够获得相对充分的数据,才有利于全面分析植物δ13C值与耐盐性的关系.     

Coccolithophore (–CaCO3) flux in the Sea of Okhotsk: seasonality, settling and alteration processes

Coccolithophore fluxes were determined in the Sea of Okhotsk using samples from a 1 year experiment (12 August 1990 to 12 August 1991) with sediment traps at 258 and 1061 m depth. A special study was made on Coccolithus pelagicus, using fragmentation and the degree of etching, as indicators of transport mechanisms. A Corrosion Index for C. pelagicus is developed. The coccolithophore flux pattern at 258 m depth was characterised by a strong seasonality, with flux peaks during autumn 1990 (late November to early December) and spring 1991 (March). The assemblage consisted almost entirely of the two species C. pelagicus and Emiliania huxleyi. During autumn, coccolithophore transportation to 258 m depth mainly occurred within cylindrical fecal pellets and marine snow aggregates of silicoflagellates, and through agglutination on tintinnids. Grazing caused severe fragmentation of coccoliths and disintegration of coccospheres. Marine snow aggregates contained many intact coccospheres of C. pelagicus. During spring, coccolithophores were probably removed from the euphotic zone by the ballast effect of sinking diatoms. The coccolithophore flux peak in spring occurred immediately after the ice had retreated from the trap station, and the trapped assemblage included coccoliths of subtropical species. These features indicate drifting from an ice-free location to the south or east.The coccolith and coccosphere flux at 1061 m was respectively 7 and 12 times lower than at 258 m depth, and maximum fluxes were recorded 2 months later. Increasing carbonate dissolution from 258 to 1061 m depth is expressed in the coccolithophore–CaCO₃ flux reduction of 82%, and in the increasing percentage of etched coccoliths of Coccolithus pelagicus from 32 to >90%.     

Convenient preparation of [CuX(PCy3)2](X = Br, I, SCN, N3) complexes. X-ray crystal structure of [Cu(N3)(PCy3)2] (Cy = cyclo-C6H11)

The labile cations [Cu(F-BF₃)(PCy₃)₂] and [Cu(OTf)(PCy₃)₂] are versatile precursors for the formation of [Cu(X)(PCy₃)₂] (X = Br, I, SCN, N₃) complexes by metathesis with NaX. The azide [Cu(N₃)(PCy₃)₂] is triclinic, space group , a = 9.755(4), B = 22.78(1), C = 9.284(6) Å, = 96.76(3), β = 115.36(3), γ = 94.20(5)°, Z = 2.     

Synthesis, structure and properties of TTF-carboxylate bridged paddlewheel dirhodium complexes, Rh2(BuCO2)3(TTFCO2) and Rh2(BuCO2)2(TTFCO2)2

Reaction of tetrathiafulvalene carboxylic acid (TTFCO₂H) with paddlewheel dirhodium complex Rh₂(Bu^tCO₂)₄ yielded TTFCO₂-bridged complexes Rh₂(Bu^tCO₂)₃(TTFCO₂) (1) and cis- and trans-Rh₂(Bu^tCO₂)₂(TTFCO₂)₂ (cis- and trans-2). Their triethylamine adducts [1(NEt₃)₂] and cis-[2(NEt₃)₂] were purified and isolated with chromatographic separation, and characterized with single crystal X-ray analysis. Trans-[2(NEt₃)₂] is not completely separated from a mixture of cis- and trans-[2(NEt₃)₂], but its single crystals were obtained from a solution of the mixture. A three-step quasi-reversible oxidation process was observed for 1 in MeCN. The first two steps correspond to the oxidation of the TTFCO₂ moiety and the last one is the oxidation of the Rh₂ core. The oxidation of cis-2 is observed as a two-step process with very similar E_1/2 values to those of the first two processes for 1. Both 1⁺ and cis-2²⁺ in MeCN at room temperature show isotropic ESR spectra with a g value of 2.008 and a_H = 0.135 mT for two equivalent H atoms and a_H = 0.068 mT for one H atom. The redox and ESR data of cis-2 suggest that the intramolecular interaction between the TTF moieties is very small.     

Synthesis and structures of the cuboidal iron-sulfur-nitrosyl-phosphine clusters [Fe4S3(NO)4(PR3)3] (R = Et, Pr, C6H11)

A series of cuboidal iron-sulfur clusters [Fe₄S₃(NO)₄(PR₃)₃]^0,1+ (R = Et, Prⁱ, Cy) were synthesized by two routes: reductive desulfurization of [Fe₄S₄(NO)₄] by tertiary phosphines, and substitution of triphenylphosphine in [Fe₄4S₃(NO)₄(PPh₃)₃] by a more basic phosphine. The structures of 3[Fe₄S₃(NO)₄(PEt₃)₃] · 0.5Et₂O, [Fe₄S₃(NO)₄(PEt₃)₃] [Fe₄S₃(NO)₇] and partially substituted [Fe₄S₃(NO)₄(PPh₃)_2⁻ (PPrⁱ₃)] have been determined by X-ray diffraction in order to define the cuboidal Fe₄S₃ core, previously known only in Roussin's black anion and its reduced form, [Fe₄S₃(NO)₇7]^1−,2−, and as a part of the iron-molybdenum cofactor of nitrogenase.