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1.
A small pond containing the charophyte Chara hispida was monitored over a one-year period for changes in growth, water chemistry, water level and stable isotopic composition. Chara growth was found to be seasonal, with maximum growth occurring from late April to July. During this period, pH rose to > 10 while the dissolved inorganic carbon (DIC) and calcium fell as a result of photosynthesis and calcification. Large gradients in pH, water temperature and irradiance were found within the Chara sward and measurements showed that most growth and photosynthesis occurred within the upper 20 cm of the water column. Chara oospore formation was also found to be seasonal but dependent upon environmental conditions.

δ18Ow rose rapidly during summer as evaporation progressed and this was correlated with the δ18ODIC, and to some extent with δ18Oc of the Chara encrusted calcite. However, extreme isotopic disequilibrium was observed between the δ18Oc and the δ18Ow and also between the δ13Cc and the δ13CDIC. This arose from the high pH allowing atmospheric CO2 to enter the water and combine directly with OH.

It is concluded that, within shallow eutrophic lakes containing Chara swards, inferences of climate (e.g. air temperature) cannot be made from observations of the isotopic composition of Chara carbonates. However in combination with other geochemical data, disequilibrium events may be identifiable in ancient lake basins and taken as evidence for lake shallowing and/or eutrophication.  相似文献   


2.
The thermal and photochemical reactions of CpRe(PPh3)2H4 and CpRe(PPh3)H4 (Cp = η5-C5H5) with PMe3, P(p-tolyl)3, PMe2Ph, DMPE, DPPE, DPPM, CO, 2,6-xylylisocyanide and ethylene have been examined. While CpRe(PPh3)2H2 is thermally inert, it will undergo photochemical substitution of one or two PPh3 ligands. With ethylene, substitution is followed by insertion of the olefin into the C-H bond of benzene, giving ethylbenzene. CpRe(PPh3)H4 undergoes thermal loss of PPh3, which leads to substituted products of the type CpRe(L) H4. Photochemically, reductive elimination of dihydrogen occurs preferentially. The complex trans-CpRe(DMPE)H2 was structurally characterized, crystallizing in the monoclinic space group P21/n (No. 14) with a = 6.249(6), b = 16.671(8), c = 13.867(7) Å, β = 92.11(6)°, V = 1443.7(2.9) Å and Z = 4. The complex trans-CpRe(PMe2Ph)2H2 was structurally characterized, crystallizing in the monoclinic space group P21/n (No. 14) with a = 7.467(3), b = 23.874(14), c = 11.798(6) Å, β = 100.16(4)°, V = 2070.2(3.4) Å3 and Z = 4.  相似文献   

3.
The viscous energy dissipation in a two generation model of the human bronchial tree is determined from inspiratory velocity and static pressure data obtained for large Reynolds numbers (104 < Re < 105). This dissipation is found to be an increasing function of both Re and distance downstream from the inlet of the model. The ratio of the dissipation in the model to the energy dissipation in an equivalent straight pipe system is determined. This ratio, Z*, for the model is compared to values in the literature for lower (laminar) Re. There is more dissipation in the branched model than in a straight pipe (Z* > 1) and turbulence keeps Z* at roughly a fixed value for large Reynolds numbers (104 < Re < 105). Z* values for curved pipes are also compared to the branching system values. It is found that the energy dissipation for the branched model behaves similarly to that in curved pipes.  相似文献   

4.
《植物生态学报》2015,39(11):1044
Aims Phragmites australis marshes in Tianjin play an important role in ecosystem functioning. Wetlands of Tianjin municipality have been suffering from serious nitrogen loading, salinization and water shortage. The foliar stable carbon isotope ratio (δ13C) is a good parameter which records environmental change information associated with the plant growth process, and reflects physiological and ecological responses of plants to environment changes. The objective of this study is to investigate the effects of environment stress on the leaf δ13C of P. australis in marsh wetlands in Tianjin municipality.Methods This study was conducted in Qilihai, Beidagang, and Dahuangpu marsh wetlands. We investigated the foliar δ13C of P. australis and sediment properties, and evaluated the relationships between the foliar δ13C and sediment environmental factors. Important findings 1) Foliar δ13C ranged from -26.3‰ to -23.6‰, with an average value of -25.8‰. 2) Sediment water and nitrogen status were the important factors affecting reed foliar δ13C. Foliar δ13C was negatively correlated to sediment relative water content, and positively correlated to sediment total nitrogen and available nitrogen content. In contrast, foliar δ13C was not significantly correlated to sediment salinity and phosphorus content. 3) Leaf δ13C were significantly positively correlated with leaf nitrogen content, and negatively correlated with leaf carbon and nitrogen ratio across all site. However, these relationships were not detected due to the wetland drainage at Qilihai site in August. Wetland drainage changed the plant water and nitrogen balance, and further affected water and nitrogen utilization strategies of P. australis. Moreover, wetland drainage had stronger effects on these processes than nitrogen loading and salinization.  相似文献   

5.
天津芦苇(Phragmites australis)沼泽具有重要的生态功能。目前天津地区水体咸化、氮污染和水资源短缺问题严重, 显著影响了芦苇湿地的植物生理生态过程。植物稳定碳同位素组成(碳稳定同位素比值(δ13C))能够记录与植物生长过程相关联的环境变化信息, 反映植物对环境变化的生理生态适应特性。该研究调查了天津七里海、北大港和大黄堡湿地芦苇叶片的δ13C分布特征, 探讨了影响该地区叶片δ13C值变化的主要因素。研究表明: 1)天津芦苇湿地植物叶片δ13C的变化范围在-26.3‰ - -23.6 ‰之间, 平均值为-25.8‰; 2)芦苇叶片δ13C与底泥相对含水量呈显著负相关关系, 与底泥有效氮和全氮含量呈显著正相关关系, 而与底泥盐度和磷含量没有显著相关关系; 水分条件和底泥氮营养状况是影响叶片的δ13C值变化的主要因素; 3)淹水条件下, 芦苇叶片δ13C与叶片质量氮含量呈显著正相关关系, 与叶碳氮比呈显著负相关关系, 8月份七里海湿地干涸打破了此相关关系。当前环境压力下, 天津沼泽湿地干涸极大地改变了芦苇的氮、水平衡和植物对水、氮资源的利用策略, 而湿地干涸对该过程的影响要高于盐度和氮负荷增加。  相似文献   

6.
The complex [Et4N][W(CO)5OMe] (1) has been prepared from the reaction of the photochemically generated W(CO)5THF adduct and [Et4N][OH] in methanol. Complex 1 was shown to undergo rapid CO dissociation in THF to quantitatively provide the dimeric dianion, [W(CO)4OMe]22−. The resulting THF insoluble salt [Et4N]2[W(CO)4OMe]2 (2) has been structurally characterized by X-ray crystallography, with the doubly bridging methoxide ligands being in an anti configuration. Complex 2 was found to subsequently react with excess methoxide ligand in a THF slurry to afford the face-sharing octahedron complex [Et4N]3[W2(CO)6(OMe)3] (3) which contains three doubly bridging methoxide groups. In the absence of excess methoxide ligand complex 2 cleanly yields the tetrameric complex [Et4N]4[W(CO)3OMe]4 (4) which has been structurally characterized as a cubane-like arrangement with triply bridging μ3-methoxide groups and W(CO)3 units. Although complex 3 was not characterized in the solid state, the closely related glycolate derivative [Et4N]3[W2(CO)6(OCH2CH2OH)3] (5) was synthesized and its structure determined by X-ray crystallography. The trianions of complex 5 are linked in the crystal lattice by strong intermolecular hydrogen bonds. Crystal data for 2: space group P21/n, a = 7.696(2), b = 22.019(4), c = 9.714(2) Å, β = 92.22(3)°, Z = 4, R = 6.43%. Crystal data for 4: space group Fddd, a = 12.433(9), b = 24.01(2), c = 39.29(3) Å, Z = 8, R = 8.13%. Crystal data for 5: space group P212121, a = 11.43(2), b = 12.91(1), c = 29.85(6) Å, Z = 8, R = 8.29%. Finally, the rate of CO ligand dissociation in the closely related aryloxide derivatives [Et4N][W(CO)5OR] (R = C6H5 and 3,5-F2C6H3) were measured to be 2.15 × 10−2 and 1.31 × 10−3 s−1, respectively, in THF solution at 5°C. Hence, the value of the rate constant of 2.15 × 10−2 s−1 establishes a lower limit for the first-order rate constant for CO loss in the W(CO)5OMe anion, since the methoxide ligand is a better π-donating group than phenoxide.  相似文献   

7.
为了探明典型荒漠灌木优势物种黑沙蒿(俗名油蒿, Artemisia ordosica)光合过程能量中分配对环境波动的相对变化及其长期调节机制, 该研究于2018年4-10月在宁夏盐池毛乌素沙地, 同时使用MONITORING-PAM多通道荧光监测仪和LI-6400XT便携式光合测量仪对黑沙蒿叶片的最小荧光产量(Fo)、最大荧光产量(Fm)、稳态荧光产量(Fs)、光下最大荧光产量(Fm′)、净光合速率(Pn)、暗呼吸速率(Rd)、蒸腾速率(E)和叶片气孔导度(gs)进行现场测定, 在实验室内计算比叶面积(SLA)、单位面积氮含量(Narea)、叶绿素含量(CChl)和叶绿素a/b (Chl a/b), 分析黑沙蒿光合过程能量分配中固碳耗能占比(ΦA)、光呼吸耗能占比(ΦPR)、调节性热耗散耗能占比(ΦNPQ)和非调节性热耗散耗能占比(ΦNO)与环境参数和叶性状参数之间的关系以及能量分配各组分之间的相对变化。结果表明, 光化学反应组分(ΦAΦPR)和热耗散组分(ΦNPQΦNO)之间呈负相关竞争关系, 两组分内部呈正相关协同关系, EΦAΦPR正相关, 和ΦNPQΦNO负相关。在低土壤含水量(SWC)和高饱和水汽压差(VPD)环境条件下, 黑沙蒿ΦAΦPRSLA显著降低, ΦNPQΦNO显著增加。研究认为, 在长期干旱或高蒸散条件下, 黑沙蒿通过降低SLA等途径避免水分的过度流失, 同时将部分过剩光能由光呼吸代谢途径转移到热耗散组分进行耗散。波动环境下黑沙蒿形态性状的变异和光合过程能量分配的长期调节机制, 反映了其利用形态与生理的协同可塑性对逆境的适应。  相似文献   

8.
Cobalt(III) complexes with a thiolate or thioether ligand, t-[Co(mp)(tren)]+ (2), t-[Co(mtp)(tren)]2+ (1Me) and t-[Co(mta)(tren)]2+ (2Me), (mp = 3-mercaptopropionate, MA = 3-(methylthio)propionate and MTA = 2-(methylthio)acetate) have been prepared in aqueous solutions. The crystal structures of 1, 2, 1Me and 2Me were determined by X-ray diffraction methods. The crystal data are as follows, t-[Co(mp)(tren)]ClO4 (1CIO4): monoclinic, P21/n, A = 10.877(8), B = 11.570(4), c = 12.173(7) Å, β = 92.20(5)°, V = 1531(1) Å3, Z = 4 and R = 0.060; t-[Co(ma)(tren)]Cl·3H2O (2Cl·3H2O): monoclinic, P21/n, a = 7.7688(8), B = 27.128(2), C = 7.858(1) Å, β = 100.63(1)°, V = 1627.7(3) Å3, Z = 4 and R = 0.066; (+)465CD-t-[Co(mtp)(tren)](ClO4)2 ((+)465CD-1Me(ClO4)2): orthorhombic, P212121, A = 10.6610(7), B = 11.746(1), C = 15.555(1) Å, V = 1947.9(3) Å3, Z = 4 and R = 0.068; (+)465CD-t-[Co(mta)(tren)](ClO4)2 ((+)465CD-2Me(ClO4)2): orthorhombic, P212121, a = 10.564(1), B = 11.375(1), C = 15.434(2) Å, V = 1854.7(4) Å3, Z = 4 and R = 0.047. All central Co(III) atoms have approximately octahedral geometry, coordinated by four N, one O, and one S atoms. All of the complexes are only isomer, of which the sulfur atom in the didentate-O,S ligands are located at the trans position to the tertiary amine nitrogen atom of tren. 1 and 1Me contain six-membered chelate ring, and 2 and 2Me do five-membered chelate ring in the didentate ligand. The chirality of the asymmetric sulfur donor atom in (+)465CD-1Me is the S configuration and that in (+)465CD-2Me is the R one. The 1H NMR, 13C NMR and electronic absorption spectral behaviors and electrochemical properties of the present complexes are discussed in relation to their stereochemistries.  相似文献   

9.
The bis(oxazoline) ligand, 2,2-bis[4(R)-phenyl-1,3-oxazolon-2-yl]propane (bpop), was introduced to the η6-benzenemthenium(II) moiety on treatment with [Ru(η6-C6H6)Cl2]2 to give [Ru(η6-C6H6)(bpop)Cl]+. Aquo and amine complexes [Ru(η6-C6H6)(bpop)(L)]2+ (L = H2O (1), NH2R; R = H (2) , Me (3) , and n-Bu (4) ) were prepared by treating the chloride complex with AgBF4 in the presence of L. X-ray structure determinations of 1 and 3 were carried out. Both complexes possessed a three-leg piano stool structure with the N or O donors located at the three comers of a pseudo octahedron. The aquo complex 1 exhibited a dynamic NMR feature in which two magnetically nonequivalent oxazoline parts observed at lower temperatures were interchanged with each other at higher temperatures. This observation was ascribed to the formation of a C2-symmetric 16-electron intermediate via Ru-OH2 cleavage, which is slower in acetone than in dichloromethane owing to more effective solvation by acetone around hydrogens of the coordinated water molecule. The two diastereotopic N-hydrogens of 4 underwent deuterium exchange with CD3OD with greatly different rates from each other owing to different energy of NHO (D) (CD3) interaction. Carboxylate and sulfonate ions (A) formed second sphere complexes with 4 by means of NHA hydrogen bonding, as evidenced by continuous shift of NH2 resonances with increasing amounts of the anions added.  相似文献   

10.
Experimental evidence is provided that selenomethionine oxide (MetSeO) is more readily reducible than its sulfur analogue, methionine sulfoxide (MetSO). Pulse radiolysis experiments reveal an efficient reaction of MetSeO with one-electron reductants, such as e-aq (k = 1.2 × 1010M-1s-1), CO·-2 (k = 5.9 × 108 M-1s-1) and (CH3)2) C·OH (k = 3.5 × 107M-1s-1), forming an intermediate selenium-nitrogen coupled zwitterionic radical with the positive charge at an intramolecularly formed Se N 2σ/1σ* three-electron bond, which is characterized by an optical absorption with λmax at 375 nm, and a half-life of about 70 μs. The same transient is generated upon HO· radical-induced one-electron oxidation of selenomethionine (MetSe). This radical thus constitutes the redox intermediate between the two oxidation states, MetSeO and MetSe. Time-resolved optical data further indicate sulfur-selenium interactions between the Se N transient and GSH. The Se N transient appears to play a key role in the reduction of selenomethionine oxide by glutathione.  相似文献   

11.
介绍了农田FACE(free-air CO2 enrichment)试验中的NO和NO2地气交换观测方法,即静态暗箱采样—NO和NO2化学发光分析法,并对观测结果进行了分析讨论.此观测方法简单、易于操作,并可获得可靠的NO和NO2净交换通量观测结果.在稻麦轮作农田的旱地阶段,无论FACE还是对照处理,NO主要表现为地面净排放,NO2主要表现为地面净吸收.逐日的NO净排放不依赖于土壤温度,但却与土壤含水量呈线性负相关(R2=0.82,P<0.001).NO2净吸收具有明显的季节变化特征,逐日的净吸收通量随土壤温度和土壤含水量的变化可分别用抛物线方程拟合(温度:R2=0.74,P<0.001;含水量:R2=0.69,P<0.001).大气CO2浓度升高200±40μmol·mol-1使NO净排放减弱19%(t检验P=0.096),NO2净吸收减弱10%(t检验P=0.26),这主要是植物生长受到促进的缘故.  相似文献   

12.
Octahedral tetraammineosmium(II) species are generated from their OsIII precursors containing an amine ligand cis to a labile alcohol or triflate. These compounds undergo reversible β-hydride eliminations resulting in the formation of cis-η2-iminium hydride complexes. Judging from NMR data, the η2-iminium group in these products lies parallel to the osmium-hydride bond with the iminium carbon eclipsing the hydride. Attempts to form η2-arene complexes of an OsII ammine system bearing a stereogenic carbon are also described.  相似文献   

13.
植物水的稳定同位素分馏过程是水在土壤-植物-大气连续体中循环的重要环节。以往研究由于叶片水18O同位素比值(δ18O l,b)和氘(D)同位素比值(δDl,b)(合称δl,b)实测数量少只能作为模型验证数据, 导致δl,b富集机制研究多集中于模型研究, 缺乏基于野外试验条件的δl,b富集的控制机制研究。叶片水δDl,bδ18O l,b的富集程度(ΔDl,bΔ18O l,b, 合称Δl,b)通常表示为δl,b与茎秆水D同位素比值(δDx)和18O同位素比值(δ18Ox) (合称δx)之差, 即Δl,b = δl,b - δx。该研究以黑河中游沙漠绿洲春玉米(Zea mays)生态系统为研究对象, 重点采集和分析了季节和日尺度δl,bδx数据, 配套开展了大气水汽δ18O和δD (合称δv)等辅助变量的原位连续观测, 探讨了季节和日尺度上的δl,b富集特征及其影响因素。结果表明: 叶片水δl,bΔl,b的季节变化趋势不明显, 而受蒸腾作用影响表现出白天富集夜间贫化的单峰日变化特征。对于D来说, 无论季节尺度上还是日尺度上, 大气水汽δv和相对湿度是δDl,bΔDl,b的主要环境控制因素; 而对于18O来说, 无论季节尺度上还是日尺度上, 相对湿度是δ18O l,bΔ18O l,b的主要环境控制因素。由于D和18O在热力学平衡分馏上有约8倍差异, 直接分析叶片水ΔDl,bΔ18Ol,b与影响因素的差异性, 有助于理解叶片水δD和δ18O富集过程以及对模型发展有一定的指导意义。  相似文献   

14.
Cuaq+ forms stable complexes with carbon monoxide in aqueous solutions. Furthermore it reacts very fast with aliphatic radicals. The reaction of Cu(CO)maq+ with methyl radicals, CH3 was studied using the pulse-radiolysis technique. The results point out that methyl radicals react with Cu(CO)aq+ to form an unstable intermediate with a CuII-C σ bond identified as (CO)CuII-CH3+, k = (1.1±0.2) × 109 M−1 s−1. This intermediate has a strong LMCT charge transfer band (λmax = 385 nm, max = 2500 M−1 cm−1) which is similar to the absorption bands of other transient complexes with CuII-alkyl σ bonds. The coordinated carbon monoxide in (CO)CuII-CH3+ inserts into the copper—carbon bond (or rather the coordinated methyl migrates to the coordinated carbon monoxide ligand) at a rate of (3.0±0.8) × 102 s−1 to form the copperacetyl complex (CO)mCuII-C(CH3)=O+max = 480 nm, max = 2100 M−1 cm−1). The rate of formation of (CO)CuII-CH3+ and of the insertion reaction are pH independent. The complex (CO)mCuII-C(CH3)=O+ is also unstable and decomposes heterolytically to yield acetaldehyde and Cuaq2+ as the final stable products. This reaction is slightly pH dependent. The same reactivity pattern has been observed for the Cu(COnaq+ complexes (n = 2 or 3). The results clearly point out that CO remains coordinated to transient complexes of the type CuII-alkyl.  相似文献   

15.
(η3-Cyclooctenyl)Co(bisphosphine) compounds react with HBF4 in the presence of alkenes with oxidation of the metal to give the novel, paramagnetic organocobalt(II) species [(η3-cyclooctenyl)Co(bisphosphine)]+BF4, (η3-2-RC3H4)Co(bisphosphine) complexes react similarly. The Co(II) compounds form adducts with CO and NO (the latter being diamagnetic) and undergo facile chemical and electrochemical reduction.  相似文献   

16.
《植物生态学报》2015,39(9):924
Leaf net photosynthesis is crucial for detecting the mechanism of photosynthesis, whereas community net photosynthesis is useful for understanding the photosynthetic capacity of communities and its relationship with environmental factors. In particular, we need to scale up eco-physiological models from leaf scale to canopy level to study carbon cycling at regional or global scale. We hypothesized that accumulated leaf net photosynthetic rate (Pc) at community scale, i.e., calculated based on leaf net photosynthetic rate (Pn) and leaf area index (LAI), equals to measured net community CO2 exchange (NCE). The purpose of this study is to verify this hypothesis. Our field study was carried out in Duolun, Nei Mongol, China, where we constructed single-species communities by sowing Medicago sativa ‘Aohan’ seeds in three plots (3 m × 5 m) on May 30, 2012. On August 16, 2014, Pn of five healthy leaves of M. sativa ‘Aohan’ in each plot were measured with a LI-6400 portable photosynthesis system at 10:00, and net ecosystem CO2 exchange (NEE) in each plot was measured simultaneously with a LI-8100 system connected with a assimilation chamber (0.5 m × 0.5 m × 0.5 m). Pc was calculated based on Pn, number of leaves (n), LAI percentage of healthy leaves (r) and percentage of received effective light by leaves (m). NCE was derived from NEE and ecosystem respiration rate (Reco). Pc was 3.52 μmol CO2·m-2·s-1, and very close to NCE (3.56 μmol CO2·m-2·s-1), suggesting that leaf-scale photosynthesis may accurately predict community-scale photosynthesis. However, our method could not separate community respiration from soil respiration, and future studies, should be designed to counteract this effect. Scaling up from leaf photosynthesis to community photosynthesis should also consider vertical structure of communities and nonlinear responses of leaf photosynthesis to changes in light quantum.  相似文献   

17.
叶片和群落尺度净光合速率关系的探讨   总被引:1,自引:0,他引:1       下载免费PDF全文
叶片净光合速率(Pn)是研究光合作用机理的基本尺度; 而群落净光合速率(Pc)是研究群落光合能力及其与外部环境因子间关系的更好尺度, 特别是区域乃至全球尺度碳循环的研究, 需要将叶片尺度的生理生态模型扩展到冠层尺度。理论上, 群落内所有叶片的累积Pn与实测群落净气体交换速率(NCE)是相等的, 但在野外实际观测中, 两者之间的相互关系目前尚未见报道。该文选取敖汉苜蓿(Medicago sativa ‘Aohan’)人工草地, 采用美国LI-COR公司生产的便携式光合测定系统LI-6400测定Pn, 结合叶面积指数等参数推算Pc, 利用LI-8100连接同化箱测定生态系统净气体交换速率(NEE), 加上土壤呼吸速率, 得到NCE。结果表明: Pc为3.52 μmol CO2·m-2·s-1, 与实测NCE (3.56 μmol CO2·m-2·s-1)基本相等。这表明: 可利用Pn, 结合叶面积指数、群落叶片数目、健康叶片比例和群落可接收有效光照的平均比例等4个关键参数, 准确地换算Pc。然而, 利用同化箱式法测定群落呼吸速率时, 不可避免地会包含土壤呼吸, 所以在观测NCE时, 需要同时测定土壤呼吸。此外, 在冠层模型中, 群落垂直结构和光量子的非线性响应不可忽视。  相似文献   

18.
The N,N-diethylcarbamato derivative of zirconium(IV), Zr(O2CNEt2)4 has been studied by X-ray crystallography. Crystal data: C20H40Na4O8Zr, monoclinic, space group C2/c, a = 14.057(1), b = 12.168(1), c = 16.746(2) Å, β = 108.071(4)°, Z = 4, Dc = 1.356, F(000) = 1168, T = 213 K. The compound is isotypic with the corresponding niobium(IV) derivative with a dodecahedral coordination at the zirconium atom. By reaction of NbCl4(THF)2 with Tl(hfacac), the hexafluoroacetylacetonato derivative of niobium (IV), Nb(hfacac)4, has been prepared and structurally characterized. The compound crystallizes in the orthorhombic space group Pna21 with the following cell constants: a = 10.399(4), b = 15.852(9), c = 119.073(1) Å. It is not isotypic with the corresponding zirconium(IV) derivative, Zr(hfacac)4. Crystal data: C20H4F24O8Zr, monoclinic, space group P21/n, a = 11.974(4), b = 20.451(6), c = 13.140(3) Å, β = 104.487(11)°, Z = 4, Dc = 1.960, F(000) = 1776, T = 223 K. Although in both compounds the central metal atom shows a square antiprismatic coordination, the coordination mode of the ligands is different and slight deviations from the D4(llll) and C2(llss) ideal geometries have been observed in the case of niobium and zirconium, respectively. An EPR study has been performed on the Nb(IV) derivatives as diluted solid solutions in frozen organic solvents or in the diamagnetic matrix of the corresponding zirconium(IV) compound. The EPR spectra have confirmed the presence of non-interacting paramagnets in the solid solutions and, in the case of Nb(O2CNEt2)4, the point symmetry of the paramagnetic centre has been found to be in agreement with the results of the X-ray investigation. An EPR spectrum of rhombic symmetry has been observed for the hexafluoroacetylacetonato derivative of Nb(IV) when diluted in frozen THF solution or in Zr(hfacac)4.  相似文献   

19.
Perfluorophenanthrene and decamethylferrocene cocrystallize as a molecular adduct in monoclinic space group P21/c with a = 8.842(2), b = 11.262(1), c = 30.695(8) Å, β = 95.89(2)°, V = 3040.3(8) Å3, Z = 4. The structure was refined to R = 0.0537 for 1567 observed reflections. The perfluoroarene is twisted and chiral; the crystal is a racemate, however.  相似文献   

20.
Karlodinium veneficum is a cosmopolitan dinoflagellate with a worldwide distribution in mesohaline temperate waters. The toxins from K. veneficum, or karlotoxins (KmTxs), which have been implicated in fish kill events, have been purified from monoalgal cultures, and shown to possess hemolytic, cytotoxic and ichthyotoxic activities. Three karlotoxins (KmTx 1–1, KmTx 1–3 and KmTx 2) have been isolated from two different North American strains of K. veneficum and characterized using liquid chromatography–mass spectrometry (LC–MS). KmTx 1 karlotoxins have a UV absorption maximum (λmax 225 nm) at lower wavelengths than KmTx 2 karlotoxins (λmax 235 nm). The exact masses and predicted empirical formulae for the karlotoxins (KmTx 1–1, 1308.8210, C67H120O24; KmTx 1–3, 1322.8637, and C69H126O23; KmTx 2, 1344.7938, C67H121ClO24) were determined using high resolution mass spectrometry. Although the individual toxins produce a single peak in reverse phase high performance liquid chromatography (HPLC), MS revealed congeners co-eluting within each peak. These congeners could be separated under normal phase chromatography and revealed a single hydroxylation being responsible for the mass differences. Multistage MS (MSn) showed that the three KmTxs and their congeners share a large portion of their structures including an identical 907 amu core fragment.

These data were used to develop a quantitative LC–MS assay for karlotoxins from cultures and environmental samples. The sensitivity afforded by MS detection compared to UV absorbance allowed toxin quantification at 0.2 ng when injected on column. Aqueous solutions of karlotoxins were found to quantitatively adsorb to PTFE and nylon membrane filters. Aliquots from whole cultures or environmental samples could be concentrated and desalted by adsorption to PTFE syringe filters and karlotoxins eluted with methanol for analysis by LC–MS. This simplified solid phase cleanup afforded new data indicating that each karlotoxin may also exist as sulfated derivatives and also provided a rapid detection method for karlotoxin from environmental samples and whole cultures.  相似文献   


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