Supercritical CO(2): a novel environmentally friendly mutagen

In order to develop mutagenic methods, supercritical CO(2) was evaluated as a new environmentally friendly mutagen. During treatment by supercritical CO(2), the survival rate and the positive mutation rate of Flavobacterium sp. strain YY25 were strongly dependent on pressure, temperature, treatment time and additive (DMSO). 8 MPa, 35 degrees C, 30 min of supercritical CO(2) and 1% of DMSO were believed as the optimum doses. After the seed liquid was treated under these conditions, a mutant strain with about 44.2% increase in lipase yield comparing with the wild strain was acquired, indicating that the novel mutagenic method by supercritical CO(2) was feasible and promising in microbial breeding field.     

Insights in starch acetylation in sub- and supercritical CO2

An in-depth study on the acetylation of starch with acetic anhydride (Ac₂O) and sodium acetate (NaOAc) as the catalyst in pressurized carbon dioxide (scCO₂) in a broad pressure range (8–25 MPa) and a temperature of 90 °C is provided. Highest degrees of substitution (DS) of 0.29 (1 h reaction time) and 0.62 (24 h reaction time) were found near the critical point of the mixture (15 MPa). The phase behavior of the system CO₂, starch and acetic anhydride (Ac₂O) was studied in a high pressure view cell. The critical points were a clear function of the temperature and increased from the range of 9.4–10 MPa to 14.5–14.8 MPa when going from 50 to 90 °C (Ac₂O mole fraction at the critical point in the range of 0.08–0.09). Acetylation experiments with a range of starch particles sizes showed a clear relation between the DS and the particle size.     

C4作物FACE(free-air CO2 enrichment)研究进展

持续迅速上升的大气二氧化碳浓度([CO₂])是全球变暖最大的驱动因子,但其作为光合作用底物直接增加了作物的生产力。相比C₃作物,人们对未来高浓度CO₂情形下C₄作物的响应规律认识较少。与封闭或半封闭气室研究相比,FACE(free-air CO₂ enrichment)试验在空气自由流动的大田条件下对作物表现进行研究,它提供了对未来作物生长环境的真实模拟,因此提供了评估CO₂肥料效应以及揭示植物响应机制的最好机会。作为人类重要的粮食和饲料来源,高粱和玉米是最重要的C₄作物。在简介美国玉米和高粱FACE系统的基础上,综述了FACE情形下高浓度CO₂(模拟本世纪中叶大气CO₂浓度,即550 μmol/mol)对两大作物生理、生长和产量以及土壤特性等方面的影响,同时比较了与气室研究结果的异同点。(1)FACE使干旱条件下两作物光合作用显著增强,但湿润条件下没有影响;FACE条件下高粱出现光合适应现象,而玉米没有;(2)FACE使两作物气孔导度大幅下降,导致叶温升高、蒸腾速率下降、蒸发蒸腾总量减少或没有变化、叶片总水势和水分利用效率增加或没有变化;(3)FACE对两作物物候期和化学组分影响很少;(4)FACE使干旱条件下两作物生长和产量略有增加,但湿润条件下没有影响;(5)FACE使高粱田土壤丛枝状菌根真菌的长度和易提取胶状物质浓度显著增加,导致水稳性土壤团聚体增加;FACE对高粱田N₂O或含氮气体(N₂O+N₂)的排放没有影响;(6)高浓度CO₂对两作物气孔导度的影响FACE试验明显大于气室试验,而对生长和产量的影响呈相反趋势。阐明CO₂与基因型、土壤湿度和大气温度间的互作效应及其机制是下一轮C₄作物FACE研究优先考虑的方向,技术的不断进步已为利用大型FACE系统来研究这些互作效应提供了可能。     

Kinetic studies of the reduction of hexaaquacobalt(III) perchlorate by a cobaloxime, [Co(dmgBF2)2(H2O)2]

The reaction of with Co(dmgBF₂)₂(H₂O)₂ in 1.0 M HClO₄/LiClO₄ was found to be first-order in both reactants and the [H⁺] dependence of the second-order rate constant is given by k_2obs = b/[H⁺], b at 25 °C is 9.23 ± 0.14 × 10² s⁻¹. The [H⁺] dependence at lower temperatures shows some saturation effect that allowed an estimate of the hydrolysis constant for as K_a = 9.5 × 10⁻³ M at 10 and 15 °C. Marcus theory and the known self-exchange rate constant for Co(OH₂)₅OH^2+/+ were used to estimate an electron self-exchange rate constant of k₂₂ = 1.7 × 10⁻⁴ M⁻¹ s⁻¹ for .     

Supercritical carbon dioxide pretreatment of corn stover and switchgrass for lignocellulosic ethanol production

Supercritical CO₂ (SC-CO₂), a green solvent suitable for a mobile lignocellulosic biomass processor, was used to pretreat corn stover and switchgrass at various temperatures and pressures. The CO₂ pressure was released as quickly as possible by opening a quick release valve during the pretreatment. The biomass was hydrolyzed after pretreatment using cellulase combined with β-glucosidase. The hydrolysate was analyzed for the amount of glucose released. Glucose yields from corn stover samples pretreated with SC-CO₂ were higher than the untreated sample’s 12% glucose yield (12 g/100 g dry biomass) and the highest glucose yield of 30% was achieved with SC-CO₂ pretreatment at 3500 psi and 150 °C for 60 min. The pretreatment method showed very limited improvement (14% vs. 12%) in glucose yield for switchgrass. X-ray diffraction results indicated no change in crystallinity of the SC-CO₂ treated corn stover when compared to the untreated, while SEM images showed an increase in surface area.     

Transesterification of sunflower oil to biodiesel on ZrO2 supported La2O3 catalyst

ZrO₂ supported La₂O₃ catalyst prepared by impregnation method was examined in the transesterification reaction of sunflower oil with methanol to produce biodiesel. It was found that the catalyst with 21 wt% loaded La₂O₃ and calcined at 600 °C showed the optimum activity. The basic property of the catalyst was studied by CO₂-TPD, and the results showed that the fatty acid methyl ester (FAME) yield was related to their basicity. The catalyst was also characterized by TG–DTA, XRD, FTIR, SEM and TEM, and the mechanism for the formation of basic sites was discussed. It was also found that the crystallite size of support ZrO₂ decreased by loading of La₂O₃, and the model of the solid-state reaction on the surface of La₂O₃/ZrO₂ catalyst was proposed. Besides, the influence of various reaction variables on the conversion was investigated.     

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.     

城市规模对大气污染物NO2和PM2.5浓度的影响

随着我国城市的快速发展,城市的区域性大气污染问题日益突出,尤其是大城市和超大城市的污染问题更加严重。那么城市规模的扩大是否必然导致空气污染的加剧?控制城市人口规模是否是防治空气污染的有效手段?这些问题成为空气污染防治中政府、公众和学者广泛关注的焦点。采用2013年冬季全国114个重点城市两种典型大气污染物-NO_2(传统)和PM_(2.5)(新型)-浓度的实时监测数据,首先分析了这两种大气污染物的空间分布特征,进而定量分析城市人口规模和大气污染物浓度的关系。结果显示:(1)仅有21%的城市NO_2浓度达到WHO的城市年均浓度标准(40μg/m~3),全部城市的PM_(2.5)浓度高于WHO年均浓度标准(10μg/m~3);(2)大气污染物的空间分布具有显著的集聚特征和区域性特征,表现为:NO_2呈较为分散的空间分布,而PM_(2.5)的空间分布呈现"北高南低、内陆高沿海低"的特征。NO_2浓度高的区域主要分布在天津、河北东南部和山东中部地区,PM_(2.5)浓度高的区域主要分布于河北西南部和山东西部;(3)常住人口规模同冬季NO_2和PM_(2.5)浓度呈倒"U"型关系;在1000到1200万的城市冬季平均NO_2和PM_(2.5)浓度最高(NO_2:69.28μg/m~3,PM_(2.5):119.58μg/m~3)。(4)总人口低于1200万的城市,冬季NO_2浓度和PM_(2.5)浓度随着城市规模增加而显著升高(NO_2:r=0.44,P0.01;PM_(2.5):r=0.43,P0.01);总人口高于1200万的城市,NO_2浓度同城市规模呈显著负相关关系(r=0.91,P0.05),PM_(2.5)浓度随城市规模增加逐渐降低。(5)常住人口密度在1000人/km~2以下的重点城市,NO_2和PM_(2.5)浓度同城市人口密度呈显著正相关关系(NO_2:r=0.23,P0.05;PM_(2.5):r=0.36,P0.01)。常住人口密度在1000人/km~2以上的城市人口密度同NO_2和PM_(2.5)浓度呈显著负相关关系(NO_2:r=-0.61,P0.05;PM_(2.5):r=0.63,P0.01)。以上研究结果可以为划定不同大气污染物的重点防治区域和制定联合防治行动计划提供理论依据,并为重点城市大气污染治理和城市人口规模控制理论完善提供参考。     

Evidence for H2O2 as the product of reduction of oxygen by alternative oxidase in mitochondria from potato tubers

Oxygen consumption by alternative oxidase (AOX), present in mitochondria of many angiosperms, is known to be cyanide-resistant in contrast to cytochrome oxidase. Its activity in potato tuber (Solanum tuberosum L.) was induced following chilling treatment at 4 °C. About half of the total O₂ consumption of succinate oxidation in such mitochondria was found to be sensitive to SHAM, a known inhibitor of AOX activity. Addition of catalase to the reaction mixture of AOX during the reaction decreased the rate of SHAM-sensitive oxygen consumption by nearly half, and addition at the end of the reaction released nearly half of the consumed oxygen by AOX, both typical of catalase action on H₂O₂. These findings with catalase suggest that the product of reduction of AOX is H₂O₂ and not H₂O, as previously surmised. In potatoes subjected to chill stress (4 °C) for periods of 3, 5 and ?8 days the activity of AOX in mitochondria increased progressively with a corresponding increase in the AOX protein detected by immunoblot of the protein.     

超临界CO_2流体萃取苦丁茶多糖的工艺优化

为了探讨超临界CO_2萃取广西苦丁茶中多糖的工艺条件,该研究采用超临界CO_2流体萃取技术分离苦丁茶多糖,利用苯酚-硫酸法对苦丁茶多糖含量进行测定,并考察不同萃取温度(35、40、45、50、55、60℃)、萃取压力(20、25、30、35、40、45、50 MPa)、萃取时间(30、60、90、120、150 min)、夹带剂(甲醇、95%甲醇、50%甲醇、无水乙醇、95%乙醇、50%乙醇)以及夹带剂(95%乙醇)用量(2.0、2.5、3、3.5、4.0、4.5、5.0 mL·min~(-1))对多糖得率的影响,通过设计正交实验方案,对超临界CO_2萃取广西苦丁茶多糖的提取工艺进行优化。结果表明:通过单因素和正交实验考察了苦丁茶多糖提取的主要影响因素,得到的最佳萃取工艺条件为萃取温度50℃,萃取压力40 MPa,夹带剂流量3.5 mL·min~(-1),萃取时间150 min;采用苯酚-硫酸法对苦丁茶多糖含量进行测定。在最优萃取条件下得到的苦丁茶多糖的提取率为7.05%。由此可知,采用超临界CO_2流体萃取,具有提取温度低、萃取率高、萃取周期短、低耗以及污染小等优点,适用于苦丁茶多糖的提取。     

Bis(O2S2 macrocycle) complexes of palladium(II)

Two isomeric dibenzo-O₂S₂ macrocycles L¹ and L² have been synthesised and their coordination chemistry towards palladium(II) has been investigated. Two-step approaches via reactions of 1:1-type complexes, [cis-Cl₂LPd] (1a: L = L¹, 1b: L = L²), with different O₂S₂ macrocycle systems (L¹ and L²) have led to the isolation of the following bis(O₂S₂ macrocycle) palladium(II) complexes in the solid state: [Pd(L¹)₂](ClO₄)₂ (2a) and a mixture of [Pd(L¹)₂](ClO₄)₂ (2a) + [Pd(L²)₂](ClO₄)₂ (2b).     

超临界CO2提取甘草地上部分总黄酮

采用单因素试验对甘草地上部分（茎叶）的超临界CO₂提取工艺进行了研究。实验考察了压力、萃取时间、温度及CO₂流量对甘草地上部分总黄酮提取率的影响,以总黄酮提取率和含量为指标,系统的研究了超临界二氧化碳萃取法提取甘草地上部分总黄酮的提取效果。得出的最佳工艺参数为：采用40~60目原料,80%乙醇为夹带剂,萃取时间：1.5 h;萃取压力：30.0 MPa;萃取温度：50℃;CO₂流量：10 kg·h^-1;分离压力: 5.8 MPa;分离温度: 40℃。实验结果表明超临界二氧化碳萃取甘草总黄酮的提取率2.09%,含量5.42%,工艺具有提取率高,纯度高的特点,为规模化生产甘草总黄酮的提取提供了研究基础。     

Starch phosphorus content in potato (Solanum tuberosum L.) cultivars and its effect on other starch properties

The research presented herein provides valuable data with respect to the phosphorus content of starches from many potato (Solanum tuberosum L.) cultivars using an energy-dispersive X-ray fluorescence technique. In all starches examined, the phosphorus content ranged from 308 to 1244 ppm. Furthermore, the estimation of the starch characteristics of representative samples differing manifestly in their phosphorus content indicated that enhancing the starch phosphate resulted in significant increases in the swelling power, peak viscosity, and breakdown and significant but small increases in the onset and peak temperatures of gelatinization. Other starch quality parameters, such as the amylose content, median granule size, and the gelatinization enthalpy, did not change significantly due to the degree of phosphate substitution of starch.     

Hyperpnoea and CO2 sensitivity of the respiratory centres during exercise

The aim of this study was to specify whether exercise hyperpnoea was related to the CO2 sensitivity of the respiratory centres measured during steady-state exercise of mild intensity. Thus, ventilation (VE), breathing pattern [tidal volume (VT), respiratory frequency (f), inspiratory time (TI), total time of the respiratory cycle (TTOT), VT/TI, TI/TTOT] and CO2 sensitivity of the respiratory centres determined by the rebreathing method were measured at rest (SCO2re) and during steady-state exercise (SCO2ex) of mild intensity [CO2 output (VCO2) = 20 ml.kg-1.min-1] in 11 sedentary male subjects (aged 20-34 years). The results showed that SCO2re and SCO2ex were not significantly different. During exercise, there was no correlation between VE and SCO2ex and, for the same VCO2, all subjects had very close VE values normalized for body mass (bm), regardless of their SCO2ex (VEbm0.75 = 1.44 l.min-1.kg-1 SD 0.10). A highly significant positive correlation between SCO2ex and VT (normalised for bm) (r = 0.80, P less than 0.01), TI (r = 0.77, P less than 0.01) and TTOT (r = 0.77, P less than 0.01) existed, as well as a highly significant negative correlation between SCO2ex and (normalised for bm-0.25) (r = -0.73, P less than 0.01). We conclude that the hyperpnoea during steady-state exercise of mild intensity is not related to the SCO2ex. The relationship between breathing pattern and SCO2ex suggests that the breathing pattern could influence the determination of the SCO2ex. This finding needs further investigation.     

杉木人工林不同深度土壤CO2通量

土壤CO₂通量具有明显的时间和空间变异性。土壤温度和含水量是影响土壤CO₂通量的重要因素,同时,不同深度的土壤CO₂通量对温度和含水量变化的响应差异较大,因此,研究土壤CO₂通量和影响因素随土壤深度的变化,对于准确评估土壤碳排放具有重要意义。选择福建三明杉木人工林(Cunninghamia lanceolata)作为研究对象,利用非散射红外CO₂浓度探头和Li-8100开路式土壤碳通量系统,并使用Fick扩散法计算了0-60cm深度土壤CO₂的通量,结果表明:(1)5种扩散模型计算的表层(5cm)CO₂通量与Li-8100测量结果均具有显著相关性(P<0.01),Moldrup气体扩散模型计算结果较好。(2)土壤CO₂浓度随深度的增加而升高,但60cm深度以下土壤CO₂浓度开始降低;不同深度土壤CO₂浓度的日变化均呈现单峰型;0-60cm土壤CO₂通量日通量均值变化范围为0.54-2.17μmol m^-2 s^-1;(3)指数拟合分析显示,5、10cm和60cm深度处土壤CO₂通量与温度具有显著相关性,Q₁₀值分别为1.35、2.01和4.95。不同深度土壤含水量与CO₂通量的相关性不显著。     

Supercritical CO(2) fluid extraction of crystal water from trehalose dihydrate. Efficient production of form II (T(alpha)) phase

Form II is a kind of metastable crystalline form of trehalose anhydrate, and it is easily converted to the dihydrate crystal by absorbing water in moist atmosphere at room temperature (Akao et al., Carbohydr. Res. 2001, 334, 233-241). It can be utilized as an edible and nontoxic desiccant, and thus its efficient production from the dihydrate is significant from a viewpoint of industrial applications. In this study, we attempt to extract crystal water from the dihydrate using supercritical CO(2). We examine the dependence of extraction efficiency on the extraction time, the temperature and pressure of the fluid. Then, FTIR measurements are carried out to detect the extracted water and to identify the polymorphic phase of the sugar sample after the extraction treatment. In particular, the so-called first derivative euclidean distance analysis for IR spectra is shown to be quite useful for the structural identification. Consequently, we demonstrate that form II is produced from the dihydrate through supercritical CO(2) fluid extraction if appropriate temperature and pressure conditions (around 80 degrees C and 20 MPa) are maintained.     

Aquaporins and membrane diffusion of CO2 in living organisms

Background

Determination of CO₂ diffusion rates in living cells revealed inconsistencies with existing models about the mechanisms of membrane gas transport. Mainly, these discrepancies exist in the determined CO₂ diffusion rates of bio-membranes, which were orders of magnitudes below those for pure lipid bilayers or theoretical considerations as well as in the observation that membrane insertion of specific aquaporins was rescuing high CO₂ transport rates. This effect was confirmed by functional aquaporin protein analysis in heterologous expression systems as well as in bacteria, plants and partly in mammals.

Scope of Review

This review summarizes the arguments in favor of and against aquaporin facilitated membrane diffusion of CO₂ and reports about its importance for the physiology of living organisms.

Major Conclusions

Most likely, the aquaporin tetramer forming an additional fifth pore is required for CO₂ diffusion facilitation. Aquaporin tetramer formation, membrane integration and disintegration could provide a mechanism for regulation of cellular CO₂ exchange. The physiological importance of aquaporin mediated CO₂ membrane diffusion could be shown for plants and cyanobacteria and partly for mammals.

General Significance

Taking the mentioned results into account, consequences for our current picture of cell membrane transport emerge. It appears that in some or many instances, membranes might not be as permeable as it was suggested by current bio-membrane models, opening an additional way of controlling the cellular influx or efflux of volatile substances like CO₂. This article is part of a Special Issue entitled Aquaporins.     

土壤CO2及岩溶碳循环影响因素综述

全球碳循环已成为全球气候变化的核心问题之一,岩溶作用对大气CO2浓度的调节以及其与土壤CO2的密切关系也受到了国内外普遍关注。岩溶作用消耗土壤CO2对大气碳库起到了重要的减源作用,对土壤CO2进行研究将有利于进一步揭示岩溶碳循环过程。因此从气候条件、土壤理化性质、土地利用类型等方面综述了土壤CO2的影响因素以及其对岩溶碳循环的影响,并提出其它酸参与到岩溶碳循环中将会减弱岩溶碳汇效应。由于各个因素之间往往相互联系,共同影响土壤CO2和岩溶碳循环,在研究岩溶碳汇时,需以地球系统科学和岩溶动力系统理论为指导,综合考虑大气圈、水圈、岩石圈、生物圈中各种因素的影响。     

胞外ATP对AlCl3诱导的细胞死亡过程中胞内H2O2和Ca2+水平的影响及其生理机制分析

该实验以烟草悬浮细胞 BY 2 为材料,在烟草悬浮细胞中分别加入0.05、0.10、0.15、0.20 mmol·L^-1AlCl₃,以等体积去离子水处理的悬浮细胞液为对照,并依据前述实验结果选择0.15 mmol·L^-1 AlCl₃,分别添加5 mmol·L^-1 DMTU(H₂O₂ 抑制剂)、20 μmol·L^-1CaCl₂、15 μmol·L^-1 LaCl₃(Ca²⁺通道抑制剂)和50 μmol·L^-1 ATP设计多项处理,分析胞外ATP(eATP)对铝离子(Al³⁺)胁迫引起的植物细胞死亡及其胞内H₂O₂、Ca²⁺的影响,以揭示Al³⁺胁迫下植物调节细胞死亡的可能机制,进一步扩展对eATP功能的认知。结果显示：(1)随着 AlCl₃ 胁迫浓度的提高,细胞死亡水平和胞内H₂O₂水平上升,而胞内Ca²⁺和eATP水平则逐渐降低。(2)外援施加H₂O₂抑制剂 DMTU(二甲基硫脲)和Ca²⁺能够有效缓解AlCl₃诱导的细胞死亡水平的上升;而Ca²⁺通道抑制剂LaCl₃(三氯化镧)则加剧了AlCl₃胁迫下的细胞死亡。(3)在AlCl₃胁迫下对细胞添加外源ATP,能够缓解AlCl₃胁迫下胞内H₂O₂水平上升和Ca²⁺水平下降的同时,并显著降低AlCl₃胁迫导致的细胞死亡。研究表明, Al³⁺以剂量依赖的模式提升细胞死亡和细胞内H₂O₂的水平并降低胞内Ca²⁺和eATP水平,AlCl₃诱导的细胞死亡受到H₂O₂和Ca²⁺水平变化的调节,eATP可以通过调节H₂O₂与Ca²⁺水平缓解AlCl₃诱导的细胞死亡。推测Al³⁺胁迫可能通过抑制钙离子通道而破坏了细胞内H₂O₂和Ca²⁺之间的协同关系,外源ATP对Al³⁺诱导H₂O₂上升的缓解作用可能是由于其提升了细胞的抗氧化能力。     

1-D coordination chains of Cu(hfac)2 and Mn(hfac)2 bridged by phenyl-nitronylnitroxide derivatives

Two alternating 1-D metal-radical linear [L:Cu(hfac)₂]_n and zig-zag [L:Mn(hfac)₂]_n chains (where L = 4-trimethylsilylethynyl-1-(4,4,5,5-tetramethyl-3-oxylimidazoline-1-oxide)benzene) and hfac = hexafluoroacetylacetonate) are described and characterized by X-ray diffraction of their crystals. Bulk magnetic measurements of L:Cu(hfac)₂ indicated a ferromagnetic interaction with J = 6 cm⁻¹ and L:Mn(hfac)₂ yielded ferrimagnetic interactions with J = −95 cm⁻¹. For the latter, a strong increase of their magnetic moment at lowest temperatures was observed only at very low static magnetic field, while for H_dc > 0.05 T saturation effect led to a downward slope after reaching a maximum.