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.     

Transesterification of Nannochloropsis oculata microalga’s lipid to biodiesel on Al2O3 supported CaO and MgO catalysts

In this study, we present the activities of Al₂O₃ supported CaO and MgO catalysts in the transesterification of lipid of yellow green microalgae, Nannochloropsis oculata, as a function of methanol amount and the CaO and MgO loadings at 50 °C. We found that pure CaO and MgO were not active and CaO/Al₂O₃ catalyst among all the mixed oxide catalysts showed the highest activity. Not only the basic site density but also the basic strength is important to achieve the high biodiesel yield. Biodiesel yield over 80 wt.% CaO/Al₂O₃ catalyst increased to 97.5% from 23% when methanol/lipid molar ratio was 30.     

Structural and functional analysis of Vitamin K2 synthesis protein MenD

Here we describe in detail the crystal structures of the Vitamin K₂ synthesis protein MenD, from Escherichia coli, in complex with thiamine diphosphate (ThDP) and oxoglutarate, and the effects of cofactor and substrate on its structural stability. This is the first reported structure of MenD in complex with oxoglutarate. The residues Gly472 to Phe488 of the active site region are either disordered, or in an open conformation in the MenD oxoglutarate complex structure, but adopt a closed conformation in the MenD ThDP complex structure. Biospecific-interaction analysis using surface plasmon resonance (SPR) technology reveals an affinity for ThDP and oxoglutarate in the nanomolar range. Biochemical and structural analysis confirmed that MenD is highly dependent on ThDP for its structural stability. Our structural results combined with the biochemical assay reveal novel features of the enzyme that could be utilized in a program of rational structure-based drug design, as well as in helping to enhance our knowledge of the menaquinone synthesis pathway in greater detail.     

Efficiency enhancement of the electrocatalytic reduction of CO2: fac-[Re(v-bpy)(CO)3Cl] electropolymerized onto mesoporous TiO2 electrodes

As the greenhouse effect increases, the development of systems able to convert with high efficiency CO₂ to energetically rich molecules owns a crucial weight in the technological and environmental domain. As catalyst, rhenium complexes, of the type fac-[Re(L)(CO)₃Cl] (i.e. L = 2,2′-bipyridyl or 4,4′-bipyridyl), have attracted a large interest demonstrating promising catalytic properties. fac-[Re(v-bpy)(CO)₃Cl]-based polymer deposited onto a solid support has been already investigated as heterogeneous catalyst in the reduction of CO₂. Here, we deposited by electrochemical polymerization fac-[Re(v-bpy)(CO)₃Cl] onto a nanocrystalline TiO₂ film on glass and we investigated by cyclic voltammetry the properties of such heterogeneous catalyst in the electrochemical reduction of CO₂. We demonstrated that the nanoporous nature of the substrate allows to increase the two-dimensional number of redox sites per surface area and hence to get a significant enhancement of the catalytic yield.     

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.     

维生素K2的临床检测方法及其评价指标

维生素K₂(VK₂)是一类具有甲基萘醌结构的脂溶性维生素,越来越多的研究表明VK₂具有多重生理功能,在抗骨质疏松、抑制血管钙化、糖尿病、肿瘤、肝病、慢性肾病、免疫性疾病、神经系统疾病和肥胖等多种疾病中发挥着重要作用。为了更好地指导人们合理地补充VK₂,迫切需要建立简单、可行、准确度和特异性高的VK₂测定方法,确定其正常值范围。本文回顾近年来VK₂的临床检测及其评价方法,对VK₂的体内血药浓度检测、血液标志物检测等进行概述总结,为临床上VK₂的合理应用提供依据。     

Kinetics and mechanisms of the CO2 and SO2 uptake by coordinate ion, cis-[Cr(C2O4)(L-L)(OH2)2] {(L-L) = methyl 3-amino-2,3-dideoxy-α-d-arabino-hexopyranoside} as studied by stopped-flow spectrophotometry

The kinetics of CO₂ and SO₂ uptake by a coordinate ion, cis-[Cr(C₂O₄)(L-L)(OH₂)₂]⁺, where L-L stands for a bidentate sugar ligand, methyl 3-amino-2,3-dideoxy-α-d-arabino-hexopyranoside has been studied, over temperature ranges of 5 - 25 and 5 - 20 °C for CO₂ and SO₂, respectively. Investigations were carried out using stopped-flow spectrophotometry in the range of 340-700 nm. Results of the kinetic measurements obtained for both gases were compared. The kinetics and mechanisms of the reactions were suggested and ΔH^‡ values for both processes were determined.     

Properties of a novel β-glucosidase from Fusarium proliferatum ECU2042 that converts ginsenoside Rg3 into Rh2

A novel β-glucosidase from Fusarium proliferatum ECU2042 (FPG) was successfully purified to homogeneity with a 506-fold increase in specific activity. The molecular mass of the native purified enzyme (FPG) was estimated to be approximately 78.7 kDa, with two homogeneous subunits of 39.1 kDa, and the pI of this enzyme was 4.4, as measured by two-dimensional electrophoresis. The optimal activities of FPG occurred at pH 5.0 and 50 °C, respectively. The enzyme was stable at pH 4.0–6.5 and temperatures below 60 °C, and the deactivation energy (E_d) for FPG was 88.6 kJ mo1⁻¹. Moreover, it was interesting to find that although the purified enzyme exhibited a very low activity towards p-nitrophenyl β-d-glucoside (pNPG), and almost no activity towards cellobiose, a relatively high activity was observed on ginsenoside Rg₃. The enzyme hydrolyzed the 3-C, β-(1 → 2)-glucoside of ginsenoside Rg₃ to produce ginsenoside Rh₂, but did not sequentially hydrolyze the β-d-glucosidic bond of Rh₂. The K_m and V_max values of FPG for ginsenoside Rg₃ were 2.37 mM and 0.568 μmol (h mg protein)⁻¹, respectively. In addition, this enzyme also exhibited significant activities towards various alkyl glucosides, aryl glucosides and several natural glycosides.     

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。     

Study on the heterogeneous degradation of chitosan with H2O2 catalyzed by a new supermolecular assembly crystal: [C6H8N2]6H3[PW12O40]·2H2O

A new supermolecular assembly crystal, [C₆H₈N₂]₆H₃[PW₁₂O₄₀]·2H₂O (DMB-PWA), was synthesized with phosphotungstic acid (PWA) and 1,2-diaminobenzene (DMB) under hydrothermal conditions and was characterized by Fourier-transform infrared spectra (FTIR) and single-crystal X-ray diffraction analysis. DMB-PWA could effectively catalyze oxidative degradation of chitosan with H₂O₂ in the heterogeneous phase. The optimum degradation conditions were determined by orthogonal tests as follows: amount of chitosan 1.00 g, 30% (wt %); H₂O₂, 3.0 mL; dosage of catalyst, 0.06 g; reaction temperature, 85 °C; and reaction time, 30 min. The water-soluble chitosan with a viscosity-average molecular weight (M_v) of 4900 was obtained under the optimum degradation conditions and was characterized by FTIR, ultraviolet-visible diffuse reflection spectra (UV-vis DRS), and X-ray powder diffraction analysis.     

SYNERGISTIC ANTITUMOUR ACTIVITY OF VITAMINS C AND K3AGAINST HUMAN PROSTATE CARCINOMA CELL LINES

Vitamins C, K₃(VC, VK₃) and a VC/VK₃combination with a VC:VK₃ratio of 100:1 were assayed for their antitumour activity against two human prostatic carcinoma cell lines. Co-administration of the vitamins enhanced the antitumour activity 5- to 20-fold even with a 1 h exposure time. While exogenous catalase destroyed the antitumour activity, hydrogen peroxide-induced lipid peroxidation was negligible. Analysis of cellular ATP and thiol levels as well as DNA and protein synthesis revealed: a transient increase in ATP production, a decrease in DNA synthesis, an increase in protein synthesis and a decrease in thiol levels. These results suggested that the increased cytotoxicity of the vitamin combination was due to redox cycling and increased oxidative stress.     

温带针阔混交林土壤碳氮气体通量的主控因子与耦合关系

中高纬度森林地区由于气候条件变化剧烈,土壤温室气体排放量的估算存在很大的不确定性,并且不同碳氮气体通量的主控因子与耦合关系尚不明确。以长白山温带针阔混交林为研究对象,采用静态箱-气相色谱法连续4a(2005—2009年)测定土壤二氧化碳(CO2)、甲烷(CH4)和氧化亚氮(N2O)净交换通量以及温度、水分等相关环境因子。研究结果表明:温带针阔混交林土壤整体上表现为CO2和N2O的排放源和CH4的吸收汇。土壤CH4、CO2和N2O通量的年均值分别为-1.3 kg CH4hm-2a-1、15102.2 kg CO2hm-2a-1和6.13 kg N2O hm-2a-1。土壤CO2通量呈现明显的季节性规律,主要受土壤温度的影响,水分次之;土壤CH4通量的季节变化不明显,与土壤水分显著正相关;土壤N2O通量季节变化与土壤CO2通量相似,与土壤水分、温度显著正相关。土壤CO2通量和CH4通量不存在任何类型的耦合关系,与N2O通量也不存在耦合关系;土壤CH4和N2O通量之间表现为消长型耦合关系。这项研究显示温带针阔混交林土壤碳氮气体通量主要受环境因子驱动,不同气体通量产生与消耗之间存在复杂的耦合关系,下一步研究需要深入探讨环境变化对其耦合关系的影响以及内在的生物驱动机制。     

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.     

共享社会经济路径下中国2020—2100年碳排放预测研究

碳排放和减碳经济代价研究日益受到学术界和决策者的关注,中国政府做出的关于争取在2060年前实现碳中和的表态引起了国际社会的热议。在此背景下,开展中国未来长时间序列碳排放的情景预测具有切实意义。基于可拓展的随机性环境影响评估模型（STIRPAT）评估了人口、经济和受教育程度对碳排放的影响,对比历史数据并验证了碳排放预测模型的准确性,结合共享社会经济路径（SSPs）情景的设定和模型参数,预测了5种情景下中国2020年至2100年的碳排放轨迹及经济代价。结果表明：（1）考虑碳排放达峰目标的实现,SSP3情景是中国未来发展的最佳情景,在此情景下,中国有望提前三年实现碳排放达峰目标;（2） SSP3情景可使中国年度总碳排放量和人均碳排放量处于相对其他四种情景的最低值,但需要付出累积GDP下降5.49%至8.80%的代价;（3）为完成在2060年前实现碳中和的承诺,中国政府在未来的40年需面对409.36-467.42 Gt的碳中和量;（4）2020年中国的碳排放强度将会较2005年水平下降40.52%至41.39%,2030年碳排放强度将会较2005年水平下降59.64%至60.75%。5种情境中,SSP5情景是降低碳排放强度的最佳情景,可最大程度地超额实现碳排放强度目标。未来,受经济发展、人口增长等重要因素影响,中国政府减碳压力将进一步加大。后疫情时代,考虑到能源供应的减少和高科技产业的发展,碳排放社会成本的上升将为中国创造一个使能源系统脱碳的机遇。中国应在"十四五"期间继续提升能源利用效率、升级产业结构、提倡低碳消费、实施隐含碳战略,以尽快实现碳减排目标。     

温度与CO2浓度升高对集胞藻PCC 6803修复UV损伤的关键基因转录量的影响

通过Taqman探针绝对定量法研究了集胞藻PCC 6803在5种不同的环境条件下:(1)25℃+400μmol/mol CO₂,(2)29℃+400μmol/mol CO₂,(3)25℃+800μmol/mol CO₂,(4)29℃+800μmol/mol CO₂,(5)25℃+1200μmol/mol CO₂,其phrA/psbA1/psbA2/psbA3等UV修复基因和16S rRNA基因的转录本拷贝数的变化情况。结果表明:温度与CO₂浓度的升高可以导致集胞藻PCC 6803的psbA2/psbA3基因和16S rRNA转录本拷贝数的大幅减少,说明温室效应将有可能导致蓝藻的UV损伤修复能力与核糖体合成能力的下降;温度升高和CO₂浓度升高对psbA2/psbA3基因和16S rRNA转录本拷贝数的联合作用表现为互相抵消,说明温度升高与CO₂浓度升高的联合作用的机制较复杂,值得深入研究。     

Sawdust pellets from coniferous species as adsorbents for NO2 removal

Carbonaceous adsorbents based on sawdust pellets from coniferous tree species were obtained by carbonisation at different temperatures and different periods of time. The effect of NO₂ adsorption in dry and wet condition on the sorption ability of the chars obtained was tested. The results have shown that NO₂ sorption properties of chars depend on the conditions of pyrolysis and the conditions of adsorption. The best NO₂ sorption capacity of 18.3 and 43.1 mg/g in dry and wet conditions, respectively, was noted for the char sample pyrolysed at 800 °C for 60 min. The FTIR spectra of the exhausted samples reveal a great increase in the intensity of the band at 1380 cm⁻¹ assigned to the vibrations of –NO₂, –ONO₂ or , while in the DTG curves a new peak appears in the range 200–400 °C assigned to the release of nitrogen compounds of low stability in high temperatures.     

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。     

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.     

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.