Cu2O纳米颗粒对小麦根系形态及遗传毒性的影响

为了阐明Cu₂O纳米颗粒(NPs)暴露对植物根系的毒性效应,本研究以小麦品种‘周麦18’为材料,采用水培试验方法,研究了10、50、100和200 mg·L^-1浓度的Cu₂O-NPs对小麦幼苗生长、根系活性、形态结构及细胞遗传学毒性的影响。结果表明: 不同浓度的Cu₂O-NPs降低了小麦幼苗的根芽长度、鲜重、根活性和根冠比,增加了初生根的数量;随着Cu₂O-NPs浓度的升高,幼苗根伸长区缩短、根系变硬变脆、根径增加、根冠变大;100 mg·L^-1浓度的Cu₂O-NPs处理下,小麦根尖有丝分裂指数显著降低,根尖细胞形状不规则化、质壁分离、细胞出现空泡化、细胞核核膜模糊、核内染色体异常。在水培条件下,Cu₂O-NPs对小麦幼苗具有一定的遗传学毒性效应,从而影响小麦幼苗的生长发育和根系形态结构。     

Copper(II) coordination polymers derived from triethanolamine and pyromellitic acid for bioinspired mild peroxidative oxidation of cyclohexane

The new inorganic 1D coordination polymer [Cu₂(H₃tea)₂(μ₄-pma)]_n has been prepared, via self-assembly in aqueous medium, from copper(II) nitrate, triethanolamine (H₃tea), pyromellitic acid (H₄pma) and lithium hydroxide, and characterized by IR spectroscopy, elemental and single-crystal X-ray diffraction analyses. This compound and the related 2D polymer [Cu₂(μ-H₂tea)₂{μ₃-Na₂(H₂O)₄}(μ₆-pma)]_n · 10nH₂O are shown to mimic the alkane partial oxidation activity of the multicopper particulate methane monooxygenase, acting as catalysts precursors for the peroxidative oxidation of cyclohexane into cyclohexanol and cyclohexanone, by hydrogen peroxide (as green oxidant) and at room temperature in acidic MeCN/H₂O medium. An overall yield (based on cyclohexane) of 29% has been achieved.     

Tetrakis-[1-methylimidazoline-2(3H)-thione]-μ2-[1-methylimidazoline- 2(3H)-thione]-Di-Copper(I) sulphate trihydrate: Preparation, thermal analysis and crystal structure

1-emthylimidazoline-2(3H)-thione (mimtH) reacts with copper(II) sulphate pentahydrate in aqueous acetone to produce the dinuclear complex, Cu₂(mimtH)₅SO₄ · 3H₂O; the formula has been established by a combination of chemical and thermal analysis. The monoclinic crystals, (space group P_c, Z = 2), contain dinuclear cations, sulphate ions and water molecules. The dinuclear cation, Cu₂(mimtH)₅²⁺, consists of two trigonal copper(I) atoms, four terminal, monodentate, S-donating mimtH molecules and one S-bridging (μ₂) mimtH molecule. Some average dimensions are:Cu---S, 2.258 Å and S---Cu---S, 120.0°; the Cu---S---Cu bridging angle is 94.8° and the Cu---Cu separation distance is 3.308 Å.     

Metabolism of nitric oxide and nitrous oxide during nitrification and denitrification in soil at different incubation conditions

Abstract NO production and consumption rates as well as N₂O accumulation rates were measured in a loamy cambisol which was incubated under different conditions (i.e. soil moisture content, addition of nitrogen fertilizer and/or glucose, aerobic or anaerobic gas phase). Inhibition of nitrification with acetylene allowed us to distinguish between nitrification and denitrification as sources of NO and N₂O. Under aerobic conditions untreated soil showed very low release of NO and N₂O but high consumption of NO. Fertilization with NH₄⁺ or urea stimulated both NO and N₂O production by nitrification. Addition of glucose at high soil moisture contents led to increased N₂ and N₂O production by denitrification, but not to increased NO production rates. Anaerobic conditions, however, stimulated both NO and N₂O production by denitrification. The production of NO and N₂O was further stimulated at low moisture contents and after addition of glucose or NO₃⁻. Anaerobic consumption of NO by denitrification followed Michaelis-Menten kinetics and was stimulated by addition of glucose and NO₃⁻. Aerobic consumption of NO followed first-order kinetics up to mixing ratios of at least 14 ppmv NO, was inhibited by autoclaving but not by acetylene, and decreased with increasing soil moisture content. The high NO-consumption activity and the effects of soil moisture on the apparent rates of anaerobic and aerobic production and consumption of NO suggest that diffusional constraints have an important influence on the release of NO, and may be a reason for the different behaviour of NO release vs N₂O release.     

Design and characterization of antitumor drug paclitaxel-loaded chitosan nanoparticles by W/O emulsions

Chitosan nanoparticles and paclitaxel loaded chitosan nanoparticles were prepared by emulsification-crosslinking method in a W/O emulsion system, using glutaraldehyde as crosslinking agent. The mean diameter of chitosan nanoparticles decreased with increase of pH value of the reaction system from 4.5 to 6.5, and increased when the pH exceeded 6.5. Ultraviolet spectrum analysis showed that the largest loading efficiency and encapsulation efficiency could be 8.55% and 94.01%, respectively. In vitro drug release profile was also determined by ultraviolet spectrometry. MTT assays revealed that the blank chitosan nanoparticles had almost none toxicity, and cell culture was carried out accordingly.     

Metabolism of nitric oxide and nitrous oxide during nitrification and denitrification in soil at different incubation conditions

Abstract NO production and consumption rates as well as N₂O accumulation rates were measured in a loamy cambisol which was incubated under different conditions (i.e. soil moisture content, addition of nitrogen fertilizer and/or glucose, aerobic or anaerobic gas phase). Inhibition of nitrification with acetylene allowed us to distinguish between nitrification and denitrification as sources of NO and N₂O. Under aerobic conditions untreated soil showed very low release of NO and N₂O but high consumption of NO. Fertilization with NH₄⁺ or urea stimulated both NO and N₂O production by nitrification. Addition of glucose at high soil moisture contents led to increased N₂ and N₂O production by denitrification, but not to increased NO production rates. Anaerobic conditions, however, stimulated both NO and N₂O production by denitrification. The production of NO and N₂O was further stimulated at low moisture contents and after addition of glucose or NO₃⁻. Anaerobic consumption of NO by denitrification followed Michaelis-Menten kinetics and was stimulated by addition of glucose and NO₃⁻. Aerobic consumption of NO followed first-order kinetics up to mixing ratios of at least 14 ppmv NO, was inhibited by autoclaving but not by acetylene, and decreased with increasing soil moisture content. The high NO-consumption activity and the effects of soil moisture on the apparent rates of anaerobic and aerobic production and consumption of NO suggest that diffusional constraints have an important influence on the release of NO, and may be a reason for the different behaviour of NO release vs N₂O release.     

A bio-inspired support of gold nanoparticles-chitosan nanocomposites gel for immobilization and electrochemical study of K562 leukemia cells

A novel nanocomposites gel was prepared by neutralizing a designer nanocomposites solution of chitosan encapsulated gold nanoparticles formed by reducing in situ tetrachloroauric acid in chitosan. The bio-inspired gel was designed for immobilization and electrochemical study of cells and monitoring adhesion, proliferation, and apoptosis of cells on electrodes. Using K562 leukemia cells as a model, an impedance cell sensor was constructed. The methods for preparation of the gel and immobilization of cells were simple and "green". The nanocomposites gel showed improved immobilization capacity for cells and good biocompatibility for preserving the activity of immobilized living cells. The living cells immobilized on glassy carbon electrode exhibited an irreversible voltammetric response and increased the electron-transfer resistance with a good correlation to the logarithmic value of concentration ranging from 1.34 x 10(4) to 1.34 x 10(8) cells mL-1 with a limit of detection of 8.71 x 10(2) cells mL-1 at 10sigma. This work implied that the nanocomposites gel based on biopolymer and nanoparticles possessed potential applications for biosensing and provided a new avenue for electrochemical investigation of cell adhesion, proliferation, and apoptosis.     

X-ray crystal structure of Cu2(medpco-2H)Cl2, (medpco = N,N′-bis(2-N,N-dimethylaminoethyl)pyridine-2,6-dicarboxamide 1-oxide. Copper(II) complexes of a deprotonated binucleating pyridine N-oxide ligand

The X-ray structure is reported for the complex Cu₂(medpco-2H)Cl₂, (medpco = N,N′-bis-N,N-dimethylaminoethyl)pyridine-2,6-dicarboxamide 1-oxide. The complex is triclinic, , a=8.313(4), B=11.403(5), C=11.611(3) Å, =91.66(3), β=108.99(4), γ=109.60(3)° and Z=2. The deprotonated ligand (medpco-2H)²⁻ acts as a binulceating ligand, producing an N-oxide-bridged complex. Each copper in Cu₂(medpco-2H)Cl₂ is five-coordinate, being coordinated by a bridging N-oxide oxygen, a deprotonated amide nitrogen, a tertiary amine nitrogen and two bridging chlorides. The complex does not exhibit significant magnetic interaction, and this may be the result of distortion of the bridging geometry from planarity. A range of other, apparently N-oxide-bridged, complexes of the type Cu₂(medpco-2H)X₂ is reported. The complex Cu₂(medpco-2H)Br₂·H₂O is strongly antiferromagnetic, with magnetic data closely fitting the expected binuclear structure.     

壳聚糖-有机累托石/海藻酸钠复合纳米粒的制备

目的:以BSA作为模型药物,制备壳聚糖季铵盐-OREC复合物纳米微粒,建立一种安全有效的药物控释传递系统。方法:超声条件下,制备不同质量比的具有壳聚糖硅酸盐插层结构的复合物纳米微粒,观察其形态学特征、进行红外光谱分析。同时,测定OREC对BSA包封率和载药量的影响。结果:成功制备了不同质量比的OREC-HTCC纳米粒子。电镜结果显示纳米粒呈圆球形,均匀,平均粒径约为30nm。红外图谱分析证实,HTCC插入了OREC插层中,BSA成功地包裹入HTCC-ALG/OREC混合材料制备的纳米微粒。加入OREC后,纳米粒子的包封率及载药量均明显提高,但随着加入量的增加,包封率及载药量逐渐减少。结论:OREC-HTCC纳米粒子是良好的蛋白药物载体,具有粒径小、包封率高、缓释效果好等优点,为CS-OREC作为潜在的药物给药系统的进一步应用提供科学依据。     

One-dimensional copper phosphonates containing μ-halide, μ-pyridyl N-oxide and phosphonate bridging ligands

This paper reports the syntheses and characterization of four copper phosphonates with chain structures based on (2-pyridyl-N-oxide)phosphonate, namely, [Cu₂X₂(C₅H₄NOPO₃)₂][Cu(H₂O)₆] · 2H₂O [X = Cl (1), Br (2)] and CuX(C₅H₄NOPO₃H) · H₂O [X = Cl (3), Br (4)]. Compounds 1 and 2 are isostructural and show a chain structure where Cu(1) and Cu(2) are triply bridged by halide, oxygen donor of the pyridyl N-oxide and O–P–O group. The [Cu(H₂O)₆]²⁺ serves as a charge-balancing cation and locate between the chains together with the water molecules. Compounds 3 and 4 are also isostructural. In these cases, one of the three phosphonate oxygen atoms is protonated, thus leading to a neutral chain structure which is very similar to the anionic chains in compounds 1 and 2. Magnetic studies of compounds 1–4 reveal that antiferromagnetic interactions are mediated between the copper ions.     

Oxidative inactivation of paraoxonase1, an antioxidant protein and its effect on antioxidant action

Paraoxonase1 (PON1), one of antioxidant proteins to protect low density lipoprotein (LDL) from the oxidation, is known to lose its activity in the oxidative environment. Here, we attempted to elucidate the possible mechanisms for the oxidative inactivation of PON1, and to examine the capability of hydroxyl radicals-inactivated PON1 to prevent against LDL oxidation. Of various oxidative systems, the ascorbate/Cu₂₊ system was the most potent in inactivating the purified PON1 (PON1) as well as HDL-bound PON1 (HDL-PON1). In contrast to a limited inactivation by Fe₂₊ (2.0 μM), the inclusion of Cu₂₊ (0.1-1.0 μM) remarkably enhanced the inactivation of PON1 in the presence of ascorbate (0.5 mM). A similar result was also obtained with the inactivation of HDL-PON1. The inactivation of PON1 by ascorbate/Cu₂₊ was pevented by catalase, but not general hydroxyl radical scavengers, supporting Cu₂₊-catalyzed oxidative inactivation. In addition, Cu₂₊ alone inactivated PON1, either soluble or HDL-bound, by different mechanisms, concentration-dependent. Separately, there was a reverse relationship between the inactivation of PON1 and its preventive action against LDL oxidation during Cu₂₊-induced oxidation of LDL. Noteworthy, ascorbate/Cu₂₊-inactivated PON1, which was charaterized by the partial loss of histidine residues, expressed a lower protection against Cu₂₊-induced LDL oxidation, compared to native PON1. Based on these results, it is proposed that metal-catalyzed oxidation may be a primary factor to cause the decrease of HDL-associated PON1 activity under oxidative stress, and radicals-induced inactivation of PON1 may lead to the decrease in its antioxidant action against LDL oxidation.     

安徽省冬小麦施肥现状与肥料利用效率

冬小麦是安徽省重要的粮食作物。合理施肥是冬小麦获得高产的重要措施,明确当前安徽省冬小麦施肥现状和存在的问题对于指导冬小麦科学施肥具有重要意义。本研究以安徽省冬小麦为对象,于2018年对全省冬小麦主产区1591户农户进行调查,调查内容包括肥料品种、肥料用量、施肥方式、种植面积和产量水平。根据调查结果统计分析安徽省冬小麦种植过程中的施肥现状及存在问题,并以全省冬小麦平均产量和平均施肥量为基准,采用Cate-Nelson方法(十字交叉法)评估安徽省冬小麦产量与氮、磷和钾肥施用的关系,以探索安徽省冬小麦进一步增产增效的主要施肥途径。结果表明: 安徽省冬小麦平均产量为5185 kg·hm^-2,氮、磷和钾肥平均施用量分别为206、80和78 kg·hm^-2。其中旱茬麦氮、磷和钾肥平均施用水平比稻茬麦分别高14、16和3 kg·hm^-2。总体上,安徽省冬小麦种植中化肥平均用量趋于合理化,但是在施肥方式、养分运筹和肥料品种上还存在不合理现象。Cate-Nelson方法结果表明,全省冬小麦氮、磷、钾肥施用量中,仅有23.8%、21.2%和25.7%低于全省平均水平却获得较高的产量,此时氮、磷、钾肥偏生产力最高;有26.3%、19.3%和22.5%的施用量低于全省平均水平但没有实现高产;有26.2%、29.6%和25.0%的施用量虽然获得了高产,但施用量较高,氮磷钾肥偏生产力较低。这说明安徽省冬小麦增产增效还有很大的空间。全省冬小麦基肥和追肥机械化比例分别为62.7%和10.0%。虽然氮肥普遍实现了分次施用,但氮肥作基肥的比例仍然占到全生育期氮肥总量的69.0%,应适当降低。此外,在肥料品种选择上存在偏施化肥、不重视有机肥等问题。     

Soils,a sink for N2O? A review

Soils are the main sources of the greenhouse gas nitrous oxide (N₂O). The N₂O emission at the soil surface is the result of production and consumption processes. So far, research has concentrated on net N₂O production. However, in the literature, there are numerous reports of net negative fluxes of N₂O, (i.e. fluxes from the atmosphere to the soil). Such fluxes are frequent and substantial and cannot simply be dismissed as experimental noise.
Net N₂O consumption has been measured under various conditions from the tropics to temperate areas, in natural and agricultural systems. Low mineral N and large moisture contents have sometimes been found to favour N₂O consumption. This fits in with denitrification as the responsible process, reducing N₂O to N₂. However, it has also been reported that nitrifiers consume N₂O in nitrifier denitrification. A contribution of various processes could explain the wide range of conditions found to allow N₂O consumption, ranging from low to high temperatures, wet to dry soils, and fertilized to unfertilized plots. Generally, conditions interfering with N₂O diffusion in the soil seem to enhance N₂O consumption. However, the factors regulating N₂O consumption are not yet well understood and merit further study.
Frequent literature reports of net N₂O consumption suggest that a soil sink could help account for the current imbalance in estimated global budgets of N₂O. Therefore, a systematic investigation into N₂O consumption is necessary. This should concentrate on the organisms, reactions, and environmental factors involved.     

不同灌溉量对华北平原菜地N2O排放及其来源的影响

以华北平原菜地为研究对象,通过控制灌溉量设置不同的土壤水分对照,利用稳定同位素¹⁵N自然丰度法,结合传统的乙炔抑制试验,对不同土壤水分条件下的N₂O排放、N₂O同位素特征值以及同位素异位体位嗜值(SP值)变化规律进行分析,以阐明不同水分条件下N₂O的排放规律及其来源.结果表明:水分条件显著影响N₂O排放,相比于50%土壤孔隙含水率(WFPS),70%WFPS的水分条件下N₂O的排放较高.N₂O的排放集中在施肥前期,在施肥中后期迅速减弱.50%WFPS条件下,N₂O的排放最初以硝化作用为主,占比约为90%,随后硝化作用迅速下降,反硝化变成主导作用,施肥7 d后即达到80%以上;而70%WFPS条件下初期则以反硝化为主,占比约为70%,随后下降至40%左右,施肥10 d后逐渐升高至80%.整体上,N₂O的排放主要以反硝化作用为主,不同水分处理对土壤硝化、反硝化作用的影响主要体现在施肥前期,后期均以反硝化为主.综上,建议华北地区的菜地生产应适当降低灌溉量,以减少N₂O排放.     

不同灌溉量对华北平原菜地N2O排放及其来源的影响

以华北平原菜地为研究对象,通过控制灌溉量设置不同的土壤水分对照,利用稳定同位素¹⁵N自然丰度法,结合传统的乙炔抑制试验,对不同土壤水分条件下的N₂O排放、N₂O同位素特征值以及同位素异位体位嗜值(SP值)变化规律进行分析,以阐明不同水分条件下N₂O的排放规律及其来源.结果表明:水分条件显著影响N₂O排放,相比于50%土壤孔隙含水率(WFPS),70%WFPS的水分条件下N₂O的排放较高.N₂O的排放集中在施肥前期,在施肥中后期迅速减弱.50%WFPS条件下,N₂O的排放最初以硝化作用为主,占比约为90%,随后硝化作用迅速下降,反硝化变成主导作用,施肥7 d后即达到80%以上;而70%WFPS条件下初期则以反硝化为主,占比约为70%,随后下降至40%左右,施肥10 d后逐渐升高至80%.整体上,N₂O的排放主要以反硝化作用为主,不同水分处理对土壤硝化、反硝化作用的影响主要体现在施肥前期,后期均以反硝化为主.综上,建议华北地区的菜地生产应适当降低灌溉量,以减少N₂O排放.     

短期落干对水稻土反硝化微生物丰度和N2O释放的影响

为了探明水稻土落干过程对温室气体排放和反硝化微生物的影响,通过模拟水稻土淹水落干过程,系统监测了落干开始后24 h内N2O的释放和氧化还原电位(Eh)的变化,并利用实时PCR(qPCR)方法测定了反硝化功能基因narG和nosZ的丰度.结果表明：落干开始后4 h N₂O释放量就明显增加,在24 h时N₂O的释放量比淹水对照增加了5倍多;narG和nosZ基因丰度也随着落干过程的推移而快速增加;而且N₂O排放通量与narG基因呈极显著相关(P<0.01).表明水稻土短期淹水落干过程中,含narG基因反硝化微生物是驱动N₂O释放的主要功能微生物.     

短期落干对水稻土反硝化微生物丰度和N2O释放的影响

为了探明水稻土落干过程对温室气体排放和反硝化微生物的影响,通过模拟水稻土淹水落干过程,系统监测了落干开始后24 h内N2O的释放和氧化还原电位(Eh)的变化,并利用实时PCR(qPCR)方法测定了反硝化功能基因narG和nosZ的丰度.结果表明：落干开始后4 h N₂O释放量就明显增加,在24 h时N₂O的释放量比淹水对照增加了5倍多;narG和nosZ基因丰度也随着落干过程的推移而快速增加;而且N₂O排放通量与narG基因呈极显著相关(P<0.01).表明水稻土短期淹水落干过程中,含narG基因反硝化微生物是驱动N₂O释放的主要功能微生物.     

Preparation and antibacterial activity of chitosan nanoparticles

Chitosan nanoparticles, such as those prepared in this study, may exhibit potential antibacterial activity as their unique character. The purpose of this study was to evaluate the in vitro antibacterial activity of chitosan nanoparticles and copper-loaded nanoparticles against various microorganisms. Chitosan nanoparticles were prepared based on the ionic gelation of chitosan with tripolyphosphate anions. Copper ions were adsorbed onto the chitosan nanoparticles mainly by ion-exchange resins and surface chelation to form copper-loaded nanoparticles. The physicochemical properties of the nanoparticles were determined by size and zeta potential analysis, atomic force microscopy (AFM), FTIR analysis, and XRD pattern. The antibacterial activity of chitosan nanoparticles and copper-loaded nanoparticles against E. coli, S. choleraesuis, S. typhimurium, and S. aureus was evaluated by calculation of minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC). Results show that chitosan nanoparticles and copper-loaded nanoparticles could inhibit the growth of various bacteria tested. Their MIC values were less than 0.25 microg/mL, and the MBC values of nanoparticles reached 1 microg/mL. AFM revealed that the exposure of S. choleraesuis to the chitosan nanoparticles led to the disruption of cell membranes and the leakage of cytoplasm.     

Photocatalytic Reduction of CO2 into Methanol over Ag/TiO2 Nanocomposites Enhanced by Surface Plasmon Resonance

Ag-loaded TiO₂ (Ag/TiO₂) nanocomposites were prepared by microwave-assisted chemical reduction method using tetrabutyl titanate as the Ti source. The prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N₂ adsorption–desorption isotherms, UV–vis absorption spectrum, X-ray photoelectron spectrum, photoluminescence spectrum, and Raman scattering spectrum, respectively. Results revealed that Ag nanoparticles (NPs) were successfully deposited on TiO₂ by reduction of Ag⁺, and the visible light absorption and Raman scattering of TiO₂ were enhanced by Ag NPs based on its surface plasmon resonance effect. Besides, Ag NPs could also effectively restrain the recombination of photogenerated electrons and holes with a longer luminescence life time. In addition, photocatalytic reduction of CO₂ with H₂O on the composites was conducted to obtain methanol. Experimental results indicated that Ag-loaded TiO₂ had better photocatalytic activity than pure TiO₂ due to the synergistic effect between UV light excitation and surface plasmon resonance enhancement, and 2.5 % Ag/TiO₂ exhibited the best activity; the corresponding energy efficiency was about 0.5 % and methanol yield was 405.2 μmol/g-cat, which was 9.4 times higher than that of pure TiO₂. Additionally, an excitation enhancement synergistic mechanism was proposed to explain the experimental results of photocatalytic reduction of CO₂ under different reaction conditions.     

Denitrification in river sediments: relationship between process rate and properties of water and sediment

1. A survey was made of denitrification and nitrous oxide (N₂O) production in river sediments at fifty sites in north‐east England during one season in order to investigate the relationship between rates and environmental factors likely to influence these processes. The sites were chosen to represent a wide range of physical and chemical conditions. Denitrification rate and N₂O production were measured within 5 h of sampling using the slurry acetylene blockage technique.
2. Denitrification rate ranged from less than 0.005–260 nmol N g^–1 DW h^–1, tending to increase in a downstream direction. N₂O production ranged from negative values (net consumption) to 13 nmol N₂O‐N g^–1 DW h^–1 and accounted for 0–115% of the N gases produced.
3. Denitrification rate and N₂O concentration in the sediment were correlated positively with nitrate concentration in the water column, water content of the sediment and percentage of fine (< 100 μm) particles in the sediment.
4. The variation in denitrification rate was satisfactorily explained (64% total variance) by a model employing measurements of water nitrate and water content of sediments. No simple or multiple relationship was found for N₂O production.