Advances in Studies on Interaction between Selenium and Heavy Metal Cadmium

Selenium is an essential functional element of the human body,and the issue of selenium accompanying heavy metals is receiving much concern.This paper expounded the form of existence of selenium and cadmium in soil and influencing factors of their bioavailability,and further elaborated the interaction between selenium and cadmium.On the basis,it provided references for further studies on the interaction between selenium and cadmium,and provided basis for establishing selenium-enriched barrier technology for crops.

The Effect of Selenium and Lycopene on Oxidative Stress in Bone Tissue in Rats Exposed to Cadmium

This study examined the effect of selenium (Se) or lycopene (Lyc) and their combination on oxidative stress in bone following cadmium (Cd) exposure in vivo. Cd exposure enhanced accumulation of Cd in femur with subsequent increase in LPO and PC and decreased antioxidative enzyme activities in rat femur, along with significant decreases in body and femur bone weights. Subcutaneous (s.c.) injection of Se or Lyc reduced Cd accumulation in bone and increased body and femur weights,when given individually or concomitantly. Antioxidant enzyme activities maintained and/or increased following Se and Lyc supplementation when given individually or concomitantly. However, lycopene dose of 10 mg/kg of body weight alone or selenium alone provided better protection to bone tissues of rats against oxidative stress compared to treatment with their combination. Selenium and lycopene could be used as a dietary supplement to protect against bone oxidative stress in areas exposed to Cd pollution.

Inhibitory Effects of Selenium on Telomerase Activity and hTERT Expression in Cadmium-transformed 16HBE Cells

To investigate the effects of sodium selenite on telomerase activity and expression of hTERT mRNA in cadmium-transformed 16HBE cells. Methods Telomerase activity and expression of genes were measured after cultured cadmium-transformed 16HBE cells were exposed to sodium selenite at different doses （0.625, 1.25, 2.50, 5.00 pmol/L） for 24 hours. Results Selenium decreased telomerase activity in cadmium-transformed 16HBE cells. There existed an obvious dose-effect relationship between the selenium concentration and these changes. The expression of hTERT and c-myc mRNA also decreased but the expression of madl mRNA increased after exposure to selenium for 24 hours. No difference was found in expression of hTRF1 and hTRF2 mRNA after incubated with sodium selenite for 24 hours, compared with control group. Conclusion Selenium inhibits telomerase activity by decreasing hTERT and c-myc mRNA expression and increasing madl mRNA expression in cadmium-transformed 16HBE cells and selenium concentration is significantly correlated with these changes.

Synthesis and Crystal Structure of a Two-dimensional Cadmium Complex Based on Terephthalate and 1-Methyl-2,2'-bibenzimidazole

The title complex, [Cd（MeHbibzim）（1,4-bdc）]n （1, MelToibzim = 1-methyl-2,2＇- bibenzimidazole, 1,4-bdc = terephthalate）, was synthesized with hydrothermal reactions. The compound crystallizes in monoclinic, space group C2/c with a = 9.822（4）, b = 18.510（7）, c = 22.372（9） A, β = 98.359（6）°, C23H16CdN4O4, Mr = 524.81, V= 4024（3） A3, Z = 8, Dc. = 1.733 g/cm3, μ（MoKa） = 1.126 mm-1, F（000） = 2096, the final R = 0.0597 and wR = 0.1374 for 3906 observed reflections （1 〉 2σ（I））. X-ray diffraction analysis reveals that the Cd atom is coordinated by two nitrogen atoms from the chelating MeHbibzim and three carboxyl oxygen atoms from three terephthalate ligands, thus forming a distorted square pyramidal coordination sphere, [CdN2O3]. Every two Cd atoms are linked together via two carboxyl groups into a dinuclear unit with Cd...Cd separation of 3.806（4） A. The dinuclear building units are linked by terephthalate ligands into two-dimensional layers, which are further aggregated into a 3D framework via hydrogen bonding interactions.

The curve of ion exchange ratio(%)-pH of the interaction between suspended particles with Cd(Ⅱ) in the Yellow River

The curve of ion exchange ratio(%) pH of the interaction between suspended particles with Cd(II) in the Yellow River was studied. The effects of lysine on this curve have been also investigated. The results showed that (1) Cadmium in Cd(OH) + form in the suspended particles exchanges with the cations. The exchange ratio of Cd 2+ is nearly at its greatest value in the range of pH (8.0—8.5) in natural aquatic system; (2) Ion exchange ratio decreases as the concentration of Cd 2+ raises from 8.9×10 -6 mol/L to 2×8.9×10 -6 mol/L; (3) At the lysine concentration of 6 8×10 -6 mol/L, it can promote the ion exchange ratio; (4) Adsorption of the suspended particles to cadmium is weaker in seawater and Jin Sha River than in the Yellow River.

Phytoextraction of Metal Contaminants by Typha Angustifolia: Interaction of Lead and Cadmium in Soil-Water Microcosms

A greenhouse study was conducted on phytoextraction and accumulation of lead (Pb) and cadmium (Cd) from contaminated soil – water microcosms by the narrow-leaved cattail, Typha angustifolia. The plants were grown in sandy loam soil containing 1,666 and 38.5 mg/L of Pb(NO3)2 and Cd(NO3)2 respectively. The trends of lead and cadmium by T. angustifolia for all soil – water microcosms suggested interaction effects as decreased soil lead concentrations and increased water cadmium concentrations over time. T. angustifolia expressed trends as increased biomass in all contaminated shoots and roots examined. Cadmium uptake in shoot and root biomass slightly decreased when lead was initially added to the soil but cadmium uptake in root biomass increased after 30 days. Data suggested an interaction between lead and cadmium and possible that lead uptake was inhibited when cadmium was present.

Interaction of Cd and citric acid, EDTA in red soil

Adsorption and desorption process of cadmium in red soil (Ferrisols) as well as the influence by media' s pH were investigated in detail with and without citric acid and EDTA. Experimental results clearly showed that Cd adsorption in red soil was affected significantly by the coexisted organic chemicals. In the presence of citric acid and EDTA, Cd adsorption in red soil increased with pH in acid media but decreased in high pH one. Further studies placed stress on the adsorbed Cd in red soil which was found to be existed mainly as exchangeable one at pH < 5.5, and desorption rate by 0.10 mol/L NaNO3 gave a peak-shaped curve due to the difference of specifically and nonspecifically adsorbed Cd with pH's change.

Synthesis and Structure of a Novel Macrocyclic Complex [Cd_2(phen)_4(phth)_2]·4H_2O

A novel complex [Cd2（phen）4（phth）2]·4H2O has been synthesized by the reaction of Hzphth（phthalic acid） and phen（1,10-phenanthroline） with Cd（Ⅱ） in ethanol-water solution. X-ray crystal structure analysis shows it crystallizes in triclinic, space group PI- with a = 10.619（3）, b = 12.560（4）, c = 12.651（4） A, a = 98.775（5）, β = 109.035（5）,γ = 113-576（5）°, C32H24CdN4O6, Mr= 672.95, V = 1381.7（7）A^3, Rint = 0.0358, Z = 2, Dc= 1.618 g/cm^3,μ = 0.845 mm^-1, -6 ≤h≤13, -15 ≤k ≤13, -15 ≤l≤14, F（000） = 680, S = 1.038, R = 0.0480 and wR = 0.0849 for 3992 observed reflections （1 〉 2σ（Ⅰ））. Phth bridges Cd（Ⅱ） to form a macrocyclic compound, and a 2D supramolecular motif is formed through hydrogen bonds and π-π interaction.

A One-dimensional Cd(Ⅱ)Coordination Polymer Constructed from 1,4-Benzene-dicarboxylic Acid and 3-(2,6-Di(pyrazin-2-yl)pyridin-4-yl)-1H-indole:Synthesis,Structure and Photoluminescence

A new coordination polymer {[Cd（C_（21）H_（14）N_6）（C_8H_4O_4）]·H_2O}_n（1） was synthesized by an elaborate design via the reaction of 3-（2,6-di（pyrazin-2-yl）pyridin-4-yl）-1H-indole（bppi）,1,4-benzene-dicarboxylic acid（H2bdc） and cadmium（Ⅱ） nitrate in CH_3OH/H_2O mixed solvents. Complex 1 crystallizes in orthorhombic,space group Ccca with a = 20.012（4）,b = 31.881（6）,c = 19.808（4） ？,V = 12638（4） ？~3,Z = 16,C_（29）H_（20）CdN_6O_5,M_r = 644.91,D_c = 1.356 g·cm^（-3）,μ = 0.735 mm^（-1）,F（000） = 5184,GOOF = 1.046,the final R = 0.0405 and wR = 0.1063 for 6870 observed reflections（I 〉 2σ（I））. The Cd（Ⅱ） centre is hepta-coordinated by three N and four O atoms from one bppi terminal ligand and two bdc2– ligands,respectively,displaying a capped trigonal prism geometry. Structure extension gives coordination polymeric chains,in which the bdc2– linkers connect Cd（Ⅱ） cations into a one-dimensional（1D） coordination polymer along the c axis,giving zigzag chains with the Cd···Cd separation of 11.178（1） ？. The adjacent bppi terminal ligands in the chains are anti-periplanar conformation. The three-dimensional（3D） structure is stabilized by π···π stacking and hydrogen-bonding interactions to form a supramolecular self-penetrating network with 1D channels. In 1,there are voids 2999.7 ？~3 with 23.7% of per unit cell volume. Thermal analysis indicates that the framework of 1 is stable until 651 K and the photoluminescence of 1 in the solid shows very weak fluorescence at 382 and 560 nm upon excitation at 310 nm.

Crystal Structure and Photoluminescence of a New Cadmium Complex with 6,7-Dicyanodipyridoquinoxalin

The reaction of CdCl2 with 6,7-dicyanodipyridoquinoxaline （DICNQ） by solvothermal reaction gives rise to a coordination polymer [CdCl2（DICNQ）]n 1. Single-crystal X-ray diffraction analysis reveals that the compound in space group Pbcn creates 1-D chloro-bridging chains. Crystal data for 1： a = 6.756（1）, b = 35.371（6）, c = 7.027（1）A , V = 1679.1（5） A^3, Z = 4.00, C16H6CdCl2N6, Mr = 465.57, Dc = 1.842 g/cm^3, μ = 1.630 mm-1, F（000） = 904, S = 1.005 and T = 293（2） K. The final R = 0.0376 and wR = 0.1029 for 1291 observed reflections with I 〉 2σ（I）, and R = 0.0499 and wR = 0.1125 for all data. The 1-D chloro-bridging chains are parallel-stacked in the a and b directions, and further stabilized through π-stacking interactions, hydrogen-bonding interactions and C≡N···π interactions to generate a 3-D structure. Compound 1 displays intense bluish-green photoluminescence from the intraligand charge-transfer of the DICNQ ligand and the Cl--to-DICNQ charge-transfer mechanism which is probed by the density of states （DOS） calculations.

Effects of Direction of Bridging of Thiocyanato on the Dimension of Coordination Polymers: Synthesis, Characterization and Single-crystal X-ray Structure Determination of [Cd(4,4'-dm-2,2'-bpy)(NCS)_2]_n and [Cd(4,4'-dmo-2,2'-bpy)(NCS)_2]_n Coordination Pol

Two new cadmium（II）-thiocyanato coordination polymers with 4,4＇-dimethyl-2,2＇-bipyridine（4,4＇-dm-2,2＇-bpy） and 4,4＇-dimethoxy-2,2＇-bipyridine（4,4＇-dmo-2,2＇-bpy） as chelating ligands were synthesized and characterized by elemental analysis, IR and 1H NMR spectroscopy and X-ray crystallography. Thermal properties were also studied as well. These complexes have formed as [Cd（4,4＇-dm-2,2＇-bpy）（NCS）2]n（1） and [Cd（4,4＇-dmo-2,2＇-bpy）（NCS）2]n（2）. The coordination numbers of CdII in 1 and 2 are six（Cd N4S2）. Direction of bridging of thiocyanato anions in 1 and 2 created one- and two-dimensional coordination polymers, respectively. The supramolecular features in these complexes were guided and controlled by weak directional intermolecular interactions.

Two Cd(Ⅱ) and Cu(Ⅱ) Complexes Based on 1-Butylbenzimidazole: Crystal Structures and Weak Interactions

1-Butylbenzimidazole L reacted with Cd（NO3）2·4H2O to afford complex [CdL（NO3）3H2O]·[HL] 1. The heptacoordinated Cd（Ⅱ） center adopts a distorted pentagongal bipyramidal geometry, and complex [CdL（NO3）3H2O]-entity and the protonated benzimidazium salt [HL]＋ are connected via N–H···O hydrogen bond to form a dimeric unit [CdL（NO3）3H2O]·[HL]. A 3-D supramolecular network of 1 is formed through N–H···O and O–H···O hydrogen bonds together with π-π stacking interactions. Reaction of L with CuCl2 afforded a mononuclear complex, [CuL2Cl2] 2, in which the tetracoordinated Cu（II） center adopts a distorted tetrahedral geometry. In contrast, 2-D supramolecular layers of 2 are formed by C–H···Cl hydrogen bonds. The fluorescent emission spectra of L, 1 and 2 are described.

STUDY OF SELENIUM CADMIUM RUBY IRON-SEALING GLASSES

Taking R2-RO-BiOSiO2 system glasses as base,cadmi-um sulfide(CdS) and selenium (Se) powders as colorants, the author has succeeded in producing ruby selenium-cadmium iron-sealing glass-es with suitable coefficient of thermal expansion and other relevant properties necessary for iron-seeling.

Cadmium adsorption in montmorillonite as affected by glyphosate

Behaviors of soil heavy metals are often affected by coexisting herbicides due to their physical and chemical interaction. Effect of glyphosate, an herbicide containing -PO 2- 3 and -COOH groups, on cadmium adsorption in montmorillonite was studied in detail. The results showed that the cadmium adsorption quantity in montmorillonite increased with increasing soil solution pH and cadmium concentration as usual, but decreased with glyphosate, which is due to the formation of a low affinity complex of Cd and glyphosate and decreasing solution pH induced by glyphosate addition. When the equilibrium solution pH was below 6.7, glyphosate has little effect on cadmium adsorption, but when the equilibrium solution pH was above 6.7, glyphosate significantly decreased cadmium adsorption quantity in montmorillonite. In addition, the adding order of Cd and glyphosate also influenced Cd adsorption quantity in montmorillonite.

Effects of Interaction Between Cadmium and Plumbum on Phytochelatins and Glutathione Production in Wheat （Triticum aestivum L.）

: Phytochelatins (PCs) may function as a potential biomarker for metal toxicity. However, less attention has been paid to the effects of metal interactions on the production of PCs and glutathione (GSH), the most prominent cellular thiol. In the present study, the effects of interactions between cadmium (Cd) and plumbum (Pb) on the production of PCs and GSH were monitored over a period of 14 d in wheat (Triticum aestivum L.) tissues. The results showed that combination of Cd and Pb led to synergistic growth inhibition in wheat. Exposure to Cd or Pb increased levels of PCs in a concentration-, tissue-, and time-dependent manner. Cadmium was more effective that Pb in increasing PCs production. Compared with the effects of Cd or Pb alone on the production of PCs, the combination of Cd and Pb acted synergistically, resulting in an enhanced production of PCs. Cadmium also stimulated GSH production in a concentration-, tissue-, and time-dependent manner. However, Pb had no obvious effects on GSH levels. The combination of Pb and Cd antagonized GSH production over the course of the growth period. The results of the present study suggest that metal interactions should be considered in the application of PCs and GSH as potential biomarkers for the evaluation of metal toxicity.

Nano-selenium controlled cadmium accumulation and improved photosynthesis in indica rice cultivated in lead and cadmium combined paddy soils

Selenium nanoparticles(Se NPs) are less toxic and more biocompatible than selenite or selenate. However, studies involving spraying with Se NPs for reducing accumulation of cadmium(Cd) and lead(Pb) in rice grains have been rarely reported as yet. Herein, indica rice seedlings cultivated in Cd + Pb-spiked paddy soils(denoted as positive control) were sprayed with Se NPs sols for four times from tillering to booting stage. Compared to positive control, 50–100 μmol/L Se NPs downregulated Cd transporters-related genes such as Os LCT 1, OsH MA 2 and Os CCX2 in leaves and OsLCT1, Os PCR1 and Os CCX2 genes in node I at filling stage. Meanwhile, Se-binding protein 1 was distinctly elevated, involving the repression of Cd and Pb transportation to rice grains. Se NPs also differentially improved RuBP carboxylase and chlorophylls especially some key genes and proteins involving photosynthetic system. Besides, 25–50 μmol/L Se NPs diminished reactive oxygen species overproduction from NADPH oxidases whereas boosted glutathione peroxidase, reducing protein carbonylation in rice seedlings. However, the antioxidant isozymes and oxidatively modified proteins were slightly rebounded at 100 μmol/L. Se contents were noticeably elevated and confirmed to exist as selenomethionine in the rice grains following all the treatments by Se NPs. Thus, the optimal dosage of Se NPs for foliar application is 50 μmol/L, which significantly decreased Cd accumulation, improved photosynthesis and Se enrichment whereas caused no distinct reduction of Pb in the grains. Thus, an appropriate dosage of Se NPs can be conducted to decrease Cd accumulation, improve photosynthesis, and organic Se contents in rice grains.

RESEARCH ON FACTORS AFFECTING THE COLOURATION OF RED GLASS-CERAMICS

In this pater, effect of alkali, zinc oxide and colorants such as cadmiun sulfide and selenium powder on the colouration of the red glass-ceramic materials in the CaO-Al2O3-SiO2 system has been studied. The relevant laws have been presented and analyzed.

中国稀散金属矿资源概况

中国稀散金属资源丰富,在全球占有重要的战略地位。对中国542处矿产地(包括759个矿床/点)的稀散金属资源调查数据分析表明,目前中国已查明稀散金属资源储量102.82万t,其中,镓矿44.65万t,锗矿1.39万t,铟矿2.52万t,铊矿2.96万t,镉矿47.12万t,硒矿2.56万t,碲矿1.53万t,铼矿893.00 t。中国稀散金属资源具有如下特征:①分布广泛,但主要集中在西南地区、中南地区和华北地区,云南、河南、广西、内蒙古、山西、贵州、广东等是稀散金属资源较丰富的省(区);②独立矿床极少,但资源储量占到全国稀散金属资源总量的6.64%;③矿床规模以中、小型为主,但大型矿床和超大型矿床资源储量占全国稀散金属资源总量的80%以上;④主要伴生在铅锌多金属矿、铝土矿和煤矿中,3类矿床中的稀散金属资源储量占全国稀散金属资源总量的80%左右;⑤总体综合利用率较低。中国镓、锗、铊资源的储备充足,但硒、碲、铼、铟、镉资源相对缺乏。

试论稀散金属矿产与新质生产力

稀散金属(锗、镓、铟、铊、铼、镉、硒、碲)并不被社会大众所熟悉,但在我国却属于优势矿产资源。稀散金属在传统产业中的用途比较局限,用量也不大,有的金属全世界一年也就用十几吨。但是,这8种金属个个“身怀绝技”,对战略性新兴产业和未来产业至关重要。比如,镓在液态金属、锗和铟在电子工业、镉在军工领域、铼在战机发动机、碲和硒在光电产业、硒和铊在生物医学领域都具有不可限量的发展潜力。战略性新兴产业和未来产业又是国际竞争的关键环节和焦点领域,需要新质生产力来支撑。加快形成与稀散金属密切相关的新质生产力,是实现高质量发展、构建新发展格局的重要路径,也是保障国家经济安全的客观需要。稀散金属也是我国矿产资源领域安全保障体系的重要组成部分。因此,加强对稀散金属矿产资源的勘查、开发与管理,理清稀散金属与新质生产力之间的内在逻辑,探索关键矿产找矿工作部署的战略构想,通过创新引领,加快新一轮找矿突破战略行动的实施步伐,加深社会各界对于稀散金属重要性的认知程度,鼓励全社会加大地质找矿投入的力度,对于保障能源资源安全、增强发展新动能具有重要的意义。

蔬菜根系土壤硒镉含量与理化性质关系研究

以贵州省观山湖区土壤-蔬菜协同样为试材,采用调查采样方法,研究了蔬菜硒镉、土壤硒镉含量及主要理化性质,进一步了解蔬菜硒镉富集情况,明确主要土壤理化指标与土壤硒镉含量的关系,以期为富硒土壤资源的综合利用提供参考依据。结果表明:在各级理化性质分级下,土壤(0~20 cm)全硒平均含量均高于富硒土壤标准(0.4 mg·kg^(-1));采集的46件蔬菜样品镉含量均未超过食品安全国家标准《食品中污染物限量》(GB2762-2022)限量值,超标率为0%,镉的安全性较高,硒含量均未检出。土壤理化性质对硒、镉的地球化学行为有重要影响,土壤有机质、pH、碱解氮与土壤硒含量呈显著相关关系,土壤速效钾与土壤镉含量呈极显著相关关系,土壤有机质、pH、碱解氮与土壤硒之间分别呈幂函数、指数函数、线性函数关系,土壤速效钾与土壤镉含量之间呈线性函数关系。研究区存在“土壤富硒作物不富硒”的问题,究其原因是土壤总硒与有效硒的关系不明确,因此在今后的研究中探究土壤中硒的形态特征及生物有效性对富硒农产品的稳定生产具有重要意义。