Insights into the adsorption performance and mechanism of hydrated Ca ion on talc(001) basal surface from DFT calculation

The utilization of Ca ion as assistant depressant of CMC on talc has been widely reported.Thus,the study on the adsorption mechanism of Ca ion on talc surface is very crucial for understanding the performance of CMC on talc depression.In this paper,mechanism insights into hydrated Ca ion adsorption on talc(001) basal surface were creatively provided using DFT calculation.[Ca(H_(2)O)_6]^(2+) and [Ca(OH)(H_(2)O)_(3)]^(+) were determined as the effective hydrate components for Ca ion adsorption,and the top O site was the most favorable position for their adsorptions on talc surface.Furthermore,the adsorption mechanisms of [Ca(H_(2)O)_6]^(2+) and [Ca(OH)(H_(2)O)_(3)]^(+) on talc surface were found to be not the Ca-O chemical bond,but the hydrogen bonding formed by the H atom of the H_(2)O ligand and the surface O atom.H_(2)O acted like a bridge to connect them to the talc surface.Moreover,the hydrogen bonding was formed due to the hybridization of H 1s orbital with the O 2s,O 2p orbitals.Simultaneously,electrons transferred between the H atom and the surface O atom.This work provides theoretical insights into the Ca ion adsorption on talc surface,which can help deeply understand the talc flotation using CMC as depression.

First-principle investigation on mechanism of Ca ion activating flotation of spodumene

Different hypotheses of the activation mechanisms of metallic ions for silicate minerals flotation were stated in this work. Spodumene and Ca ion were taken to illustrate this issue. Flotation test results and diagram of Ca ion species distribution vs pH show that the dominant hydrolyzed species are Ca（OH）？and Ca（OH）2, which is in correspondence with the maximum flotation recovery of spodumene. Density functional theory（DFT） calculation results reveal further that the precipitation of calcium hydroxide on spodumene surface is the effective process to activate the flotation of spodumene.

Ca and Sr co-doping induced oxygen vacancies in 3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts for boosting low-temperature oxidative coupling of methane

It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.

Precision spectroscopy with a single ^(40)Ca^+ ion in a Paul trap

Precision measurement of the 4s2 S1/2-3d2 D5/2 clock transition based on 40Ca＋ ion at 729 nm is reported. A single 40Ca＋ ion is trapped and laser-cooled in a ring Paul trap, and the storage time for the ion is more than one month. The linewidth of a 729 nm laser is reduced to about 1 Hz by locking to a super cavity for longer than one month uninterruptedly. The overall systematic uncertainty of the clock transition is evaluated to be better than 6.5 ×10^-16. The absolute frequency of the clock transition is measured at the 10^-15 level by using an optical frequency comb referenced to a hydrogen maser which is calibrated to the SI second through the global positioning system （GPS）, The frequency value is 411 042 129 776 393.0（1.6） Hz with the correction of the systematic shifts. In order to carry out the comparison of two 40Ca＋ optical frequency standards, another similar 40Ca＋ optical frequency standard is constructed. Two optical frequency standards exhibit stabilities of 1 × 10^-14 T-1/2 with 3 days of averaging. Moreover, two additional precision measurements based on the single trapped 40Ca＋ ion are carried out. One is the 3d2Ds/2 state lifetime measurement, and our result of 1174（10） ms agrees well with the results reported in [Phys. Rev. A 62 032503 （2000）] and [Phys. Rev. A 71 032504 （2005）]. The other one is magic wavelengths for the 4s2S1/2-3d2Ds/2 clock transition; λ ｜mj｜=1/2= 395.7992（7） nm and λ｜m｜=3/2 = 395.7990（7） nm are reported, and it is the first time that two magic wavelengths for the 40Ca＋ clock-transition have been reported.

Ca^(2+)离子浓度对煤泥浮选调浆效果的影响机理研究

为明确矿浆中Ca^(2+)离子浓度对煤泥浮选调浆效果的影响机理,以临涣选煤厂不同变质程度的三种煤样为研究对象,通过自建煤与捕收剂的水溶液间相互作用力测量系统以及煤与捕收剂接触角测试装置,并利用紫外分光光度计和分子动力学模拟,从煤与捕收剂的水溶液间润湿力和脱附力,煤与捕收剂间接触角,煤对捕收剂吸附率,以及煤-正十二烷、煤-水、正十二烷-水体系中分子的分布等角度展开了研究。结果表明:随离子浓度的增大,煤与油-水溶液间润湿力和脱附力均减小,而且相同时间内,对同体积煤样的润湿程度增大;同时,离子浓度增大,油-水界面张力减小,油滴与煤片间接触角减小,油滴在煤片表面铺展程度增大。此外,高离子浓度还会减弱煤和正十二烷的分子间作用力,降低正十二烷在煤表面的径向分布峰值;而煤和水分子间的相互作用力则会随离子浓度的增高呈先增大后减小的趋势,进而综合影响调浆过程中煤与正十二烷间的吸附效果。

Equilibrium and kinetics of adsorption of Ca(Ⅱ) ions onto KCTS and HKCTS

The adsorption of Ca（ II ） ions from aqueous solution by ehitosan a-ketoglutaric acid （KCTS） and hydroxamated chitosan a-ketoglutaric acid （HKCTS） was studied in a batch adsorption system. The Langmuir and Freundlich adsorption models were applied to describing the equilibrium isotherms, and isotherm constants were determined. The kinetics of the adsorption with respect to the initial Ca（II） ions concentration, temperature and pH was investigated. The pseudo-first-order and second-order kinetic models were used to describe the kinetic data and the rate constants were evaluated. The results show that the experimental data fit well to the Langmuir isotherms with a high correlation coefficient （R2）. The pseudo-second-order rate expression provides the best fitting kinetic model. The pseudo second-order kinetic model is indicated with the activation energy of 26.22 kJ/mol and 6.16 kJ/mol for KCTS and HKCTS, respectively. It is suggested that the overall rate of adsorption of Ca（ II ） ions is likely to be controlled by the chemical process.

内质网相关降解系统通过Ca^(2+)调控肝细胞线粒体能量代谢活性

肝细胞含有丰富的内质网和线粒体,两者以相互作用的方式调控肝细胞生命活动,但相互作用的机制尚未完全阐明。内质网中存在一套高度保守的蛋白质质量控制系统,即内质网相关降解(endoplasmic reticulum associated degradation,ERAD)。最新研究发现,ERAD可通过线粒体相关膜性结构(mitochondria associated membranes,MAMs)调控脂肪细胞线粒体功能,但在肝细胞中,关于ERAD与线粒体之间的相互作用及机制目前仍不明确。本研究选用HepG2作为细胞模型,通过化学药物诱导和基因敲除2种方法构建ERAD功能障碍肝细胞模型。采用荧光标记、流式分析和免疫印迹等技术手段,探究ERAD在肝细胞线粒体中的作用。结果发现,ERAD功能障碍会降低HepG2肝细胞线粒体膜电位和ATP水平(P<0.01);而且,ERAD功能障碍还会破坏HepG2细胞内质网与线粒体Ca^(2+)稳态,当减少内质网Ca^(2+)释放时,可改善线粒体能量代谢功能(P<0.05)。这些发现在ERAD功能障碍小鼠原代肝细胞中得到进一步验证。上述结果表明,ERAD在肝细胞内质网与线粒体相互作用中具有重要的调控作用,增强ERAD功能可能提升肝细胞线粒体活性,为线粒体功能障碍相关疾病提供新的研究思路。

Ca^(2+)与苹果花粉萌发和花粉管生长的关系

以苹果的花药、花粉为试材，观测Ca(2+)与花粉萌发和花粉管生长的关系。结果表明，不同品种和花芽萌动期的花药中Ca(2+)含量与花粉萌发率和花粉管长度无明显的相关关系。花粉培养过程中花粉壁渗出的Ca(2+)量与萌发率和花粉管长度呈极显著正相关。10(－4)mol·1(－1)的游离Ca(2+)最有利于花粉萌发，1mmol．1(－1)EGTA对花粉萌发和花粉管生长的抑制作用强于0．1mmol．1(-1)．外源CaCl2、Ca（NO3）2、SrCl2在低浓度时对花粉萌发与花粉管生长的作用不大；高浓度时具抑制效应，并且在同等浓度时，SrCl2的抑制作用最大。

K、Ca、Zn离子对烤烟种子萌发及幼苗抗旱性的影响

用１９８．０２ｍｍｏｌ／ＬＫ＋、１．２４ｍｍｏｌ／ＬＺｎ＋＋浸种均可促进种子萌发，提高发芽率。高浓度的Ｃａ＋＋（２２．５２ｍｍｏｌ／Ｌ）对种子产生一定的渗透胁迫，并起到筛选作用。Ｋ＋、Ｃａ＋＋、Ｚｎ＋＋均能提高种子活力指数和烟苗素质；浸种和液培对幼苗生长有促进作用，并能提高烟苗的抗旱能力，但其机理有所差异。在干旱胁迫时，Ｋ＋对烟苗的主要作用表现在增加细胞的保水能力上，而Ｃａ＋＋则表现为稳定细胞膜的结构，减少可溶性物质的大量渗出，使相对电导率下降，并能显著提高细胞中的ＣＡＴ活性；Ｚｎ＋＋在增强ＳＯＤ活性上有显著作用。Ｚｎ＋＋和Ｃａ＋＋均使可溶性蛋白质含量增加。试验还表明，ＮＣ８９的抗旱性好于Ｋ３２６。

壳聚糖衍生物与Ca(Ⅱ)螯合反应的动力学及机理研究

利用吸附体系研究了Ca(Ⅱ)与壳聚糖衍生物的吸附动力学行为,动力学模式函数为1/c=kt,螯合反应的速率方程为:dcdt=-kc2用13CNMR和广角X射线衍射(WXRD)分析等对壳聚糖衍生物进行了结构表征,通过红外光谱(IR)和X射线光电子能谱(XPS)研究了壳聚糖衍生物与Ca(Ⅱ)的配位机理。结果表明:配合物中Ca(Ⅱ)与α-酮戊二酸缩壳聚糖(KCTS)中氨基氮原子配位,与羟胺α-酮戊二酸缩壳聚糖(HKCTS)配位的配位原子为—NH—中的氮原子、羟肟酸中的氧原子及羰基中的氧原子。

Ca^(2+)对双酶法水解玉米淀粉的影响

考察了α-淀粉酶和β-淀粉酶的酶学性质,探讨了Ca2+/淀粉于50℃和pH4.5的条件下的β-淀粉酶热稳定性。研究表明,向可溶性淀粉溶液中添加30mmol/LCa2+,能大大提高β-淀粉酶的活性和稳定性;而液化过程中的外加Ca2+盐可使还原性糖的生成量略有提高。双酶法(α-淀粉酶和β-淀粉酶)水解玉米淀粉液的对照实验显示,向底物中加一定量的钙盐,可以获得更多的可发酵性还原糖。

肉鸡腹水症发病机理研究:Ⅳ.低温处理对肉鸡心肌肌浆网钙泵活性与Ca^(2+)摄取的影响

采用超速离心法分离提纯右心室肌原纤维和肌浆网 ,测定低温处理早期肉鸡心肌肌浆网钙泵 (Ca2 + ATP酶 )活性和肌浆网Ca2 +离子浓度 ,以揭示低温处理早期肉鸡右心室功能增强和肉鸡肺动脉高压的机制。结果表明 :1) 19、2 7、33和 4 0d低温处理组SRCa2 + ATP酶活性较对照组显著性升高 ,33d时活性达到最高。肺动脉高压组、肺动脉低压组SRCa2 + ATP酶活性较对照组显著性升高 ,其中肺动脉高压组SRCa2 + ATP酶活性是低压组的 3倍 ,且差异极显著 (P <0 .0 1)。 2 )低温处理组 19和 2 1d心肌肌浆网Ca2 +含量明显升高 ,与对照组相比差异显著 (P <0 .0 5 )。33和 4 0d低温处理组肌浆网Ca2 +摄取趋向减少 ,与对照组相比 ,差异不显著。肺动脉高压组与对照组相比 ,肌浆网摄取Ca2 +的浓度显著性升高 ,差异显著 (P <0 .0 5 ) ;而且肺动脉高压组心肌肌浆网摄取Ca2 +的量显著性高于肺动脉低压组 (P <0 .0 5 )。

Ca^(2+)对普通念珠藻(Nostoc commune Vanch.)生长影响的试验

对普通念珠藻(NostoccommuneVanch.)进行了生长条件的探索研究。初步研究结果表明:普通念珠藻的生长需要最适光照强度为2200lux左右,最适温度25℃,生长最适点pH=8;在0.02%的Ca2+浓度下的生长状况最好。

惰性气体离子辅助产生Ca^+、He^+及其注入钛箔和纳米钛膜的微结构分析

介绍了由弗里曼离子源在惰性气体辅助下产生Ca+、He+的研究及其分别注入钛箔和纳米钛膜的微结构分析。Ca+ 注入Ti箔样品的XPX分析表明:在1×1018/cm2注入剂量下,Ca的含量达到33﹪,注入Ca在钛表面主要形成CaTiO3、CaO和TiO2的化学结合的方式与钛基体连接;He+注入纳米钛样品的XRD的衍射谱在15—40°范围内明显分裂及变得较为尖锐,由谢乐公式计算出的纳米膜样品在(100)(101)晶面晶粒粒度大小分别为20.2nm和19.3nm,表明纳米钛膜注氦后仍保持纳米尺度。而AFM在微米视场下观察到纳米钛膜的表层粒子粒度虽有所长大,但在纳米视场却观察到大量的亚结构,结合AFM观察和XRD的分析结果证明在高剂量注入下,存在纳米钛膜表层粒子同时又被碎化成微晶使注氦纳米钛晶粒仍保持纳米尺度的重要现象。

水溶液环境下手性配合物Phe·Ca^(2+)对映异构机理的DFT研究

采用DFT(density functional theory)的M06-2X、MN15方法和处理溶剂效应的SMD模型方法,研究了水溶液中S-苯丙氨酸(S-Phe)与二价钙(Ca^(2+))配合物(Phe·Ca^(2+))的对映异构。反应通道研究发现,S-Phe·Ca^(2+)的对映异构可在质子以N和O分别为桥以及O和N联合为桥迁移的3个通道上实现。计算表明:最优势通道是质子以N为桥迁移,隐性水溶剂效应下决速步自由能垒是227.5 kJ/mol,显性水溶剂效应下该能垒降至108.0~117.6 kJ/mol。结果表明:水溶液中手性Phe·Ca^(2+)的消旋过程十分缓慢,将其用于生命体同补苯丙氨酸和钙元素可能比较安全。

Ca^(2+)对磁黄铁矿浮选的“屏蔽效应”

以磁黄铁矿纯矿物为研究对象,采用SEM-EDS、ICP和XPS等分析方法,研究了矿浆中Ca^(2+)对磁黄铁矿可浮性的影响,并分析了其产生机制。对比普通水体和高钙水体中磁黄铁矿的浮选效果,发现高钙水体中磁黄铁矿回收率降低了14个百分点。通过多种检测分析手段证明Ca^(2+)能够在磁黄铁矿被氧化后的表面上形成一层CaSO_4薄膜,这层亲水薄膜极大地阻碍了CuSO_4对磁黄铁矿的活化,进而导致难以在高钙水体中浮选磁黄铁矿。

CaF_2对MgO-CaO材料缺陷形成及烧结性能的影响

以分析纯Mg(OH)2和Ca(OH)2为原料,CaF2为添加剂,通过行星球磨机混合后机压成型,经1650℃×3 h烧成,制备了MgO-CaO材料。采用XRD和SEM对试样进行了分析表征。结果表明:随着CaF2加入量的增大,试样的体积密度逐渐增大,显气孔率减小,试样的致密化程度增强,而CaF2加入量超过2wt%后,试样的致密化程度降低。CaF2促进MgO-CaO材料致密的实质在于,CaF2晶体结构中存在大量的八面体空隙,由于自身的热缺陷,F-进入间隙位而形成填隙离子,留下带正电的F-空位,在迁移过程中易与O2-发生静电吸引,增大了O2-的扩散速度,增强了MgO的扩散,进而促进方镁石晶粒的长大。

不同Ca/P摩尔比碳羟基磷灰石对Cu^2＋的吸附特性

利用废弃蛋壳为原料、尿素为添加剂,合成不同Ca/P摩尔比的碳羟基磷灰石(CHAP)用于吸附水中Cu2+,利用红外光谱、扫描电子显微镜、X射线能谱测试技术对CHAP样品表面化学进行了表征,考察了环境因子pH值、温度对CHAP吸附Cu2+的影响。结果表明,通过改变尿素用量可以增加CHAP的Ca/P,提高其比表面积,Ca/P越高的CHAP,吸附能力越强。Ca/P为1.80的CHAP,在pH=7、温度40℃、反应时间为60min时,其对Cu2+吸附量高达37.66mg/g。随着CHAP的Ca/P比增大,CHAP对Cu2+吸附的固相-水相分配系数也增大,对吸附量增大很有利。

掺稀土离子的CaS：Bi荧光粉的发光性质

采用固相反应法合成了单掺和双掺稀土离子Ｔｍ３＋、Ｅｒ３＋的ＣａＳ：Ｂｉ荧光粉，测定了试样的荧光光谱和有效余辉。与ＣａＳ：Ｂｉ相比，掺入Ｔｍ３＋、Ｅｒ３＋的荧光粉，Ｂｉ３＋特征发射峰４４７ｎｍ增强，有效余辉延长。表明Ｔｍ３＋、Ｅｒ３＋对Ｂｉ３＋在ＣａＳ中的发光产生了敏化作用，Ｔｍ３＋、Ｅｒ３＋在基质晶格中造成了缺隙深能级，讨论了Ｔｍ３＋、Ｅｒ３＋对ＣａＳ：Ｂｉ发光敏化作用的大小和在基质中造成缺隙能级。的深浅。

水液相下两性α-丙氨酸Ca(Ⅱ)配合物旋光异构的理论研究

采用密度泛函理论的M06-2X方法,结合自洽反应场理论的SMD模型方法,研究了水液相下两性α-丙氨酸与二价钙配合物(S-Ala·Ca^(2+))的旋光异构.研究发现:S-Ala·Ca^(2+)的旋光异构有a、b和c 3个通道,a是α-氢迁移到羰基氧后,质子再从质子化氨基迁移到α-碳;b是质子只以羰基氧为桥迁移;c是质子从质子化氨基迁移到羰基氧后,再以氨基氮为桥迁移.势能面计算表明,隐性溶剂效应下,c通道具有优势,决速步内禀能垒是232.8 kJ·mol^(−1);a和b通道是劣势通道,决速步内禀能垒均是268.6 kJ·mol^(−1).显性溶剂效应下,a和b通道略具优势,决速步内禀能垒在141.3~145.0 kJ·mol^(−1)之间;c通道略具劣势,决速步内禀能垒在153.1~161.0 kJ·mol^(−1)之间.结果表明,水液相下丙氨酸钙配合物很难消旋,用于生命体补充钙和丙氨酸具有较好的安全性.