高氟铝和铝引起低龄鸡骨发育不全

进行了高氟铝和铝对低龄鸡骨损害的实验。５７日龄鸡９６只随机分为８组,毒物加进饲料,实验期３个月。结果表明,各高氟、高氟铝组骨氟均数倍于对照组,低铝组骨氟显著升高;单饲ＮａＦ组骨铝增高近３倍,高氟铝组骨氟比ＮａＦ组和病区玉米组低１／３以上,骨铝低约５０％;单饲铝达对照４～２１倍的骨铝与对照组接近。饲氟与骨氟ｒ＝０．７７,与骨铝ｒ＝０．６５;饲铝与骨铝ｒ＝－０．４６,与骨氟ｒ＝－０．５３;骨氟与骨铝ｒ     

受腐蚀的不锈钢片和铝片中微量氟的分离和测定

大量铁或铝存在时欲分离微量氟颇为困难,即使采用氟离子选择电极测定微量氟亦需避免其影响。至于用茜素络合剂比色测定氟,自1959年Belcher提出后已得到广泛的应用。虽然,Feigl早就建议借提高溶液的pH值可使铁(Ⅲ)和铝(Ⅲ)的氟络合离子解蔽。向井等曾用8-羟基喹啉沉淀分离和测定共存的铝和氟。但两者均无分离微量氟的结果。而且,单凭提高pH并不能使氟离子与铝(Ⅲ)完全分离。本文用沉淀法使微量氟离子解蔽而分别与大量铁(Ⅲ)和铝(Ⅲ)分离,继借二苯胍阳离子对茜素络合剂-铈(Ⅲ)-氟离子三元络合物中亲水基团的封闭作用,以有机溶剂萃取分光光度测定微量氟。此法     

氧化铝中少量氟的测定

石油化工应用催化剂中,常需分析氧化铝中低至万分之几的氟,过去采用蒸馏法分离,因铝与氟强烈络合,氟往往蒸馏不完全,数据不稳。遵照科研为生产服务的方针,我们试用氟离子电极解决这一课题。问题的关键是采用一种掩蔽剂,夺取铝氟络合物中的铝,使氟释放出来。文献中报道过多种铝的掩蔽剂,但柠檬酸钠或柠檬酸钠加上 CYDTA 只能掩蔽小于5毫克的铝;磺基水杨酸能掩蔽25毫克的铝,但需在 pH 9才能掩蔽,由于受 pH 的影响,氟的浓度必须大于1×10~(-4)M,铝氟比例还在500倍左右。Wilson 用氟离子电极测定氧化铝中氟,但氟量为百     

基于多级络合反应的电位滴定法——氟电极指示、电位滴定法测定铝

本文根据氟离子与铝离子的络合反应,提出了氟与铝的络合比和溶液中游离氟离子浓度之间的函数关系式,阐明了基于多级络合反应的电位滴定分析法的基本原理。对滴定方法和主要影响因素也进行了讨论。方法用于钛合金中铝的测定,获得了满意的结果。     

高铝引起性发育成熟前人和动物的排斥性损害和主动调节保护及自身平衡稳定反应

在铝氟联合中毒的系列研究中 ,发现性发育成熟前头发和血尿高铝的骨软化畸形病人 ,肝、肾铝显著升高的大鼠和鸡的骨铝、脑铝含量在接近或明显甚至显著低于正常对照组时 ,出现了铝骨病和铝危害的其它表现 ;AlCl3 ·6H2 O对童鸡非蓄积危害阈值范围指数 >5 (2 1 40 41 9) ,较低浓度比较高浓度饲铝组病变更为显著 ,铝在一定浓度或剂量范围与反应强度可呈非正相关关系 ;一定浓度以上 ,摄铝与高氟促成铝吸收和蓄积的数倍到 1 0数倍浓度差别的病情差异并不明显。表明人和动物在地壳高铝环境中的长期进化与适应 ,于生长发育旺盛的性成熟前形成并完善了对自然条件下进入内环境高铝的排斥和主动调节保护及自身平衡稳定反应的机制 ,以避免铝危害和减轻铝的危害程度     

铝和铝氟病鸡模型全血骨元素和血清生化骨矿含量骨形态学的相关研究

复制了铝危害和铝氟病鸡模型。将100日龄84只雄性种鸡随机分为7个组,毒物加进配合饲料自由摄食,实验3个月。结果表明,高铝、高氟、高氟铝组在实验3周内全血多种元素和7周内的血清生化物质含量及其相关性便发生显著变化,实验13周性成熟后出现逆转并接近正常。均引骨骼元素含量、骨细胞、骨胶元、骨组织形态、骨矿代谢、骨塑形和骨骼力学机能的病理变化。性成熟后饲料加氟与未加氟各3个组的全血铁、磷、血清钙、GRT才出现分异,并与骨矿代谢动态参数的分异相吻合。表晨本实验性成熟前诸多病变主要是铝危害引起。铝可较长期使全血锌和和骨锌含量下降。全血元素含量和相关性的变化是受机体内环境影响较大的动态变化过程。骨代谢联系着广泛的生物无机化学基础。性成熟后高氟、高氟铝、高铝的危害尚有各自的特点。     

控制电位氟-金属离子配位滴定法同时测定铝和镓

1引言铝和镓作为同族元素,有很多相似的性质。对它们的同时测定,无论在理论上或在实际应用中,均有一定的意义。本实验以氟离子溶液作滴定剂,氟离子选择性电极作指示电极,利用氟铝及氟镓之间的配位反应及控制电位滴定法,对铝和镓的同时测定进行了研究。用氟离子溶液滴定铝离子和     

包头磁尾矿的铝盐混合焙烧-酸浸萃取稀土的研究

以包头白云鄂博磁尾矿为原料,利用氟-铝极强的配位能力,进行铝盐混合焙烧,使氟-铝在焙烧过程中发生固相配位作用,达到活化稀土目的。然后利用酸溶液浸出稀土和氟的实验,考察稀土与氟的浸出率,最后P204萃取稀土。结果表明:采用Al2(SO4)3为磁尾矿抑氟剂,n(F)/n(Al)=3.0时,稀土矿的活化效果最佳。包头磁尾矿与铝盐混合物于700℃焙烧1.0 h,经2.0 mol·L-1H2SO4在80℃条件下浸出3.0h,氟和稀土的浸出效果较好。其中稀土浸出率在86.57%左右,氟可全部浸出。以该条件下产生的含氟稀土溶液为原料进行萃取实验,稀土全部进入有机相,而氟存留在浸出液中,基本实现了稀土和氟的分离。     

基于铝氟配位反应的动力学-电位法对铝的测定

以氟离子选择性电极作指示电极,用动力学电位法对铝的测定进行了研究.在低pH条件下,铝氟反应E～t曲线的斜率△E/△t与铝的浓度cAl成正比.实验步骤为:第一步,根据铝的校正溶液与氟反应的△E/△t,作出△E/△t～cAl工作曲线;第二步,根据铝试液与氟反应的△E/△t,求出铝的浓度.合适的实验条件是:pH范围1～2;温度范围288～303 K;铝的浓度范围1×10-3～5×10-2mol/L;加入的氟的浓度范围5×10-4～5×10-2mol/L.此外,对动力学电位法测定铝的计算式进行了理论推导,对该法存在的问题、可以采取的措施及误差的分布进行了讨论.     

高氟铝暨铝引起性发育前人和动物高钙及高骨矿性骨软化

对铝氟联合中毒27例2－11岁儿童和100日龄雄鸡实验3个月进行了动态观察。结果表明，骨软化伴 骨硬化的病人有22例，占81％；随着年龄增长，骨硬化渐渐突出；患儿全血钙、磷升高，血清Ca^2 正常范围偏高，血清P^5 下降。铝氟联合作用实验鸡性发育前、后全血钙一直较高，全血磷与血清Ca^2 、P^5 及其相关关系出现由高到低到高的交错变化；单独铝作用全血钙一直较高，碱到性成熟期下降，血清Ca^2 、P^5 一直较低。在性发育完成阶段，高铝可使类骨质矿化过度延迟，小幅度减少骨钙、磷含量，但骨部矿物元素和骨矿含量及骨密度不一定降低，甚至可小幅度升高，又有同软化；铝氟联合作用时类骨质矿化延迟时间仍过长，骨矿沉积率已高于对照，存在明显分离。氟可提高矿物元素含量，使骨矿化与骨硬化在骨组织不同层面茯结合成年病人的情况，认为铝氟联合 作用骨损害的表现与骨代谢速度及细胞生物化学和物理化学骨形成方式偏转的变化密切相关。     

Lewis acid stabilized OPI3: implications for the nature of free OPI3

While reinvestigating the published synthesis of OPI(3), it became evident from the experiments that phosphoryl triodide may only be formed as an intermediate and that the end products of the reaction of OPCl(3) with LiI are P(V) oxides, PI(3), I(2), and LiCl. This is also in agreement with MP2/TZVPP calculations, which assign Delta(r)H degrees (Delta(r)G degrees ) [Delta(r)G degrees in CHCl(3)] for the disproportionation of OPI(3) as -7 (-18) [-17 kJ mol(-1)] (assuming P(4)O(10) as the P(V) oxide). The first products of this reaction visible in a low-temperature in situ (31)P NMR experiment are P(2)I(4) and PI(3), as well as traces of a compound that may be OPCl(2)I. By contrast, it was possible to prepare and structurally characterize Lewis acid [A] stabilized [A]<--OPX(3) adducts, where [A] is Al(OR(F))(3) for X=Br and Al(OR(F))(2)(mu-F)Al(OR(F))(3) for X=I (R(F)=C(CF(3))(3)). These adducts are formed on decomposition of PX(4) (+)[Al(OR(F))(4)](-); high yields of Br(3)PO-->Al(OR(F))(3) (delta((31)P)=-65) were obtained, while I(3)PO-->Al(OR(F))(3) (delta((31)P)=-337) and I(3)PO-->Al(OR(F))(2)(mu-F)Al(OR(F))(3) (delta((31)P)=-332) are only formed as by-products. The main product of the room-temperature decomposition of PI(4) (+)[Al(OR(F))(4)](-) is PI(4) (+)[(R(F)O)(3)Al(mu-F)Al(OR(F))(3)](-), which was also characterized by X-ray crystallography and was independently prepared from Ag(+)[(R(F)O)(3)Al(mu-F)Al(OR(F))(3)](-), PI(3), and I(2).     

Structure resolution of Ba5Al3F19 and investigation of fluorine ion dynamics by synchrotron powder diffraction, variable-temperature solid-state NMR, and quantum computations

The room temperature structure of Ba(5)Al(3)F(19) has been solved using electron microscopy and synchrotron powder diffraction data. One-dimensional (1D) (27)Al and ultrafast magic-angle-spinning (MAS) (19)F NMR spectra have been recorded and are in agreement with the proposed structural model for Ba(5)Al(3)F(19). The (19)F isotropic chemical shift and (27)Al quadrupolar parameters have been calculated using the CASTEP code from the experimental and density functional theory geometry-optimized structures. After optimization, the calculated NMR parameters of both the (19)F and (27)Al nuclei show improved consistency with the experimental values, demonstrating that the geometry optimization step is necessary to obtain more accurate and reliable structural data. This also enables a complete and unambiguous assignment of the (19)F MAS NMR spectrum of Ba(5)Al(3)F(19). Variable-temperature 1D MAS (19)F NMR experiments have been carried out, showing the occurrence of fluorine ion mobility. Complementary insights were obtained from both two-dimensional (2D) exchange and 2D double-quantum dipolar recoupling NMR experiments, and a detailed analysis of the anionic motion in Ba(5)Al(3)F(19) is proposed, including the distinction between reorientational processes and chemical exchange involving bond breaking and re-formation.     

An Aluminum Fluoride Complex with an Appended Ammonium Salt as an Exceptionally Active Cooperative Catalyst for the Asymmetric Carboxycyanation of Aldehydes

Al−F bonds are among the most stable σ bonds known, exhibiting an even higher bond energy than Si−F bonds. Despite a stability advantage and a potentially high Lewis acidity of Al−F complexes, they have not been described as structurally defined catalysts for enantioselective reactions. We show that Al−F salen complexes with appended ammonium moieties give exceptional catalytic activity in asymmetric carboxycyanations. In addition to aromatic aldehydes, enal and aliphatic substrates are well accepted. Turnover numbers up to around 10⁴ were achieved, whereas with previous catalysts 10¹–10² turnovers were typically attained. In contrast to Al−Me and Al−Cl salen complexes, the analogous Al−F species are remarkably stable towards air, water, and heat, and can be recovered unchanged after catalysis. They possess a considerably increased Lewis acidity as shown by DFT calculations.     

Structural role of fluoride in aluminophosphate sol-gel glasses: high-resolution double-resonance NMR studies

The local structure of Na-Al-P-O-F glasses, prepared by a novel sol-gel route, was extensively investigated by advanced solid-state NMR techniques. 27Al{19F} rotational echo double resonance (REDOR) results indicate that the F incorporated into aluminophosphate glass is preferentially bonded to octahedral Al units and results in a significant increase in the concentration of six-coordinated aluminum. The extent of Al-F and Al-O-P connectivities are quantified consistently by analyzing 27Al{31P} and 27Al{19F} REDOR NMR data. Two distinct types of fluorine species were identified and characterized by various 19F{27Al}, 19F{23Na}, and 19F{31P} double resonance experiments, which were able to support peak assignments to bridging (Al-F-Al, -140 ppm) and terminal (Al-F, -170 ppm) units. On the basis of the detailed quantitative dipole-dipole coupling information obtained, a comprehensive structural model for these glasses is presented, detailing the structural speciation as a function of composition.     

Structures and electronic properties of Al7x0,- and Al13 X1,2,12- clusters with X=F, Cl, and Br

The structures, binding energies, and electronic properties for Al7X, Al7X-, Al13X-, Al13X2-, and Al13X12- (X = F, Cl, Br) were studied at the B3LYP/6-311+G(2d,p) level. Among the systems studied, Al7 and Al13 clusters in Al7X and Al13X- reveal alkali-like and halogen-like superatom characters, respectively. Al7 can bind with one halogen atom to form a salt-like compound as Al7+delta-X-delta. Al13- can combine with one halogen atom to form a diatomic halogen anion Al13X-. However, when adding more halogens, the superatom structure would be destroyed, resulting in low-symmetry compounds with the center Al atom moving toward the cluster surface. The structures of Al13X1,2,12- (X = F, Cl, Br) are similar to those of X = I; however, their binding energies and electron structures are much different. In addition, the analyses of the calculated NBO charges show that Cl and Br have similar properties, but much different from F, when interacting with the Al clusters. The Al-Cl and Al-Br bonds have more covalent character in Al7X and Al13X2,12-, in contrast to the corresponding Al-F bond, which has prominent ionic character.     

H(2) activation and hydride transfer to olefins by al(c(6) f(5) )(3) -based frustrated lewis pairs

Frustrated delivery: Frustrated Lewis pairs derived from tBu(3) P and Al(C(6) F(5) )(3) activate H(2) to give [tBu(3) PH][(μ-H)(Al(C(6) F(5) )(3) )(2) ], which reacts with unactivated olefins to give RAl(C(6) F(5) )(2) (R=Et or Cy) and [tBu(3) PH][Al(C(6) F(5) )(4) ]. The proposed mechanism involves olefin activation by aluminum, which is supported by the isolation of the cyclohexene complex [Al(C(6) F(5) )(3) ?(C(6) H(10) )].     

骨的微量元素代谢

雌激素可通过影响骨骼细胞的新陈代谢而促进微量元素在骨骼中的储存,微量元素代谢与骨质疏松的形成发展有密切关系。近年来不少学者对一些必需微量元素如硼(5B)、氟(9F)、钒(23V)、锰(25Mn)、铁(26Fe)、钴(27Co)、铜(29Cu)、锌(30Zn)、硒(34Se)、锶(38Sr)等和一些非必需微量元素如铝(13Al)、镓(31Ga)、锗(32Ge)、镉(48Cd)、铅(82Pb)等与骨质疏松关系的研究取得了令人瞩目的成果。     

New crystalline aluminum alkoxide oxide fluorides: evidence of the mechanism of the fluorolytic sol-gel reaction

This study reports three new crystalline aluminum isopropoxide oxide fluorides with molar ratios of Al:F equal to 1:1 and 1:1.25. These are the first three representatives isolated without the incorporation of external donor molecules. Compound 1 Al(4)F(4)(μ(4)-O)(μ-O(i)Pr)(5)[H(O(i)Pr)(2)] contains a tetranuclear unit consisting of two different five fold coordinated AlFO(4)-units, with F exclusively in the terminal position. Compound 2, Al(4)F(4)(μ(4)-O)(μ-O(i)Pr)(5)[H(O(i)Pr)(2)]·Al(5)F(5)(μ(5)-O)(μ-O(i)Pr)(8), contains both a tetranuclear unit (as in 1) and a pentanuclear Al-unit. Al-atoms in the latter are five- and six fold coordinated. Compound 3, Al(16)F(20)(μ(4)-O)(4)(μ-O(i)Pr)(20)·2((i)PrOH), exhibits a slightly higher fluorination degree and contains an oligomeric chain of four F-linked tetranuclear Al-units. In addition to X-ray structure analysis, compound 1 was characterized by different solid state MAS NMR techniques, including (27)Al triple quantum MAS NMR and (1)H, (1)H→(13)C CP, (19)F and (27)Al MAS NMR. On the basis of the collected data, a reliable decomposition of (27)Al single pulse MAS NMR spectra and an unambiguous assignment of the resonances to the respective structural AlFO(4)-units are given. The new crystalline aluminum isopropoxide oxide fluorides are direct evidence of the fluorolytic sol-gel mechanism previously discussed.     

The reaction of alf3 solution with aluminium hydroxide and some reactions of the aluminium hydroxyfluoride obtained

AlF₃ solution (150 g/l) reacts with Al(OH)₃ in the m.ratio 2:1 in excess of ca. 115°C to produce Al(OH,F)₃.H₂O with an F/Al at. ratio > 2. At lower temperatures, e.g. 110°C, or at higher reactants ratios, e.g. 3-11, formation of Al(OH,F)₃.H₂O may be accompanied by crystallization of AlF₃-hydrates as AlF₃.3H₂O and/or /gb-AlF₃.H₂O. When crystallization of β - AlF₃.H₂O occurs to a greater extent, Al(OH,F)₃.H₂O may vary in its F/Al at.ratio from ca. 2.5 to 1, during the reaction.Al(OH)F₂.H₂O reacts readily with NaOH, NaF and NH₄F solutions to give sodium and ammonium cryolite. Reactions with NaHF₂ and H₂SiF₆ were unsuccessful, while with AlF₃ solution an increase of the F/Al ratio in the Al basic fluoride used resulted.