氟、铈对磷酸三钙水解过程及其产物抗酸性的影响

研究了不同浓度的F- 和Ce3 +对磷酸三钙 (Ca3 (PO4) 2 ,TCP)的水解过程和水解产物的影响。XRD及IR实验结果表明 ,TCP在NaF溶液中的水解产物为羟基磷灰石 (Ca1 0 (PO4) 6(OH) 2 ,HAP)和氟基磷灰石 (Ca1 0 (PO4) 6F2 ,FAP)的混合物。氟离子浓度越高 ,FAP的含量越多。TCP水解过程的pH值变化随氟离子的起始浓度不同而不同。氟离子浓度越高 ,pH值越低。TCP在CeCl3 溶液中的水解产物为铈取代的羟基磷灰石 (CexCa1 0 -y(PO4) 6-z(OH) 2 ,Ce HAP)。溶解实验表明 ,氟处理比铈处理更有效地增强了TCP水解产物的抗酸性。当F -浓度为 0 1%或Ce3 +浓度为 5× 10 - 2 %时 ,TCP水解产物的抗酸性最强     

湿法磷酸生产饲料级磷酸二氢钙的研究

磷酸二氢钙[Ca(H2PO4)2.H2O](MCP)是一种优良的高效性磷酸盐饲料添加剂。本文论述了利用价廉的湿法磷酸为原料生产低成本的饲料级磷酸二氢钙的研究。     

电流密度对钙磷沉积层组成和结构的影响(英文)

用X射线衍射、激光拉曼光谱以及等离子体原子发射光谱等技术研究了电化学沉积钙磷陶瓷过程中 ,电流密度对电沉积层组成和结构的影响 .实验表明阴极表面得到的沉积物是几种钙磷盐组成的混合物 ,且其成份随电流密度的改变而发生较大的变化 .在电解液温度为 75℃条件下 ,当控制电流密度较低时 ,沉积层主要由CaHPO4· 2H2 O (DCPD)和Ca8H2 (PO4) 6· 5H2 O (OCP)组成 ;随着电流密度的增加 ,阴极表面逐渐生成Ca3 (PO4) 2 ·nH2 O (TCP)和Ca10 (PO4) 6(OH) 2 (HAP) .当电流密度大于 5mA/cm2 时 ,电沉积层的主要成份为羟基磷灰石 (HAP) .     

油包水型微乳中层柱状磷酸锆的制备与表征

以氧氯化锆(ZrOCl2·8H2O)和磷酸三丁酯(C4H9O)3PO为原料, 在正庚烷(C7H10)-十六烷基三甲基溴化铵(CTAB)/正丁醇(C4H9OH)-水的反向微乳体系中制备了Zr(HPO4)2·H2O, (H3O)+Zr2(PO4)3和Zr(HPO4)8·H2O三种不同结构的层柱状磷酸锆. 运用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射仪(XRD)等仪器对产物进行了表征, 考察了不同微乳组成对磷酸锆结构及尺寸的影响. 结果表明, 微乳体系对层柱状磷酸锆的可控制合成具有广泛意义.     

银掺杂纳米羟基磷灰石抗菌粉体的水热合成及结构表征

采用水热法,以硝酸钙(Ca(NO3)2 4H2O)、硝酸银(AgNO3)和磷酸氢二铵((NH4)2HPO4)为主要原料,制备纳米级银掺杂羟基磷灰石(Ag-HA)抗菌粉体.考察了硝酸银加入量、反应温度、反应时间对产物结构和形貌的影响.XRD分析结果显示Ag-HA与HA具有相同的晶体结构.EDS和XRF分析结果说明Ag+取代Ca2+在HA晶体中的位置,生成AgxCa10-x(PO4)6(OH)2.抗菌试验结果表明,所制备的Ag-HA抗菌粉体具有良好的抗菌性能,最小抑菌浓度MIC值≤50μg/mL(对大肠杆菌、黄色葡萄球菌).     

纳米级β-磷酸钙的合成

通过Ca(OH)2/H3PO4/H2O体系合成了一系列的纳米级β-磷酸钙,研究了反应物浓度、反应时间对β-磷酸钙中Ca/P比的影响,应用IR,TEM,XRD对其形态和组成进行了表征并和Ca(NO3),4H2O/(NH4)2HPO4/H2O体系所制得的β-磷酸钙进行了比较.研究表明:两种方法都可以直接制备纳米级β-磷酸钙,烧结后晶体结构更完善.     

Ce3(PO4)4在酸性溶液加热条件下化学形态转化及机理研究

磷酸高铈(Ce3(PO4)4)是一种难溶于水的化合物,本文测定磷酸高铈在常温pH=0.4的Ksp值为1~8×10-34,但在测定过程中发现Ce3(PO4)4的溶解度受温度变化的影响较大,尤其在50℃以上时,Ce3(PO4)4饱和溶液体系中的Ce4 、PO43-和pH值均变化异常。根据测得的Ce4 、PO43-浓度以及pH值,推断出50℃以上时Ce3(PO4)4转化为Ce(HPO4)2,并建立了相应的转化机理,测定出Ce(HPO4)2的Ksp为3~7×10-13。     

猪肝酯酶杂化“纳米花”的制备及其对菊酯类农药的水解性能研究

采用生物矿化策略,在磷酸盐缓冲液中制备了猪肝酯酶(Porcine liver esterase,PLE)杂化"纳米花"(Ca3(PO4)2-PLE)。利用扫描电镜、元素能谱分析及红外光谱对所制备的杂化"纳米花"进行了形貌和成分分析。对杂化"纳米花"制备过程中的参数进行优化,结果表明:在10 mmol/L磷酸盐缓冲液(p H 7. 4)中,猪肝酯酶质量浓度为0. 3 g/L,钙离子浓度为500 mmol/L,制备温度为20℃时,所制备的Ca3(PO4)2-PLE具有最高酶活,其酶活为同等酶浓度下液酶酶活的169%。将制备的Ca3(PO4)2-PLE用于4种菊酯类农药的酶解性能研究,发现相同条件下,Ca3(PO4)2-PLE的酶解率均优于液酶。此外,制备的Ca3(PO4)2-PLE用于菊酯农药酶解循环2次后仍保持70%以上的活力。     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

混合型甘氨酸-N，N-双亚甲基膦酸-磷酸锆：合成、表征及插层

采用氢氟酸络合法,在nP/nZr=2.0条件下,以甘氨酸-N,N-双亚甲基膦酸(DMPG)和H3PO4为原料,按不同投料物质的量的比制备了2个α、γ-混合型甘氨酸-N,N-双亚甲基膦酸-磷酸锆层状主体化合物Zr(PO4)0.41(HPO4)0.043[(O3PCH2)2NCH2COOH]0.67.H2O(1)和Zr(PO4)0.21(HPO4)0.038[(O3PCH2)2NCH2COOH]0.82.2H2O(2),用元素分析、X射线衍射、红外光谱、热分析、固体核磁磷谱等对化合物进行了表征,同时研究了与正丁胺客体分子的插层组装性能。     

第23届国际化学奥林匹克竞赛试题理论部分

1.用适当的公式,通过计算,解释下列事实(要求:必须用数据证明你的每个结论是合理的。假定:（a）所谓“溶解”一词是指在298K时在1L溶液中溶解0.1mol硫化物;（b）Cu2+（aq·）不与Cl-形成稳定的络合物):（1）Tl2S可溶解在浓度为1mol·L-1的任何无络合性、无氧化性的一元强酸中;（2）CuS不溶于1mol·L-1HCl,但溶于1mol·L-1HNO3。     

第24届国际化学奥林匹克竞赛试题(1992.7.匹兹堡和华盛顿)

注意事项:(1)当监考人员将“开始(start)”写在黑板上后才开始答题。(2)请用黑色笔(黑墨水笔或黑圆珠笔)答题。(3)请在每页答卷的右上角写上你的参赛编号。(4)请将计算过程和答案写在每题后面的空白处,勿写在纸的反面。若需另页,可向监考人员索取。     

第25届国际化学奥林匹克竞赛试题答案及应答分析

本次实验得到的产品的熔点的平均值是82—84=83℃。△4-3-甾酮的熔点是82℃。评分标准:≥86℃,5分;86—85℃,12分;85—84℃,14分;84—83℃,16分;83—82℃,18分;82℃,20分;82—80℃,18分;80—78℃,16分;78—76℃,14分;……。附加分:测定的熔点值与验证值的差值在1℃以内的加4分,差1—2℃的,加2分,超过4分的,不加分。     

Diaryldichalcogenide radical cations

One-electron oxidation of two series of diaryldichalcogenides (C₆F₅E)₂ (13a–c) and (2,6-Mes₂C₆H₃E)₂ (16a–c) was studied (E = S, Se, Te). The reaction of 13a and 13b with AsF₅ and SbF₅ gave rise to the formation of thermally unstable radical cations [(C₆F₅S)₂]˙⁺ (14a) and [(C₆F₅Se)₂]˙⁺ (14b) that were isolated as [Sb₂F₁₁]^– and [As₂F₁₁]^– salts, respectively. The reaction of 13c with AsF₅ afforded only the product of a Te–C bond cleavage, namely the previously known dication [Te₄]²⁺ that was isolated as [AsF₆]^– salt. The reaction of (2,6-Mes₂C₆H₃E)₂ (16a–c) with [NO][SbF₆] provided the corresponding radical cations [(2,6-Mes₂C₆H₃E)₂]˙⁺ (17a–c; E = S, Se, Te) in the form of thermally stable [SbF₆]^– salts in nearly quantitative yields. The electronic and structural properties of these radical cations were probed by X-ray diffraction analysis, EPR spectroscopy, and density functional theory calculations and other methods.     

A hexanuclear gold carbonyl cluster

The hexanuclear gold carbonyl cluster [PPh₄]₂[Au₆(CF₃)₆Br₂(CO)₂] (4) has been obtained by spontaneous self-assembly of the following independent units: CF₃AuCO (1) and [PPh₄][Br(AuCF₃)₂] (3). The cyclo-Au₆ aggregate 4, in which the components are held together by unassisted, fairly strong aurophilic interactions (Au···Au ∼310 pm), exhibits a cyclohexane-like arrangement with chair conformation. These aurophilic interactions also result in significant ν(CO) lowering: from 2194 cm^–1 in the separate component 1 to 2171 cm^–1 in the mixed aggregate 4. Procedures to prepare the single-bridged dinuclear component 3 as well as the mononuclear derivative [PPh₄][CF₃AuBr] (2) are also reported.     

Conducting polyfurans by electropolymerization of oligofurans

Polyfurans have never been established as useful conjugated polymers, as previously they were considered to be inherently unstable and poorly conductive. Here, we show the preparation of stable and conducting polyfuran films by electropolymerization of a series of oligofurans of different chain lengths substituted with alkyl groups. The polyfuran films show good conductivity in the order of 1 S cm^–1, good environmental and electrochemical stabilities, very smooth morphologies (roughness 1–5 nm), long effective conjugation lengths, well-defined spectroelectrochemistry and electro-optical switching (in the Vis-NIR region), and have optical band-gaps in the range of 2.2–2.3 eV. A low oxidation potential needed for polymerization of oligofurans (compared to furan) is a key factor in achievement of improved properties of polyfurans reported in this work. DFT calculations and experiments show that polyfurans are much more rigid than polythiophenes, and alkyl substitution does not disturb backbone planarity and conjugation. The obtained properties of polyfuran films are similar or superior to the properties of electrochemically prepared poly(oligothiophene)s under similar conditions.     

Expanding discriminative dimensions for analysis and imaging

Eliminating the contribution of interfering compounds is a key step in chemical analysis. In complex media, one possible approach is to perform a preliminary separation. However purification is often demanding, long, and costly; it may also considerably alter the properties of interacting components of the mixture (e.g. in a living cell). Hence there is a strong interest for developing separation-free non-invasive analytical protocols. Using photoswitchable probes as labelling and titration contrast agents, we demonstrate that the association of a modulated monochromatic light excitation with a kinetic filtering of the overall observable is much more attractive than constant excitation to read-out the contribution from a target probe under adverse conditions. An extensive theoretical framework enabled us to optimize the out-of-phase concentration first-order response of a photoswitchable probe to modulated illumination by appropriately matching the average light intensity and the radial frequency of the light modulation to the probe dynamics. Thus, we can selectively and quantitatively extract from an overall signal the contribution from a target photoswitchable probe within a mixture of species, photoswitchable or not. This simple titration strategy is more specifically developed in the context of fluorescence imaging, which offers promising perspectives.     

Biosynthetic insights provided by unusual sesterterpenes from the medicinal herb Aletris farinosa

A series of novel sesterterpenes (2–6) have been isolated from the roots of Aletris farinosa and structurally characterized by MS, NMR, and X-ray crystallography in conjunction with computational modeling. Their structures provide new insights into the mechanisms of sesterterpene biosynthesis. Specifically, we propose with support from density functional theory computations that the configuration at a single stereocenter determines the fate of a key tetracyclic carbocationic intermediate, derived from an oxidogeranylfarnesol precursor. Whereas one epimer of the carbocation undergoes H⁺ elimination to give 6, the other undergoes a spectacular cascade of seven 1,2-methyl and hydride migrations leading to the previously unreported carbon skeleton of 5. Theoretical calculations suggest that the cascade is triggered by substrate preorganization in the enzyme active site.     

Azasugar inhibitors as pharmacological chaperones for Krabbe disease

Krabbe disease is a devastating neurodegenerative disorder characterized by rapid demyelination of nerve fibers. This disease is caused by defects in the lysosomal enzyme β-galactocerebrosidase (GALC), which hydrolyzes the terminal galactose from glycosphingolipids. These lipids are essential components of eukaryotic cell membranes: substrates of GALC include galactocerebroside, the primary lipid component of myelin, and psychosine, a cytotoxic metabolite. Mutations of GALC that cause misfolding of the protein may be responsive to pharmacological chaperone therapy (PCT), whereby small molecules are used to stabilize these mutant proteins, thus correcting trafficking defects and increasing residual catabolic activity in cells. Here we describe a new approach for the synthesis of galacto-configured azasugars and the characterization of their interaction with GALC using biophysical, biochemical and crystallographic methods. We identify that the global stabilization of GALC conferred by azasugar derivatives, measured by fluorescence-based thermal shift assays, is directly related to their binding affinity, measured by enzyme inhibition. X-ray crystal structures of these molecules bound in the GALC active site reveal which residues participate in stabilizing interactions, show how potency is achieved and illustrate the penalties of aza/iminosugar ring distortion. The structure–activity relationships described here identify the key physical properties required of pharmacological chaperones for Krabbe disease and highlight the potential of azasugars as stabilizing agents for future enzyme replacement therapies. This work lays the foundation for new drug-based treatments of Krabbe disease.     

Boronic acids facilitate rapid oxime condensations at neutral pH

We report here the discovery and development of boron-assisted oxime formation as a powerful connective reaction for chemical biology. Oximes proximal to boronic acids form in neutral aqueous buffer with rate constants of more than 10⁴ M^–1 s^–1, the largest to date for any oxime condensation. Boron''s dynamic coordination chemistry confers an adaptability that seems to aid a number of elementary steps in the oxime condensation. In addition to applications in bioconjugation, the emerging importance of boronic acids in chemical biology as carbohydrate receptors or peroxide probes, and the growing list of drugs and drug candidates containing boronic acids suggest many potential applications.