亲油性硫化锰纳米微粒的化学制备和结构

采用表面修饰的方法,在醇水体系中制备了双十八烷基二硫代磷酸（DDP）表面修饰的硫化锰（MnS）纳米微粒,用XPS、FTIR、TGA、TEM和HREM等技术对用表面修饰法得到的MnS纳米微粒的结构、化学稳定性和热稳定性进行研究,结果表明：表面修饰得到的MnS纳米微粒有较好的化学稳定性和热稳定性,并且微粒的分散件好、不团聚,制备出的MnS纳米晶核具有γ－MnS的晶型结构。     

锰元素促进的人工合成化学及其应用

光合作用是大自然中最重要的合成反应,其产氧中心包括关键的锰-氧-钙结构单元。锰元素在地壳中储量大、毒性低、氧化态丰富,具有独特的反应性,因此,人工利用锰元素实现自然界不能实现的物质合成具有重要的意义和广阔的前景。本文简述了锰元素促进的合成化学的发展历史,及其近年来在无机电化学、有机合成等领域中的应用。     

钢铁在磷砷硅锰联合快速测定的改进

对钢铁中砷含的快速测定方法提出了改进意见，提高了稳定性和准确度，拟定了硅、锰、磷、砷四元素的联合快速测定新规程。     

配合物[Mn(4,4′-bipy)_2(H_2O)_4](HtsgluO)_2·2H_2O的合成及性质研究

<正>金属-有机框架材料(MOFs)是一类具有高度结晶性的配位聚合物,具有很好的稳定性、大的空穴体积和尺寸均一可调的孔洞。近年来,由于其在储氢、分离以及固相催化方面的潜在应用而引起人们的广泛兴趣[1-4]。MOFs的合成条件温和,可以通过选择合适金属离子和有机配体使之更符合特定性能的要求,即金属离子和有机配体的选择是关键。一     

掺锰氢氧化镍的结构与电化学性能

采用化学共沉淀法制备了锰取代的氢氧化镍样品，应用XRD技术对不同锰含量样品的相结构进行了表征，并用恒电流充放电、电流脉冲弛豫法和电化学阻抗技术研究了样品的电化学行为. XRD结果显示：锰含量少于20％时，样品主要由β相组成；而当锰含量达到28.3%时，可以得到具有纯α相结构的样品. 电化学研究结果表明：掺锰的氢氧化镍样品具有优良的电化学循环稳定性；锰的掺杂提高了氢氧化镍电极的析氧电位，增大了样品的质子扩散系数； 具有较低锰含量的氢氧化镍样品显示了较大的放电容量和较高的放电电位.     

锰纯度定值及其单元素溶液标准物质的研制

以高纯锰为原料研制锰单元素溶液标准物质。采用电感耦合等离子体质谱法、电感耦合等离子体发射光谱法以及元素分析仪3种方法测定高纯锰中杂质元素的含量,并通过杂质扣除法确定了高纯锰的纯度为(99.95±0.04)%(k=2)。采用重量–容量法制备了锰单元素溶液标准物质,以配制值作为锰单元素溶液标准物质的标准值。对溶液标准物质的均匀性和稳定性进行了检验,其均匀性与稳定性良好。对标准物质的不确定度进行了评定。锰单元素溶液标准物质的浓度值为100μg/mL,相对扩展不确定度为0.8%(k=2)。该标准物质的量值准确,可用于锰元素的分析检测、检测方法评价与仪器校准。     

钢铁中磷砷硅锰联合快速测定的改进

对钢铁中砷含量的快速测定方法提出了改进意见,提高了稳定性和准确度,拟定了硅、锰、磷、砷四元素的联合快速测定新规程.     

钡镁锰矿/水羟锰矿型锂离子电池阴极材料的结构和电化学性能研究

利用ＸＲＤ、ＴＥＭ、ＩＣＰ、低速ＣＶ以及恒流充放电等方法研究了一种３Ｖ锂离子电池阴极材料的结构及其电化学性能。样品主要由大隧道型结构的钡镁锰矿和层状结构的水羟锰矿组成,该样品的微观形貌为层间距约１０ｎｍ的叠片状结构。Ｌｉ＾＋在样品中的嵌入脱出过程具有较好的可逆性和循环稳定性。未经提纯的样品前３０次循环的放电比容量达到１２９ｍＡｈ／ｇ,１００次循环后为９６ｍＡｈ／ｇ。材料结构中嵌入隧道及层间的杂质金     

咪唑修饰硅胶配位固载锰(Ⅲ)卟啉对环己烷空气氧化的催化作用

应用3-氯丙基三甲氧基硅烷和咪唑成功地对硅胶表面进行了修饰,并通过咪唑基纵轴配位方式固载了四苯基锰(Ⅲ)卟啉.在无任何外加溶剂及共还原剂的条件下,应用此高分子金属卟啉作为催化剂,选择性地催化空气氧化环己烷为环己酮和环己醇.研究结果表明,与未固载金属卟啉相比,固载金属卟啉具有更高的催化活性和催化选择性,反应具有更高的酮醇比,催化剂的稳定性有了较大的提高,便于回收和重复使用.另外还探讨了载体在此催化体系中对催化性能的影响.     

交流示波极谱法测定锰铁合金中锰铁分量

锰铁合金是常用的合金材料,合金中的锰一般采用亚砷酸钠-亚硝酸钠法测定,手续繁琐、速度较慢。对该合金材料分析方法的报道极少,在LaNi_5、SmCo_5合金分量分析的基础上,本文提出用交流示波极谱法连续快速测定合金中锰、铁分量的新方法。该法至今尚未见报道,与其它方法相比,具有终点敏锐、直观、重现性好、准确等特点。用于该合金的测定,结果满意。     

A flow-injection chemiluminescence method for the determination of some estrogens by enhancement of luminol-hydrogen peroxide-tetrasulfonated manganese phthalocyanine reaction

A novel flow-injection chemiluminescence (FI-CL) method for the determination of estrogens is proposed, based upon its enhancing effect on the CL reaction of luminol with hydrogen peroxide catalyzed by tetrasulfonated manganese phthalocyanine (MnTSPc) in alkaline solution. Under the selected experimental conditions, a linear relationship was obtained between the CL intensity and the concentration of estrone in the range of 1.0 × 10⁻⁷ to 1.0 × 10⁻⁶ mol/l, estradiol in the range of 9.0 × 10⁻⁸ to 1.0 × 10⁻⁶ mol/l and estriol in the range of 3.0 × 10⁻⁷ to 2.0 × 10⁻⁶ mol/l, respectively. The detection limits were 5.1 × 10⁻⁸ mol/l for estrone, 7.2 × 10⁻⁹ mol/l for estradiol and 6.5 × 10⁻⁸ mol/l for estriol with a relative standard deviation of 2.8% for 5.0 × 10⁻⁷ mol/l estrone, 2.4% for 1.0 × 10⁻⁷ mol/l estradiol, and 3.1% for 7.0 × 10⁻⁷ mol/l estriol (n = 11). This method has been applied to the determination of estrogen in pharmaceutical injections and tap water with satisfactory results.     

四苯氧基酞菁镁、锰、铝和锌的合成和性质

合成了新的酞菁配合物４，４，４，４－四苯氧基酞菁镁［ＴＰｈＯＰｃＭｇ（Ⅱ）］，锰［ＴＰｈＯＰｃＭｎ（Ⅱ）Ａｃ］，铝［ＴＰｈＯＰｃＡｌ（Ⅲ）Ｃｌ］，锌［ＴＰｈＯＰｃＺｎ（Ⅱ）］测定了它们的ＩＲ，ＵＶ－Ｖｉｓ光谱，在ＤＭＦ中的氧化还原半波电势（Ｅ１／２），电子转移速度常数，在乙腈中的荧光性质及锰的配合物在不同电位下的光谱变化情况。     

在DBU存在下酞菁锰配合物的合成及溶剂影响

在强有机碱１，８－二氮杂双环［５，４，０］十一－７烯（简称ＤＢＵ）存在下，ＭｎＣｌ２与邻二氰基苯在某些二元醇溶剂中可高效合成Ｍｎ（Ⅱ）Ｐｃ（Ｐｃ表示酞菁），同时研究了不同溶剂对合成产物的物种及产率的影响和不同氧化态锰的酞菁配合物在一些醇溶剂中的互变现象     

锌酞菁掺杂C60在InP电极上的光电性能研究

Ｃ＿（６０）球烯是具有高度对称性的全碳原子簇，它既是电子受体，又是电子给体，表现出特有的光物理与光化学性能￣［１，２］．近十多年来众多的研究者对具有电子给体和电子受体的共轭π电子体系化合物在光照下的行为进行了深入研究￣［３］，认为用它作为有机光电子功能材料具有十分广阔的前景。随着人们对球烯研究的不断深入，尤其是宏观量球烯的合成与分离已日趋完善，以球烯为基础的有机光电材料必将越来越受到重视．金属酞青化合物由于拥有众多π电子的共轭体系，具有良好的光敏、半导体等性能，是较好的有机光电材料￣［４．５］．但在可见光区，其光敏性仍不够强，本文以ＺｎＰｃ掺杂Ｃ＿（６０）探索其光电性能，以期提高其光敏性．同类研究尚未见文献报道．     

The molecular structure of high‐spin (S = ) manganese(II) phthalocyanine in tetrabutylammonium bromido(phthalocyaninato)manganese(II)

The title complex salt, (C₁₆H₃₆N)[MnBr(C₃₂H₁₆N₈)] or (TBA)[Mn^IIBr(Pc)] (TBA is tetrabutylammonium and Pc is phthalocyaninate), has been obtained as single crystals by the diffusion technique and its crystal structure was determined using X‐ray diffraction. The high‐spin (S = ) [Mn^IIBr(Pc)]⁻ macrocycle has a concave conformation, with an average equatorial Mn—N(Pc) bond length of 2.1187 (19) Å, an axial Mn—Br bond length of 2.5493 (7) Å and with the Mn^II cation displaced out of the 24‐atom Pc plane by 0.894 (2) Å. The geometry of the Mn^IIN₄ fragment in [Mn^IIBr(Pc)]⁻ is similar to that of the high‐spin (S = ) manganese(II) tetraphenylporphyrin (TPP) in [Mn^II(1‐MeIm)(TPP)] (1‐MeIm is 1‐methylimidazole).     

Sensitive fluorimetric method for the determination of aniline by using tetra-substituted amino aluminium phthalocyanine

This is the first report of the determination of aniline with tetra-substituted amino aluminium phthalocyanine (TAAlPc) by a fluorimetric method. In KBr-HCl solution, nitrite ion diazotizes TAAlPc, thus, the fluorescence of TAAlPc is dramatically quenched. However, there is less quenching in the presence of aniline and the recovery in fluorescence intensity is linear with the concentration of aniline. Based on this, a novel method has been developed for the determination of aniline in aqueous solutions. Under the optimal conditions, the calibration graph for aniline is from 5 to 300 ng ml⁻¹ with a 3σ limit of detection of 1.8 ng ml⁻¹. The relative standard deviation for nine replicate measurements of 100 ng ml⁻¹ aniline is 1.7%. The method was applied to the analysis of water samples with satisfactory results.     

Determination of proteins at nanogram levels by a resonance light-scattering technique with tetra-substituted sulphonated aluminum phthalocyanine

This is the first report on the determination of proteins with tetra-substituted sulphonated aluminum phthalocyanine (AlS₄Pc) by resonance light-scattering (RLS). At pH 3.0, the weak RLS of AlS₄Pc can be enhanced by the addition of proteins. Based on this, a novel quantitative method has been developed for the determination of proteins in aqueous solutions. Under optimal conditions, the linear ranges of the calibration curves were 0.050–2.0 μg ml⁻¹ for both human serum albumin (HSA) and human r-IgG. The detection limits were 12.7 ng ml⁻¹ for HSA and 16.1 ng ml⁻¹ for human r-IgG. The method has been applied to the analysis of total protein in human serum samples collected from the hospital and the results were in good agreement with those reported by the hospital, which indicates that the method presented here is not only sensitive, simple, but also reliable and suitable for practical applications.     

A Photoelectrochemical Sensor for Firstly the Detection of Amlodipine Besylate Based on an MnC4Pc Coated ZnO Composite Materials

In this study, tetracarboxylic manganese phthalocyanine coated nano-zinc oxide (MnC₄Pc-ZnO) composite material was prepared by in-situ growth method and modified with indium tin oxide (ITO) glass electrode to construct a photoelectrochemical (PEC) sensor. A PEC sensor for the determination of amlodipine besylate (AB) was developed for the first time based on the principle of precipitation reaction between heavy metal ions and dihydropyridine and the recombination suppression effect of the material. The morphology and optical properties of the MnC₄Pc-ZnO composites were characterized by scanning electron microscopy (SEM) and ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS). Chronoamperometry (i-t) and electrochemical impedance spectroscopy (EIS) were used to study the PEC behavior of ITO electrodes modified by MnC₄Pc-ZnO composite material. The study found that the MnC₄Pc-ZnO composite material has a good photocurrent response to AB, and there was a good linear relationship between the concentration range of 75 nM-250 μM, the linear equation was I(μA)=−5.2×10⁻⁸×lgC+3.2×10⁻⁸ (r=0.9947), a limit of detection (LOD) of 20 nM. In addition, MnC₄Pc-ZnO/ITO also has good selectivity and stability. The PEC sensor detects amlodipine besylate tablets, amlodipine besylate dispersible tablets, and biological samples, with standard addition recovery rates of 96.11 % and 103.96 %, respectively. The determination result has good accuracy, and the PEC sensor provides a new method for detecting AB.     

THE INTERACTION OF 2-AMINO-2-HYDROXYMETHYL-1,3-PROPANEDIOL WITH COBALT(II) AND MANGANESE(II) IONS

Abstract

The stepwise complex formation between 2-amino-2-hydroxymethyl-1,3-propanediol (TRIS) with Co(II) and Mn(II) was studied by potentiometry at constant ionic strength 2.0 M (NaClO₄) and T = (25.0 ± 0.1)°C, from pH measurements. Data of average ligand number (Bjerrum's function) were obtained from such measurements followed by integration to obtain Leden's function, F ₀(L). Graphical treatment and matrix solution of simultaneous equations have shown two overall stability constants of mononuclear stepwise complexes for the Mn(II)/TRIS system (β₁ = (5.04 ± 0.02) M^?1 and β₂ = (5.4 ± 0.5) M^?2) and three for the Co(II)/TRIS system (β₁ = (1.67 ± 0.02) × 10² M^?1, β₂ = (7.01 ± 0.05) × 10³ M^?2 and β₃ = (2.4 ± 0.4) × 10⁴ M^?3). Slow spontaneous oxidation of Co(II) solutions by dissolved oxygen, accelerated by S(IV), occurs in a buffer solution TRIS/HTRIS⁺ 0.010/0.030 M, with a synergistic effect of Mn(II).     

Darstellung und Charakterisierung von Chrom(V)- und Mangan(V)- nitridophthalocyaninen(1-) und -(2-): [MNPc(1-)]+; und [MNPc(2-)] (M=Cr,Mn)

Preparation and Characterization of Chromium of Chromium(V)- and Manganese(V)- nitridophthalocyanines(1-) and -(2-): [MNPc(1-)]⁺ and [MNPc(2-)] (M=Cr, Mn) Nitridophthalocyaninatochromium(V), [CrNPc(2-)], is prepared by oxidation of [Cr(OH)₂PC(2-)] with chlorine in the presence of excess ammonia as a paramagnetic (μ_eff = 1,99 B.M.), Microcrystalline blue powder. Through chemically very stable it reacts as well as the isostructural nitridophthalocyaninatomanganese(V) with bromine or concentrated nitric acid giving ring- oxidized darkblue nitridophthalocyaninatomental(poly)bromides or -nitrates, [MNPc(1-)]X (M=Cr, Mn; X=Br_y, NO₃; y≈?2). The nitrido-metal stretching vibration (ν(N?M)) is independent of the oxidation state of the Pc-ligands at ca. 1017 cm^?1 for the chromium and at ca. 1055 cm^?1 for the manganesenitridophthalocyanines. ν(N?Mn) is resonance Raman (r.r.) enhanced, ν(N?Cr) not. The characteristic differences in the u.v. -vis., f.i.r./m.i.r. and r.r. spectra of [MNPc(2-)] and [MNPc(1-)⁺ and the influence of aggregation of phthalocyanine-radicals are discussed.