Holographic Storage Properties of In：Fe：Mn：LiNbO3 Crystals

In:Fe:Mn:LiNbO3(LN) crystals were grown in air atmosphere by Czochralski method with different concentration of In (0,1,2,3 mol%) in the melts,while the contents of Fe2O3 and MnO were 0.1 and 0.5 mol%,respectively. The location of doping ions was analyzed by Ultraviolet-visible absorption spectra and differential thermal analysis. The diffraction efficiency (η),writing time (τw) and erasure time (τe) of the crystals were measured by two-beam coupling experiment. The dynamic range and photorefractive sensitivity have also been calculated. The results showed that with the increase of In ions in the melt,the absorption edge of In:Fe:Mn:LN crystal shifts to the violet firstly and then makes the Einstein shift,the Curie temperature of crystal increases firstly and then decreases,the storage ratio speeds up,diffraction efficiency decreases,and dynamic range and photorefractive sensitivity increase. The mechanism of holographic storage properties of In:Fe: Mn:LN crystal with different doping concentration of In3+ was investigated,suggesting the In: Fe:Mn:LN crystals are excellent holographic storage materiel with better synthetical properties than Fe:Mn:LN crystals.     

A new flavonoid with a benzoic acid substituent from Selaginella uncinata

6-（5-Carboxyl-2-methoxyphenyl）-apigenin （1）, a new flavonoid, was isolated from the 60% ethanol extract of Selaginella uncinata （Desv.） Spring. Its structure was established by spectroscopic methods. Compound 1 represents the first example of the flavonoids possessing a benzoic acid substituent at C-6.     

基团共轭效应研究Ⅱ：^13C核磁共振的化学位移与取代基的共轭效应强度

引言在定量和定性研究有机化合物的结构与性质的关系中,最广泛使用的是Hammett等所提出的σ_m、σ_p等取代基常数以及基团的诱导(场)效应和共轭效应常数。在建立基团的共轭效应常数方面,人们做了大量的工作,但多数工作是基于对基团的Hammett常数σ的人为分解上,建立的模型和分解方式(系数因子)不同,则得到不同的结果。另一方面纯理论计算工作大多引入较多参数,使计算复杂和使用不便。作者曾在建立表征诱导效应大小的     

Effect of Manganese Incorporation Manner on an Iron-Based Catalyst for Fischer-Tropsch Synthesis

A systematic study was undertaken to investigate the effects of the manganese incorpo- ration manner on the textural properties,bulk and surface phase compositions,reduction/carburization behaviors,and surface basicity of an iron-based Fischer-Tropsch synthesis(FTS)catalyst.The cata- lyst samples were characterized by N_2 physisorption,X-ray photoelectron spectroscopy(XPS),H_2(or CO)temperature-programmed reduction(TPR),CO_2 temperature-programmed desorption(TPD),and M(?)ssbauer spectroscopy.The FTS performance of the catalysts was studied in a slurry-phase continuously stirred tank reactor(CSTR).The characterization results indicated that the manganese promoter incor- porated by using the coprecipitation method could improve the dispersion of iron oxide,and decrease the size of the iron oxide crystallite.The manganese incorporated with the impregnation method is enriched on the catalyst's surface.The manganese promoter added with the impregnation method suppresses the reduction and carburization of the catalyst in H_2,CO,and syngas because of the excessive enrichment of manganese on the catalyst surface.The catalyst added manganese using the coprecipitation method has the highest CO conversion(51.9%)and the lowest selectivity for heavy hydrocarbons(C_(12 )).     

Zinc Borohydride-Ionic Liquid： Stable and Efficient System for Reductive Reaction of Aldehydes with Primary Amines to Corresponding Secondary Amines

Ionic liquids（ILs） are attracting much attention in various fields of chemical synthesis, electrochemical applications, liquid-liquid extractions, as well as biotransformations. Among those fields, the application of ILs as the potential green solvent for a wide variety of synthetic processes is an area of intense researches. High yield, high selectivity, and good catalytic charac-teristics have usually been achieved. After the isolation of products, ILs can usually be recovered and recycled many times by simple treating procedures, such as, filtration, extraction, and dryness.     

Appended corrole manganese complexes:Catalysis and axial-ligand effect

A series of N-base appended corroles and their manganese complexes were synthesized and their binding constants with three different nitrogenous ligands, triethylamine, N-methylimidazole and pyridine, were evaluated by spectroscopy. Kinetic studies indicated that the presence of appended N- donor ligands may cause a significant enhancement of the rate of oxygen atom transfers （OAT） from （oxo）manganese（V） corrole to alkene, and the stronger axial ligand binding has impact on the rate of the oxidation reaction. Turnover frequency （TOF） for the catalytic oxidation of alkenes by appended manganese corroles varies with the following ligand order： acetamido 〈 pyridyl 〈 imidazolyl. The influence of the external axial ligands on the catalytic epoxidation was investigated by using appended acetamido manganese corrole as catalyst, with the results revealing that N-methylimidazole gave the best enhancement on the yields of total oxidation products among the investigated nitrogenous ligands.     

The substituent effect of π-electron delocalization in N-methylamino-nitropyridine derivatives: crystal structure and DFT calculations

Structural Chemistry - The crystal and molecular structures of 3-(N-methylamino)-2-nitropyridine, 5-(N-methylamino)-2-nitropyridine and 2-(N-methylamino)-5-nitropyridine have been characterized by...     

Organic Reactions in Ionic Liquids： Ionic Liquid-promoted Efficient Synthesis of Disubstituted and Trisubstituted Thioureas Derivatives

In ionic liquid [Bmim][BF4], a series of disubstituted and trisubstituted thiourea derivatives were synthesized from phenyl and butyl isothiocyanate with a variety of amine in excellent yield.     

Mg1.75Al0.25Ni1-xCrx (0≤x≤0.2)合金的制备及其性能

用扩散烧结法制备了Mg1.75Al0.25Ni1-xCr（0≤x≤0．2）系列合金,XRD结构分析表明,用Cr部分替代Mg1.75Al0.25Ni中的Ni,合金的晶体结构并不发生改变,主相为具有立方Ti2Ni结构的Mg3AlNi2相,只是其晶格常数α变大,Cr的替代提高了合金的放电容量,经过一个充放电循环后达到最大值。当x为0．1时,有利于提高合金电极的循环稳定性。测试4种合金阳极极化曲线发现,其腐蚀电位由正到负的顺序为Mg1.75Al0.25Ni0.9Cr0.1〉Mg1.75Al0.25Ni〉Mg1.75Al0.25Ni0.8Cr0.2〉Mg2Ni,说明Mg1.75Al0.25Ni0.9Cr0.1合金具有相对较好的抗腐蚀性．该系列合金循环稳定性结果也支持这一结论．用球磨方法改变合金性能,发现合金的相组成和相结构在球磨后均发生了变化,合金不再需要活化过程,但其放电容量并没有得到提高。     

从软锰矿到锰同位素：锰元素的发现及其概念的发展

1771年,瑞典化学家托伯恩·伯格曼明确提出软锰矿中含有新元素的假说,并将之初步命名为manganese(锰)。1774年,瑞典矿物学家甘恩首次制取出锰单质,锰元素假说得以验证。同年,瑞典化学家舍勒对锰单质的性质进行了表征,并确认manganese(锰)一词为该元素命名,锰元素的概念正式形成。同位素化学兴起后,1923年至今共发现25种锰的同位素,锰元素被明确定义为质子数为25的所有原子的总称。锰元素的发现浓缩了19世纪初系统分析法形成以前早期分析化学的发展,其概念的演变渗透出系统分析法的形成以及同位素化学的兴起,在定性到定量的研究过程中体现了科学思想和方法的进步。     

DNA cleavage mediated by water-soluble manganese corrole

The DNA nuclease-like activity of a water soluble manganese corrole 5,10,15-tris(N-methyl-4-pyridyl)- corrolatomanganese (Ⅲ)(Mn~ⅢTMPyC) has been investigated.Mn~ⅢTMPyC may bind strongly to DNA via outside groove binding mode as indicated by absorption spectra,viscosity measurements and CD spectra.Mn~ⅢTMPyC exhibited excellent catalytic activity in the DNA oxidative cleavage in the presence of hydroperoxide.     

The heavy atom effect on photocleavage of DNA by mono-hydroxyl halogenated corroles

<正>DNA photocleavage properties of halogenated mono-hydroxyl corrole 1-5 were investigated.It was found that these corroles were able to photocleavage supercoiled pBR 322 DNA(SC) into nicked-circular DNA(NC).The activity of these corroles follows an order of 432≈15.The photosensitized singlet oxygen(Φ_△) quantum yield by these corroles also follows that same order,showing the photocleavage activity is related to the heavy atom effect of halogen atoms on corroles.     

Unusual demetalation of iron from [2]ferrocenophane skeleton of di-nuclear ferracycle carbonyl complex

Photolysis of a hexane solution containing 1,1′- bis (trimethylsilylethynyl)ferrocene ( 1 ) and Fe (CO)₅, under argon at 0 °C led to the formation of dinuclear complexes [Fe (CO)₂{η²:η² – C (SiMe₃) = C(C₅H₄)FeC(C₅H₄) = C (SiMe₃)Fe (CO)₃}–μ–CO] ( 2 ) and [Fe (CO)₂{η²:η²–C (SiMe₃) = C(C₅H₅)–C(C₅H₅) = C (SiMe₃)Fe (CO)₃}–μ–CO] ( 3 ). DFT calculations support the experimentally observed demetalation of ferrocene unit of 2 to 3 in presence of water. These compounds were comprehensively characterized by IR and ¹H and ¹³C NMR spectroscopy and crystallographically ( 1 and 3 ).     

Halogenido and Pseudohalogenido Complexes of (2,3,7,8,12,13,17,18‐Octaethyl‐5,15‐di‐p‐tolylcorrolato)manganese(IV)

A set of porphyrinoid manganese(IV) complexes with the 2,3,7,8,12,13,17,18‐octaethyl‐5,15‐di‐p‐tolylcorrolato ligand [(oedtc)Mn^IVX] (X = Cl, Br, I) was prepared by oxidation of a manganese(III) precursor. The most unexpected complex in this series, [(oedtc)Mn^IVI], was found to display significant thermal stability despite the unusual Mn^IV‐I bond and could be investigated by X‐ray diffraction. Attempted ligand exchange reactions of the chlorido derivative with the pseudohalide anions cyanide, azide, cyanate and thiocyanate yielded the desired [(oedtc)Mn^IVX] complex only as the isothiocyanate derivative while for the other species the reduction to manganese(III) was observed.     

High-valent imido complexes of manganese and chromium corroles

The oxidation reaction of M(tpfc) [M = Mn or Cr and tpfc = tris(pentafluorophenyl)corrole] with aryl azides under photolytic or thermal conditions gives the first examples of mononuclear imido complexes of manganese(V) and chromium(V). These complexes have been characterized by NMR, mass spectrometry, UV-vis, EPR, elemental analysis, and cyclic voltammetry. Two X-ray structures have been obtained for Mn(tpfc)(NMes) and Cr(tpfc)(NMes) [Mes = 2,4,6-(CH(3))(3)C(6)H(2)]. Short metal-imido bonds (1.610 and 1.635 Angstroms) as well as nearly linear M-N-C angles are consistent with triple M triple-bond NR bond formation. The kinetics of nitrene [NR] group transfer from manganese(V) corroles to various organic phosphines have been defined. Reduction of the manganese(V) corrolato complex affords phosphine imine and Mn(III) with reaction rates that are sensitive to steric and electronic elements of the phosphine substrate. An analogous manganese complex with a variant corrole ligand containing bromine atoms in the beta-pyrrole positions, Mn(Br(8)tpfc)(NAr), has been prepared and studied. Its reaction with PEt(3) is 250x faster than that of the parent tpfc complex, and its Mn(V/IV) couple is shifted by 370 mV to a more positive potential. The EPR spectra of chromium(V) imido corroles reveal a rich signal at ambient temperature consistent with Cr(V) triple-bond NR (d(1), S = 1/2) containing a localized spin density in the d(xy) orbital, and an anisotropic signal at liquid nitrogen temperature. Our results demonstrate the synthetic utility of organic aryl azides in the preparation of mononuclear metal imido complexes previously considered elusive, and suggest strong sigma-donation as the underlying factor in stabilizing high-valent metals by corrole ligands.     

锰(Ⅲ)Corrole配合物催化DNA氧化断裂

报道了这类单羟基Corrole锰(Ⅲ)配合物对DNA的催化氧化断裂作用.     

Corrole锰-氧配合物的稳定性研究

对5,10,15-三(五氟苯基)-Corrole(tpfc)Mn(V)≡O配合物的稳定性进行了研究. 以二氯甲烷溶剂为参考,乙醇、正辛醇、乙醚、四氢呋喃、二甲基亚砜、甲苯能加速(tpfc)MnV≡O的衰减,而N’N二甲基甲酰胺、水、乙酸乙酯、丙酮能减缓(tpfc)MnV≡O的衰减. (tpfc)MnV≡O与盐酸、醋酸反应生成(tpfc)MnIV-Cl、(tpfc)MnIV-O2CCH3. (tpfc)MnIII能与咪唑、四甲基咪唑、吡啶形成1:1的配合物,轴向配位常数按Imidazole >4-Methylimidazole >Py顺次减弱,在这些轴向配体存在时,(tpfc)MnV≡O的稳定性显著降低. 轴向配体与(tpfc)MnIII的结合导致其MnIII/MnIV半波电位降低. XPS实验结果显示(tpfc)MnIII与轴向配体结合后,其中心金属锰的结合能Mn2p3/2减少,减少程度与轴向配体的给电子能力有关.     

Catalase mimics of a manganese(II) complex: The effect of axial ligands and pH

The mononuclear [Mn(indH)Cl₂](CH₃OH) (indH: 1,3-bis(2′-pyridylimino)-isoindoline) complex has been prepared and characterized by various techniques such as elemental analysis, IR, UV–vis, ESR spectroscopy and X-ray diffraction. The title compound in the presence of a base such as 1-methylimidazole, imidazole or pyridine is efficient catalyst for the disproportionation of H₂O₂ in CH₃CN. Among the various nitrogenous bases investigated in this study imidazole and substituted imidazoles with strong π-donating ability show better co-catalytic effect.

In case of aqueous solution the complex [Mn(indH)Cl₂](CH₃OH) shows much higher catalytic activity, and the initial rate of the disproportionation of H₂O₂ increases with increasing pH and goes through a maximum, which was found at pH  9.6. In this pH value the reaction shows first-order dependence on the catalyst, and saturation kinetics on [H₂O₂] with V_max = 8.1 × 10⁻³ Ms⁻¹, K_M = 489 mM, k_cat = 38 ± 2 s⁻¹ and k₂(k_cat/K_M) = 79 ± 4 M⁻¹s⁻¹.     

Reductive dissolution of microparticulate manganese oxides

Electrochemical dissolution of immobilised microparticulate Mn(III,IV) oxides in slightly acidic solution (pH 4.4) was found to be a very general reaction, which is responsible for well-defined voltammetric peaks. Dissolution of six Mn(III,IV) oxides is initiated by the reduction of Mn(IV) to Mn(III) in the solid phase, which is followed by a massive dissolution via further reduction of Mn(III) to Mn(II), which finally yields soluble Mn²⁺. The reactivity of manganese oxides depends on their structure: the most reactive are amorphous (δ-MnO₂) and layered structures (birnessite); more resistant toward reductive dissolution are α- and λ-MnO₂ and electrochemical manganese dioxide; and least reactive is β-MnO₂. Reductive dissolution of LiMn₂O₄ resembles that of λ-MnO₂, whereas CaMnO₃ dissolves via a different reaction mechanism.