Thermodynamics of the hydrolysis reactions of adenosine 3′,5′-(cyclic)phosphate(aq) and phosphoenolpyruvate(aq); the standard molar formation properties of 3′,5′-(cyclic)phosphate(aq) and phosphoenolpyruvate(aq)

Molar calorimetric enthalpy changes Δ_rH_m(cal) have been measured for the biochemical reactions {cAMP(aq) + H₂O(l)=AMP(aq)} and {PEP(aq) + H₂O(l)=pyruvate(aq) + phosphate(aq)}. The reactions were catalyzed, respectively, by phosphodiesterase 3^′,5^′-cyclic nucleotide and by alkaline phosphatase. The results were analyzed by using a chemical equilibrium model to obtain values of standard molar enthalpies of reaction Δ_rH_m^∘ for the respective reference reactions {cAMP⁻(aq) + H₂O(l)=HAMP⁻(aq)} and {PEP³⁻(aq) + H₂O(l)=pyruvate⁻(aq) + HPO²⁻₄(aq)}. Literature values of the apparent equilibrium constants K^′ for the reactions {ATP(aq)=cAMP(aq) + pyrophosphate(aq)}, {ATP(aq) + pyruvate(aq)=ADP(aq) + PEP(aq)}, and {ATP(aq) + pyruvate(aq) + phosphate(aq)=AMP(aq) + PEP(aq) + pyrophosphate(aq)} were also analyzed by using the chemical equilibrium model. These calculations yielded values of the equilibrium constants K and standard molar Gibbs free energy changes Δ_rG_m^∘ for ionic reference reactions that correspond to the overall biochemical reactions. Combination of the standard molar reaction property values (K, Δ_rH_m^∘, and Δ_rG_m^∘) with the standard molar formation properties of the AMP, ADP, ATP, pyrophosphate, and pyruvate species led to values of the standard molar enthalpy Δ_fH_m^∘ and Gibbs free energy of formation Δ_fG_m^∘ and the standard partial molar entropy S_m^∘ of the cAMP and PEP species. The thermochemical network appears to be reasonably well reinforced and thus lends some confidence to the accuracy of the calculated property values of the variety of species involved in the several reactions considered herein.     

MaterialSO2与Fe2O3生成Fe(Ⅱ)(aq)和硫酸盐的复相反应机理

使用DRIFTS, XPS, HPLC和IC考察了常温、常压和氧气存在下SO2与Fe2O3的复相反应, 结果表明, SO2在Fe2O3表面的反应活性与Fe2O3表面含水量密切相关, 表面含水量增加有助于Fe(Ⅱ)(aq)和硫酸盐的生成.室温下(T=291 K, 相对湿度68%), 每毫克Fe2O3在30 min内可消耗53.6 μg SO2, 生成12.6 ng Fe(Ⅱ)(aq)和56.2 μg SO2-4.反应产物 SO2-4的浓度比Fe(Ⅱ)(aq)的浓度高3个数量级, 表明在生成硫酸盐的复相反应中铁对SO2氧化具有非常高的催化活性.提出了Fe(Ⅱ)(aq) 和硫酸盐的生成机理.     

Osmotic and Activity Coefficients of CH3SO4Na(aq) and CH3SO4K(aq) at 25°C

The osmotic and activity coefficients of aqueous sodium and potassium methyl sulfates have been determined at 25°C by the isopiestic method, in the molality range from ca.0.2 to 25 and 19 mol-kg^–1, respectively. The results have been discussed in terms of the ion–ion and ion–water interactions on the basis of the Pitzer and Mayorga model and a method developed in our laboratory.     

Thermodynamics of the oxidation–reduction reaction {2 glutathionered(aq) + NADPox(aq)=glutathioneox(aq) + NADPred(aq)}

Microcalorimetry, spectrophotometry, and high-performance liquid chromatography (h.p.l.c.) have been used to conduct a thermodynamic investigation of the glutathione reductase catalyzed reaction {2 glutathione_red(aq) + NADP_ox(aq)=glutathione_ox(aq) + NADP_red(aq)}. The reaction involves the breaking of a disulfide bond and is of particular importance because of the role glutathione_red plays in the repair of enzymes. The measured values of the apparent equilibrium constant K^′ for this reaction ranged from 0.5 to 69 and were measured over a range of temperature (288.15 K to 303.15 K), pH (6.58 to 8.68), and ionic strength I_m (0.091 mol · kg⁻¹ to 0.90 mol · kg⁻¹). The results of the equilibrium and calorimetric measurements were analyzed in terms of a chemical equilibrium model that accounts for the multiplicity of ionic states of the reactants and products. These calculations led to values of thermodynamic quantities at T=298.15 K and I_m=0 for a chemical reference reaction that involves specific ionic forms. Thus, for the reaction {2 glutathione_red⁻(aq) + NADP_ox³⁻(aq)=glutathione_ox²⁻(aq) + NADP_red⁴⁻(aq) + H⁺(aq)}, the equilibrium constant K=(6.5±4.4)·10⁻¹¹, the standard molar enthalpy of reaction Δ_rH^o_m=(6.9±3.0) kJ · mol⁻¹, the standard molar Gibbs free energy change Δ_rG^o_m=(58.1±1.7) kJ · mol⁻¹, and the standard molar entropy change Δ_rS^o_m=−(172±12) J · K⁻¹ · mol⁻¹. Under approximately physiological conditions (T=311.15 K, pH=7.0, and I_m=0.25 mol · kg⁻¹ the apparent equilibrium constant K^′≈0.013. The results of the several studies of this reaction from the literature have also been examined and analyzed using the chemical equilibrium model. It was found that much of the literature is in agreement with the results of this study. Use of our results together with a value from the literature for the standard electromotive force E^o for the NADP redox reaction leads to E^o=0.166 V (T=298.15 K and I=0) for the glutathione redox reaction {glutathione_ox²⁻(aq) + 2 H⁺(aq) + 2 e⁻=2 glutathione_red⁻(aq)}. The thermodynamic results obtained in this study also permit the calculation of the standard apparent electromotive force E^′o for the biochemical redox reaction {glutathione_ox(aq) + 2 e⁻=2 glutathione_red(aq)} over a wide range of temperature, pH, and ionic strength. At T=298.15 K, I=0.25 mol · kg⁻¹, and pH=7.0, the calculated value of E^′o is −0.265 V.     

经Fe(NO3)3处理的Fe3O4纳米微粒分析

Fe3O4纳米微粒是一种制备磁性液体的重要组成部分。但Fe3O4纳米微粒不稳定,极易氧化成γ-Fe2O3,其磁化强度也会明显降低[1-2]。铁氧体还易为酸溶解,化学反应式为:MFe2O4 8H M2 2Fe3 4H2O式中M为Fe、Co、Mn等二价金属。在Massart法制备酸性离子型磁性液体的方法中,采用了Fe(NO     

Fe(CO)_3(PR_3)_2和Fe(CO)_2(PR_3)_3的结构与性质的理论研究

采用B3LYP和BP86方法,对铁羰基衍生物Fe(CO)_3(PR_3)_2和Fe(CO)_2(PR_3)_3(R=Cy,OPh和Ph)的几何和电子结构、成键特点以及热力学稳定性等进行了理论研究.计算结果表明,Fe(CO)_3(PR_3)_2的基态结构都为三角双锥的轴向双取代;对于Fe(CO)_2(PR_3)_3来说,三角双锥的腰部三取代(D_(3h))和腰部+轴向双取代(C_(2v))结构能量差别非常小.自然键轨道(NBO)分析显示,膦配体向羰基铁基团存在电荷转移,使得Fe—CO之间的共价作用有效增强.含膦配体铁羰基化合物Fe(CO)_3(PR_3)_2的第一膦配体解离能比第一羰基解离能低,预示Fe(CO)_3(PR_3)_2的反应活性比Fe(CO)_5有明显提高.     

SO2与Fe2O3生成Fe（Ⅱ）（aq）和硫酸盐的复相反应机理

使用DR IFTS,XPS,HPLC和IC考察了常温、常压和氧气存在下SO2与Fe2O3的复相反应,结果表明,SO2在Fe2O3表面的反应活性与Fe2O3表面含水量密切相关,表面含水量增加有助于Fe(Ⅱ)(aq)和硫酸盐的生成.室温下(T=291 K,相对湿度68%),每毫克Fe2O3在30 m in内可消耗53.6μg SO2,生成12.6 ngFe(Ⅱ)(aq)和56.2μg SO42-.反应产物SO42-的浓度比Fe(Ⅱ)(aq)的浓度高3个数量级,表明在生成硫酸盐的复相反应中铁对SO2氧化具有非常高的催化活性.提出了Fe(Ⅱ)(aq)和硫酸盐的生成机理.     

Synthesis and Characterization of [Fe3(As3)3(As4)]3−, a Binary Fe/As Zintl Cluster With an Fe3 Core

We report here the synthesis and structural characterization of the first binary iron arsenide cluster anion, [Fe₃(As₃)₃(As₄)]³⁻, present in both [K([2.2.2]crypt)]₃[Fe₃(As₃)₃(As₄)] ( 1 ) and [K(18-crown-6)]₃[Fe₃(As₃)₃(As₄)]⋅en ( 2 ). The cluster contains an Fe₃ triangle with three short Fe−Fe bond lengths (2.494(1) Å, 2.459(1) Å and 2.668(2) Å for 1 , 2.471(1) Å, 2.473(1) Å and 2.660(1) Å for 2 ), bridged by a 2-butene-like As₄ unit. An analysis of the electronic structure using DFT reveals a triplet ground state with direct Fe−Fe bonds stabilizing the Fe₃ core.     

螯合物(FcCOCHCOCH3)2Cu与(FcCOCHCOCH3)3Fe的合成及其燃烧催化活性

含有铁、铬、铜等过渡元素的一些化合物,如铁的氧化物、铜的亚铬酸盐、二茂铁及其衍生物等都可作为复合固体推进剂的燃速催化剂.在二茂铁衍生物中主要是烷基衍生物,如叔丁基二茂铁、正辛基二茂铁、γ-二茂铁丁酸丁酯以及1,7-二(二茂铁基)庚烷、2,2-双(乙基二茂铁基)丙烷等.上述催化剂的变化趋势是由单二茂铁基向双二茂铁基发展,     

Heterometallic “butterfly” cluster [Fe3(CO)9(μ3-OBut)Au(PPh3)]

Alkylation of the [Fe₃(μ₃-O)(CO)₉]²⁻ dianion withtert-butyl iodide afforded the [Fe₃(μ₃OBu¹)(CO)₉]⁻ monoanion. The reaction of the latter with Au(PPh₃)Cl in the presence of TIBF₄ yielded the new heterometallic “butterfly” cluster [Fe₃(CO)₉(μ₃-OBu^t)Au(PPh₃)]. According to the X-ray data, both clusters synthesized contain the unchanged Fe₃(μ₃-O) fragment of the initial dianion. The addition of the Au(PPh₃) fragment to the monoanion occurred in such a way as to minimize steric changes. As a result, a “turned inside out” heterometallic “butterfly”, which contains the μ₃-O ligand on the outside rather than on the inside, was obtained. The dihedral angle characterizing the “butterfly” is 151°. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1779–1783, September, 1999.     

Multiple Bonding Between Group 3 Metals and Fe(CO)3−

Heteronuclear Group 3 metal/iron carbonyl anion complexes ScFe(CO)₃⁻, YFe(CO)₃⁻, and LaFe(CO)₃⁻ are prepared in the gas phase and studied by mass-selective infrared (IR) photodissociation spectroscopy as well as quantum-chemical calculations. All three anion complexes are characterized to have a metal–metal-bonded C_3v equilibrium geometry with all three carbonyl ligands bonded to the iron center and a closed-shell singlet electronic ground state. Bonding analyses reveal that there are multiple bonding interactions between the bare group-3 elements and the Fe(CO)₃⁻ fragment. Besides one covalent electron-sharing metal–metal σ bond and two dative π bonds from Fe to the Group 3 metal, there is additional multicenter covalent bonding with the Group 3 atom bonded to Fe and the carbon atoms.     

Transformationen von clustern mit dem (μ3-RP)Fe3(CO)9-Gerüst. Synthese und reaktionen von [(μ3-RP)Fe3(CO)9]2−

The clusters (μ₃-RP)Fe₃(CO)₁₀ (1) or (μ₃-RP)Fe₃(CO)₉(μ₂-H)₂ (2) can reversibly be transformed into the cluster anions [(μ₃-RP)Fe₃(CO)₉ (μ₂-H)]⁻ (3) and [(μ₃-RP)Fe₃(CO)₉]²⁻ (4). The pyrophoric clusters 4 react with the divalent electrophile CH₂I₂ to give the complexes (μ₃-η²-RP=CH₂)Fe₃(CO)₁₀ (5), which contain a cluster-stabilized phosphaalkene, RP=CH₂, as a ligand. With monovalent electrophiles R′X, such as Me₂SO₄, compound 4 (R = anisyl), yields, upon protolytic work-up, the complexes (μ₃-η³-R′P-anisyl)Fe₃(CO)₉(μ₂-H) (6) in which the phosphorus-bound aryl residue of the μ₂-bridging phosphide ligand (R′P-anisyl) forms an η²-coordination to the third iron atom of the cluster. The η²-coordination of the aryl substituent may be reversibly released by two-electron ligands L under formation of (μ₂-R′P-anisyl)(μ₂-H)Fe₃(CO)₉L (7). In addition, the transformation sequence of 5 into 6 is accomplished by an H⁻, H⁺ addition sequence. The experiments are documented by analytic and spectroscopic data as well as by X-ray analyses.     

关于Fe(OH)3略有两性的实验研究

本文通过实验得到Fe(OH)3略有两性的尺度,解决了Fe(OH)3能溶于多少浓度的强碱中的问题。现行教材中讲Fe(OH)3略有两性,但碱性强于酸性,只有新沉淀出来的Fe(OH)3能溶于浓的强碱溶液中。然而,对初学无机化学的人来说,这略有两性的尺度如何把握呢?Fe(OH)3能部分溶于多少浓度的强碱中呢?为此做了如下的实验。     

New Fe3+/Cr3+ perovskites with anomalous transport properties: the solid solution La(x)Bi(1-x)Fe(0.5)Cr(0.5)O3 (0.4 ≤ x ≤ 1)

In this work, the sol-gel synthesis, structural characterization, and transport properties of a new solid solution of the general formula La(x)Bi(1-x)Fe(0.5)Cr(0.5)O(3) (0.4 ≤ x ≤ 1) are presented. The solubility limit x has been determined and variation of the lattice parameters measured through profile fitting. The cell parameters, space group, and atomic positions, as obtained by the Rietveld refinement of X-ray diffraction data, are reported. This analysis and electron diffraction studies as well do not reveal any evidence of Fe/Cr ordering. Regarding the transport properties, magnetic and electric characterizations are described. The electrical response with the temperature and frequency has been studied, and a "positive temperature coefficient" for the resistivity has been found for temperatures between 270 and 400 °C. The magnetic behavior is striking because, for all materials studied, zero-field-cooling curves appear above field-cooling ones, an anomalous feature that is interpreted as being due to complex ferromagnetic/antiferromagnetic interactions in the B perovskite sublattice.     

A structural and Mössbauer study of complexes with Fe(2)(micro-O(H))(2) cores: stepwise oxidation from Fe(II)(micro-OH)(2)Fe(II) through Fe(II)(micro-OH)(2)Fe(III) to Fe(III)(micro-O)(micro-OH)Fe(III)

Dinuclear non-heme iron clusters containing oxo, hydroxo, or carboxylato bridges are found in a number of enzymes involved in O(2) metabolism such as methane monooxygenase, ribonucleotide reductase, and fatty acid desaturases. Efforts to model structural and/or functional features of the protein-bound clusters have prompted the preparation and study of complexes that contain Fe(micro-O(H))(2)Fe cores. Here we report the structures and spectroscopic properties of a family of diiron complexes with the same tetradentate N4 ligand in one ligand topology, namely [(alpha-BPMCN)(2)Fe(II)(2)(micro-OH)(2)](CF(3)SO(3))(2) (1), [(alpha-BPMCN)(2)Fe(II)Fe(III)(micro-OH)(2)](CF(3)SO(3))(3) (2), and [(alpha-BPMCN)(2)Fe(III)(2)(micro-O)(micro-OH)](CF(3)SO(3))(3) (3) (BPMCN = N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane). Stepwise one-electron oxidations of 1 to 2 and then to 3 demonstrate the versatility of the Fe(micro-O(H))(2)Fe diamond core to support a number of oxidation states with little structural rearrangement. Insight into the electronic structure of 1, 2', and 3 has been obtained from a detailed M?ssbauer investigation (2' differs from 2 in having a different complement of counterions). Mixed-valence complex 2' is ferromagnetically coupled, with J = -15 +/- 5 cm(-)(1) (H = JS(1).S(2)). For the S = (9)/(2) ground multiplet we have determined the zero-field splitting parameter, D(9/2) = -1.5 +/- 0.1 cm(-)(1), and the hyperfine parameters of the ferric and ferrous sites. For T < 12 K, the S = (9)/(2) multiplet has uncommon relaxation behavior. Thus, M(S) = -(9)/(2) <--> M(S) = +(9)/(2) ground state transition is slow while deltaM(S) = +/-1 transitions between equally signed M(S) levels are fast on the time scale of M?ssbauer spectroscopy. Below 100 K, complex 2' is trapped in the Fe(1)(III)Fe(2)(II) ground state; above this temperature, it exhibits thermally assisted electron hopping into the state Fe(1)(II)Fe(2)(III). The temperature dependence of the isomer shifts was corrected for second-order Doppler shift, obtained from the study of diferrous 1. The resultant true shifts were analyzed in a two-state hopping model. The diferric complex 3 is antiferromagnetically coupled with J = 90 +/- 15 cm(-)(1), estimated from a variable-temperature M?ssbauer analysis.     

Solvate Molecule Effects and Unusual (57)Fe Mössbauer Line Broadening in the Valence Detrapping of Mixed-Valence [Fe(3)O(O(2)CCH(3))(6)(3-Et-py)(3)].S

A new series of mixed-valence &mgr;(3)-oxo-bridged Fe(3)O complexes with the composition [Fe(3)O(O(2)CCH(3))(6)(3-Et-py)(3)].S, where 3-Et-py is 3-ethylpyridine and the solvate molecule S is either 0.5C(6)H(5)CH(3) (1), 0.5C(6)H(6) (2), CH(3)CN (3), or CH(3)CCl(3) (4), is reported. The complex [Fe(3)O(O(2)CCH(3))(6)(3-Et-py)(3)].0.5C(6)H(5)CH(3) (1) crystallizes in the orthorhombic space group Fdd2 which at 298 K has a unit cell with a = 22.726(8) ?, b = 35.643(14) ?, c = 20.816(6) ?, and Z = 16. Refinement with 5720 observed [F > 5sigma(F(o))] reflections gave R = 0.0337 and R(w) = 0.0390. An analysis of the bond lengths in complex 1 shows that it is the most valence-trapped Fe(3)O complex reported at room temperature. The complex [Fe(3)O(O(2)CCH(3))(6)(3-Et-py)(3)].CH(3)CCl(3) (4) crystallizes in the triclinic space group P&onemacr; which at 238 K has a unit cell with a = 12.764(2) ?, b = 13.1472(2) ?, c = 15.896(3) ?, alpha = 78.01(2) degrees, beta = 89.38(2) degrees, gamma = 61.38(1) degrees, and Z = 2. Refinement with 6264 observed [F > 5sigma(F(o))] reflections gave R = 0.0435 and R(w) = 0.0583. In this &mgr;(3)-oxo-bridged complex all three iron ions are inequivalent. Powder X-ray diffraction patterns taken at room temperature show that complexes 1 and 2 are isostructural and that complexes 3 and 4 are isostructural. Variable-temperature (57)Fe M?ssbauer spectra were collected for all four complexes. The data for complexes 1 and 2 clearly indicate that these two complexes are totally valence trapped. On the other hand, M?ssbauer spectra (43-293 K) for complexes 3 and 4 show that these two complexes become valence detrapped at temperatures near room temperature. Two doublets are seen at low temperature and they move together to become a single doublet at approximately 293 K. Examination of the line width versus temperature for each of the two components of the two doublets points to a curiosity. The two components of the "Fe(III)" doublet and the lower-velocity component of the "Fe(II)" doublet do not exhibit any line broadening, whereas the higher velocity "Fe(II)" component shows a surge in line width in the approximately 70-150 K range. Possible explanations for these unusual line width responses are discussed.     

(μ3-S)Fe2CoCu(PPh3)2(CO)8催化苯乙烯环丙烷化反应研究

以异核金属原子簇合物为催化剂的配位催化反应, 已在均相催化反应中得到应用. 簇合物中不同金属间的协同作用使其在催化领域展现出广阔的应用前景[1]. 然而,催化反应中簇合物是否以完整的骨架起催化作用,一直是人们关注的焦点. 在金属原子簇作催化剂前体的均相催化反应中,迄今只在少数的例子中有确凿的证据表明原子簇整体分子起催化作用[2]. 一般认为,在配位饱和的金属簇合物的催化反应中,簇合物稳定性越好,催化活性越差;而活性好的催化剂前体,簇合物骨架常解体.     

流动注射分光光度法同时测定Fe(Ⅱ)和Fe(Ⅲ)

将流动注射技术引入邻菲罗啉分光光度法测定Fe2+分析体系,采用单阀双带镀镉锌片还原柱带隔离的阀体流路,建立了同时测定微量Fe2+和Fe3+的分析方法。Fe2+的测定范围为0~10 mg/L,检出限为1.2×10-6mg/L;Fe3+的测定范围为0~12 mg/L,检出限为1.8×10-6mg/L。方法用于水中Fe2+和Fe3+的同时测定。