共查询到20条相似文献,搜索用时 531 毫秒
1.
Hasan Marai Ewa Kita Emilia Kiersikowska Sylwia Kuchta Anna Bajek Tomasz Drewa 《Transition Metal Chemistry》2012,37(4):337-344
Three chromium(III) complexes with asparagine (Asn) and histidine (His) of the [Cr(ox)2(Aa)]2− type, where Aa = N,O–Asn, N,O–His or N,N′–His, were obtained and characterized in solution. The complexes with N,O–Aa undergo acid-catalysed aquation to give a free amino acid and cis-[Cr(ox)2(H2O)2]−, whereas the complex with N,N′–His undergoes parallel reaction paths: (1) isomerization to the N,O–His complex and (2) liberation of an oxalate ligand. Kinetics of the N,O–Aa complexes in HClO4 media were studied spectrophotometrically under pseudo-first-order conditions. The absorbance changes were attributed to
the chelate ring opening at the Cr–N bond. The linear dependence of rate constants on [H+] was established, and a mechanism for the chelate ring cleavage was postulated. The existence of a metastable intermediate
with O-monodentate Aa ligand was proved experimentally. Effect of [Cr(ox)2(Aa)]2− on 3T3 fibroblasts proliferation was studied. The tests revealed low cytotoxicity of the complexes. Complexes with Ala, His
and Cys are good candidates for biochromium sources. 相似文献
2.
Sumitava Khan Subhasis Roy Kishalay Bhar Partha Mitra Alexandra M. Z. Slawin Barindra Kumar Ghosh 《Transition Metal Chemistry》2011,36(1):99-106
Two hexacoordinated mononuclear Co(III) compounds of the type cis-[Co(L)(N3)2] X [1, X = ClO4; 2, X = PF6; L = N,N′-(bis(pyridine-2-yl)benzylidine)-1,4-butanediamine] have been synthesized and characterized by physicochemical and spectroscopic
methods. The crystal structures of complexes 1 and 2 both have distorted octahedral geometry with two terminal azides in mutual cis orientations. In the crystalline state, two
mononuclear units of 1 are associated by weak C–H…π interactions to produce a dimeric unit, which packs through C–H…O hydrogen bonds and π…π interactions
leading to a 2-D continuum. The mononuclear units in 2 are engaged in weak cooperative intermolecular C–H…π interactions and multiple C–H…F hydrogen bonds giving rise to a 3-D
network structure. These diamagnetic compounds are redox active and show luminescence in DMF solutions. 相似文献
3.
R. F. Balabaeva 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2011,85(7):1288-1290
Using the experimental values ΔH
Hexc and ΔS
Hexc (ΔH
Nexc and ΔS
Nexc) for solid solutions of hydrogen and nitrogen in molybdenum, we calculate the parameters ɛHMand ɛNM of interaction between hydrogen (nitrogen) and molybdenum lattice doped with small additives of transition metals M; the
values of the activity coefficients on hydrogen and nitrogen γHM and γNM, ΔH
H, ΔH
N, ΔS
H, ΔS
N; enthalpy (ηHM and ηNM) and entropy (σHM and σNM) parameters of interaction over the 1100–1300 K range for alloys of Mo1 − y
M
y
H
x
and Mo1 − y
M
y
N
x
types (y = 0.01 and 0.02; x = 0.01 and 0.02). 相似文献
4.
A series of hybrid mesoporous SBA-15 materials containing four iron(III) Schiff base complexes of the type [FeL
x
(NO3)] (x = 4–7, L = N,N′-bis(salicylidene)ethylenediamine, N,N′-bis(salicylidene)diethylenetriamine, N,N′-bis(salicylidene)o-phenylenediamine, N,N′-bis(3-nitro-salicylidene)ethylenediamine) was synthesized by a post-grafting route. The XRD, N2 adsorption/desorption and TEM measurements confirmed the structural integrity of the mesoporous hosts, and the spectroscopic
characterization techniques (FT-IR, UV–vis spectroscopy, 1H NMR) confirmed the ligands and the successful anchoring of iron(III) Schiff base complexes over the modified mesoporous
support. Quantification of the supported ligand and metal was carried out by TG/DSC and ICP-AES techniques. The catalyst FeL7-SBA resulting from N,N′-bis(3-nitro-salicylidene)ethylenediamine) ligand was considerably active for the aerobic epoxidation
of styrene, in which the highest conversion of styrene reached 83.6%, and the selectivity to styrene oxide was 83.0%. Moreover,
it was also found that the catalytic activity increases with the decrease in the electron-donating ability of the Schiff bases,
and the selectivity varies according to the types of substituents in the ligands. 相似文献
5.
To date, no reference method for the extraction of labile Mn species from biological tissues is published which provides sufficient
extraction efficiency combined with monitoring speciation. Here, an extraction method is reported using cryogenic conditions
(+N) under inert gas atmosphere. Fresh brain and liver tissues were used, then stored either 1 day (+N) or 1 month in N2liq (+N 1 m) to evaluate degradation effects during long-term storage. Both attempts were compared to a previous extraction method
(−N) using neither N2liq nor storage ability. Mn and Fe concentrations in extracts and pellets were determined with inductively coupled plasma (ICP)-atomic
emission spectroscopy (AES) and compared to acid digests of the same sample. Element ratios of extracts/digest indicated the
extraction efficiency, which was increased from 17% (−N) to 26% (+N) for Mn in brain or from 28% (−N) to 44% (+N) in liver extracts. For Fe species, the increase was only from 40% (−N) to 44% (+N) in brain but from 64% (−N) to 74% (+N) in liver. Size exclusion chromatography (SEC)-ICP-mass spectrometry (MS) was employed to screen for Mn and Fe species pattern
in extracts. In brain, surplus extracted Mn (+N, +N 1 m) was assigned to organic Mn species, mainly from the 0.7–4 kDa fraction, while in the liver, it was seen in the 70–80 kDa
fraction. Fe speciation was similar for −N and +N methods in brain extracts. In liver, higher amounts of Fe species were extracted from the 140–160 kDa fraction. Storage at
−196 °C for 1 month did neither affect Mn speciation in brain nor in liver extracts. Fe species pattern showed a negligible
shift (≤5%) from 140–160 to 70–80 kDa fraction in liver extracts stored 1 month in N2liq. 相似文献
6.
Peroxydisulfate (PDS) oxidizes N,N′-ethylenebis(isonitrosoacetyleacetoneimine)copper(II) complex, CuIIL, to the corresponding copper(III) complex, [CuIIIL]+. The kinetic runs were performed in the presence of EDTA to scavenge any trace metal impurities. The kinetics of the reaction
at constant pH, ionic strength, and temperature obeys the rate law d[CuIIIL]/dt = 2k
2[CuIIL][S2O8
2−] with k
2 having a value of (8.85 ± 0.32) × 10−2 M−1 s−1 at μ = 0.30 M and T = 25.0 °C. The rate constant k
2 is not affected by variation of pH over the range 3.60–5.20. The second order rate constant is also unaffected by changing
ionic strength. The values of k
obs were determined over the temperature 25.0–40.0 °C range. The enthalpy of activation, ∆H*, and entropy of activation, ∆S*, have been calculated as 34.9 ± 0.5 kJ mol−1 and −173.3 ± 11.4 J K−1 mol−1, respectively. The kinetics of this reaction, as far as we know, is the first evidence that copper(III) is the likely reactive
species in copper catalyzed PDS oxidation reactions. 相似文献
7.
P. O. Dunstan 《Journal of Thermal Analysis and Calorimetry》2009,97(2):755-760
The [InCl3(L)
n
] (where L is 2,2′-bipyridine (bipy), 2,2′-bipyridine N,N′-dioxide (bipyNO), N,N-dimethylacetamide (dma), urea (u), thiourea (tu) or 1,1,3,3-tetramethylthiourea (tmtu); n = 1.5, 3 or 4) were synthesized and characterized by melting points, elemental analysis, thermal analysis and IR spectroscopy.
The enthalpies of dissolution of the adducts, Indium(III) chloride and ligands in 1.2 M aqueous HCl were measured and by using
thermochemical cycles, the following thermochemical parameters for the adducts have been determined: the standard enthalpies
for the Lewis acid/base reactions (Δr
H
θ), the standard enthalpies of formation (Δf
H
θ), the lattice standard enthalpies (ΔM
H
θ), and the standard enthalpies of decomposition (ΔD
H
θ). 相似文献
8.
Callus induction and plant regeneration from different explants of Actinidia deliciosa 总被引:1,自引:0,他引:1
In this study, an efficient procedure was developed for callus induction and regeneration of kiwifruit (Actinidia deliciosa) using different organs of shoots developed under in vitro conditions. Effects of explants source and media (M1, 1.0 mg l−1 BA + 2.0 mg l−1 2,4-D–M2, 1.0 mg l−1 NAA + 2.0 mg l−1 2,4-D) on initiation of callus were examined in order to obtain callus for organogenesis. The best callus for plant regeneration
was obtained from leaf explants on Murashige and Skoog’s medium (MS) supplemented with M2. Formation of callus from leaf of kiwifruit (A. deliciosa) was cultured in MS medium containing different concentration of N6-benzylaminopurin (BA; 0.0, 1.0, 2.0, 4.0, 6.0, 8.0 mg l−1) for callus proliferation and plant regeneration. Although the first shoot formation was appeared in medium containing 6.0
and 8.0 mg l−1 BA, the best shoots formation was obtained in medium with 4.0 mg l−1 BA. 相似文献
9.
New divalent transition metal 3,5-pyrazoledicarboxylate
hydrates of empirical formula Mpz(COO)2(H2O)2,
where M=Mn, Co, Ni, Cu, Zn and Cd (pz(COO)2=3,5-pyrazoledicarboxylate),
metal hydrazine complexes of the type Mpz(COO)2N2H4
where M=Co, Zn or Cd and Mpz(COO)2nN2H4·H2O,
where n=1 for M=Ni
and n=0.5 for M=Cu
have been prepared and characterized by physico-chemical methods. Electronic
spectroscopic data suggest that Co and Ni complexes adopt an octahedral geometry.
The IR spectra confirm the presence of unidentate carboxylate anion (Δν=νasy(COO–)–νsym(COO–)>215
cm–1) in all the complexes and bidentate
bridging hydrazine (νN–N=985–950 cm–1)
in the metal hydrazine complexes. Both metal carboxylate and metal hydrazine
carboxylate complexes undergo endothermic dehydration and/or dehydrazination
followed by exothermic decomposition of organic moiety to give the respective
metal oxides as the end products except manganese pyrazoledicarboxylate hydrate,
which leaves manganese carbonate. X-ray powder diffraction patterns reveal
that the metal carboxylate hydrates are isomorphous as are those of metal
hydrazine complexes of cobalt, zinc and cadmium. 相似文献
10.
Hongmei Shi Shipeng Liu Shigang Shen Shuying Huo Weijun Kang 《Transition Metal Chemistry》2009,34(8):821-826
Kinetics of oxidation of dl-pipecolinate by bis(hydrogenperiodato)argentate(III) complex anion, [Ag(HIO6)2]5−, has been studied in aqueous alkaline medium in the temperature range of 25–40 °C. The oxidation kinetics is first order
in the silver(III) and pipecolinate concentrations. The observed second-order rate constant, decreasing with increasing [periodate]
is virtually independent of [OH−]. α-Aminoadipate as the major oxidation product of pipecolinate has been identified by chromatographic analysis. A reaction
mechanism is proposed that involves a pre-equilibrium between [Ag(HIO6)2]5− and [Ag(HIO6)(H2O)(OH)]2−, a mono-periodate coordinated silver(III) complex. Both Ag(III) complexes are reduced in parallel by pipecolinate in rate-determining
steps (described by k
1 for the former Ag(III) species and k
2 for the latter). The determined rate constants and their associated activation parameters are k
1 (25 °C) = 0.40 ± 0.02 M−1 s−1, ∆H
1≠ = 53 ± 2 kJ mol−1, ∆S
1≠ = −74 ± 5 J K−1 mol−1 and k
2 (25 °C) = 0.64 ± 0.02 M−1 s−1, ∆H
2≠ = 41 ± 2 kJ mol−1, ∆S
2≠ = −110 ± 5 J K−1 mol−1. The time-resolved spectra, a positive dependence of the rate constants on ionic strength of the reaction medium, and the
consistency of pre-equilibrium constants derived from different reaction systems support the proposed reaction mechanism. 相似文献
11.
Prithwiraj Byabartta 《Transition Metal Chemistry》2007,32(3):304-313
Reaction of [Au(PPh3)2(tht)2](OSO2CF3)3 with RaaiR′ in CH2Cl2 medium following ligand addition leads to [Au(PPh3)2(RaaiR′)](OTf)3 [RaaiR′ = p-R–C6H4–N=N–C3H2–NN–1–R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH2CH3
(2), CH2Ph (3), PPh3 is triphenylphosphine, OSO2CF3 is the triflate anion, tht is tetrahydrothiophen]. The maximum molecular peak of the corresponding molecule is observed in
the ESI mass spectrum. The 1H-nmr spectral measurements suggest methylene, –CH2–, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph it shows AB type quartets. 13C-nmr spectrum suggests the molecular skeleton. In the 1H–1H COSY spectrum as well as contour peaks in the 1H–13C heteronuclear multiple-quantum coherence (HMQC) spectrum assign the solution structure. Electrochemistry assign ligand reduction
part rather than metal oxidation. 相似文献
12.
Sangeeta Yadav Pramod Kumar Yadav Dinesh Yadav Kapil Deo Singh Yadav 《Applied biochemistry and biotechnology》2009,159(1):270-283
An indigenously isolated fungal strain identified as Aspergillus terricola with assigned fungal strain number MTCC 7588 has been used as source for pectin lyase production. The extracellular pectin
lyase was purified to homogeneity from the culture filtrate of A. terricola by ion exchange and gel filtration chromatography. The determined molecular weight was 35 ± 01 kDa. The K
m and k
cat (turnover) values of the purified enzyme at 37 °C using citrus pectin as the substrate were found to be 1.0 mg/ml and 110.0 s−1, respectively. The pH and temperature optima of the enzyme were 8.0 and 50 °C, respectively. The retting ability of the purified
pectin lyase for natural fibers viz. Cannabis sativa and Linum usitatissimum has been demonstrated for the first time. 相似文献
13.
Pritha Talukder Shyamapada Shit Heinrich N?th Matthias Westerhausen Alexander Nikolai Kneifel Samiran Mitra 《Transition Metal Chemistry》2012,37(1):71-77
A heterobimetallic cyano-bridged 1D coordination polymer of the composition [Ni(baepn)(μ-NC)Fe(CN)3(NO)(μ-CN)]n·3H2O has been synthesized by the reaction of nickel(II) nitrate hexahydrate, baepn (baepn = N, N′-bis(2-aminoethyl)-1,3-propanediamine), and sodium nitroprusside dihydrate in a methanol–water mixture. The complex was characterized
by physicochemical and spectroscopic methods. The crystal structure was established by single-crystal X-ray diffraction analysis.
It reveals cyano-bridged heterometallic chains consisting of alternating arrays of Ni(II) and Fe(II) atoms, both being embedded
in distorted octahedral environments. Low-temperature susceptibility measurements show the presence of weak antiferromagnetic
exchange interactions between paramagnetic Ni(II) centers (J = −0.46 cm−1) through long diamagnetic [Fe(CN)5(NO)]2− bridges. Spin state of the iron atom was established by 57Fe M?ssbauer spectroscopy. 相似文献
14.
Jaya Ram Simkhada Seung Sik Cho Seong Ju Park Poonam Mander Yun Hee Choi Hyo Jeong Lee Jin Cheol Yoo 《Applied biochemistry and biotechnology》2010,162(5):1457-1470
Organic solvent- and detergent-resistant proteases are important from an industrial viewpoint. However, they have been less
frequently reported and only few of them are from actinomycetes. A metalloprotease from Streptomyces olivochromogenes (SOMP) was purified by ion exchange with Poros HQ and gel filtration with Sepharose CL-6B. Apparent molecular mass of the
enzyme was estimated to be 51 kDa by sodium dodecyl sulfate–polyacrylamide gel electrophoresis and gelatin zymography. The
activity was optimum at pH 7.5 and 50 °C and stable between pH 7.0 and 10.0. SOMP was stable below 45 °C and Ca2+ increased its thermostability. Ca2+ enhanced while Co2+, Cu2+, Zn2+, Mn2+, and Fe2+ inhibited the activity. Ethylenediaminetetraacetic acid and ethylene glycol-bis (β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid, but not phenylmethylsulfonyl fluoride, aprotinin, and pefabloc SC, significantly suppressed the activity,
suggesting that it might be a metalloprotease. Importantly, it is highly resistant against various detergents, organic solvents,
and oxidizing agents, and the activity is enhanced by H2O2. The enzyme could be a novel protease based on its origin and peculiar biochemical properties. It may be useful in biotechnological
applications especially for organic solvent-based enzymatic synthesis. 相似文献
15.
Ming-Li Liu Jian-Min Dou Da-Cheng Li Da-Qi Wang Jian-Zhong Cui 《Transition Metal Chemistry》2012,37(1):117-124
The thiosemicarbazide and hydrazide Cu(II) complexes, [Cu3L21(py)4Cl2] (1), [Cu(HL2)py] (2) and [Cu(HL3)py] (3), (H2L1 = 1-picolinoylthiosemicarbazide, H3L2 = N′-(2-hydroxybenzylidene)-3-hydroxy-2-naphthohydrazide, H3L3 = 2-hydroxy-N′-((2-hydroxy-naphthalen-1-yl)methylene)benzohydrazide) have been prepared and characterized through physicochemical and spectroscopic
methods as well as X-ray crystallography. Complex 1 has a centrosymmetric structure with –N–N– bridged Cu3 skeleton. Neighboring molecules are linked into a 3D supermolecular framework by π–π stacking interactions, N–H···Cl and
C–H···Cl hydrogen bonds. Complexes 2 and 3 have similar planar structures but different dimers formed by concomitant Cu···N and Cu···O interactions, respectively. Solvent
accessible voids with a volume of 391 ?3 are included in the structure of complex 2, indicating that this complex is a potential host candidate. Thermogravimetric analysis shows that the three complexes are
stable up to 100 °C. 相似文献
16.
Two new neodymium complexes, [Nd2(abglyH)6(2,2′-bipy)2(H2O)2] · 4H2O 1 and {[Nd(abglyH)3(H2O)2] · (4,4′-bipy) · 7H2O}n
2 (abglyH2 = N-P-acetamidobenzenesulfonyl-glycine acid, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been synthesized and
their structures have been measured by X-ray crystallography. In 1, nine-coordinated Nd(III) ions are bridged by two syn–syn bidentate and two tridentate bridging carboxylate groups from four different abglyH− anions to form dinuclear motifs, which are further connected into a 3-D supramolecular framework via hydrogen bonds between
the binuclear motifs and the uncoordinated water molecules. In 2, eight-coordinated Nd(III) ions are linked by six carboxylate groups adopting a syn–syn bidentate bridging fashion to form a 1-D inorganic–organic alternating linear chain. These polymeric chains generate microchannels
extending along the a direction, and these cavities are occupied by discrete tetradecameric water clusters, which interact with their surroundings
and finally furnish the 3-D supramolecular network via hydrogen bonds. At the same time, π–π stacking interactions between
benzene rings from abglyH− anions also play an important role in stabilizing the network. 相似文献
17.
Galactomannans with galactose:mannose ratios 1:1.48 and 1:1.33, [α]D +67.9 and +76.4°, [η] 870.3 and 1337.1 mL/g, and molecular weights 999 and 1549 kDa, respectively, were isolated in 0.59
and 4.65% yields (of seed mass) from seeds of Astragalus alpinus and A. tibetanus (Fabaceae). Physicochemical methods (CrO3 oxidation; methylation–GC/MS; IR, NMR, and 13C spectroscopy) found that the main polysaccharide chain consisted of 1,4-β-D-mannopyranose units substituted 67.5% (A. alpinus) and 75.2% (A. tibetanus) at the C-6 position by single α -D-galactopyranose units. The contents of mannobiose blocks Man–Man, (Gal)Man–Man/Man–Man(Gal), and (Gal)Man–Man(Gal) variously
substituted with galactose were according to 13C NMR spectroscopy 15.9, 55.5, and 28.6% in A. alpinus galactomannan and 9.9, 42.3, and 47.8% in A. tibetanus galactomannan. 相似文献
18.
Photooxidation of water by the uranyl ion was studied. Solutions of uranyl in 0.01–4.0M H2SO4, HClO4, or 0.1–1.0M Na2SO4 and NaClO4 containing “lacunary” heteropolytungstate (HPT) K10P2W17O61 or K8SiW11O39 were irradiated with a nitrogen laser, a mercury or xenon lamp, or visible light. Spectrophotometric analysis showed that
the irradiation results in the accumulation of UIV. Simultaneously the formation of H2O2 proceeds. The quantum yield Φ of the reaction increases as the concentration of the acid or salt increases. For aerated solutions
of 1M H2SO4 or 1M HClO4, irradiation by light with λ=337.1 Φ is close to (1.5–2)·10−3. The irradiation of solutions with pH −4 for many days leads to an almost quantitative transformation of UO2
2+ into UIV. When the irradiation was carried out in the absence of HPA, UIV was not detected, although hydrogen peroxide was observed in the solution.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 2, pp. 282–287, February, 2000. 相似文献
19.
Georg Süss-Fink Farooq-Ahmad Khan Lucienne Juillerat-Jeanneret Paul J. Dyson Anna K. Renfrew 《Journal of Cluster Science》2010,21(3):313-324
Arene ruthenium complexes containing long-chain N-ligands L1 = NC5H4–4-COO–C6H4–4-O–(CH2)9–CH3 or L2 = NC5H4–4-COO–(CH2)10–O–C6H4–4-COO–C6H4–4-C6H4–4-CN derived from isonicotinic acid, of the type [(arene)Ru(L)Cl2] (arene = C6H6, L = L1: 1; arene = p-MeC6H4Pr
i
, L = L1: 2; arene = C6Me6, L = L1: 3; arene = C6H6, L = L2: 4; arene = p-MeC6H4Pr
i
, L = L2: 5; arene = C6Me6, L = L2: 6) have been synthesized from the corresponding [(arene)RuCl2]2 precursor with the long-chain N-ligand L in dichloromethane. Ruthenium nanoparticles stabilized by L1 have been prepared by the solvent-free reduction of 1 with hydrogen or by reducing [(arene)Ru(H2O)3]SO4 in ethanol in the presence of L1 with hydrogen. These complexes and nanoparticles show a high anticancer activity towards human ovarian cell lines, the highest
cytotoxicity being obtained for complex 2 (IC50 = 2 μM for A2780 and 7 μM for A2780cisR). 相似文献
20.