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1.
The electrospray mass spectrum (ESI-MS) of cis-[Ru(NO)Cl(bpy)2]Cl2 (bpy=2,2-bipyridine), obtained from 50% CH3OH/50% H2O as the mobile solvent, exhibited ruthenium-containing ions derived from a {[RuII(NO+)Cl(bpy)2]2+, Cl}+ ion pair (m/z=514) and [RuII(NO+)Cl(bpy)2]2+ (m/z=239.5). [RuIIICl(bpy)2]2+, from the loss of NO from the 239.5 ion, is detected at m/z=224.5. Only the m/z 514 ion pair is detected when 100% CH3OH mobile solvent is used, but the presence of even small amounts of water prompted the additional detection of the m/z 239.5 and m/z 224.5 ions under tandem MS-MS conditions. Ruthenium-chloro-containing ions appear as a characteristic collection of eight main, and four lesser, intense ions created from combinations 104Ru, 102Ru, 101Ru, 99Ru, 98Ru, 96Ru, 35Cl and 37Cl isotopes with minor contributions from 13C, etc. For convenience of discussion, only the most abundant m/z species are mentioned herein as representative of all the isotopically distributed ions.Four fragmentation channels are detectable from the m/z=514 chloride ion pair: (1) the loss of HCl (main channel; ca. 50% of fragmentation events), (2) the loss of NO (ca. 12% ), (3) the loss of bpy (minor pathway), and (4) the loss of Cl atom (ca. 38% ).Loss of NO from ion m/z 514 yields ion m/z 484, which is the precursor of ions m/z 448 (by loss of HCl), m/z 328 (by loss of bpy) and m/z 292 (by loss of HCl and bpy). Loss of HCl from ion m/z 514 generates ion m/z 478, [RuII(NO+)Cl(bpyH)(bpy-H)]+, deprotonated at the ortho C-H of one bpy ligand. In MS-MS experiments, the m/z 478 ion was established to undergo loss of NO, producing ion m/z 448, rejoining further fragmentation process for ion m/z 448 at this point. Loss of neutral bipyridine from m/z 514 in low yield produces ion m/z 358, which undergoes further loss of NO to form [RuCl2(bpy)]+ ion (m/z=328). MS-MS “neutral loss of 30” spectra confirmed the NO loss events as part of the fragmentation sequence for all four pathways.A fourth species of m/z=479 from the “514” ion is obtained by an internal electron transfer from Cl of the ion pair, and loss of the resultant neutral Cl atom. The product [RuII(NO·)Cl(bpy)2]+ “479” fragment undergoes facile loss of NO to generate [RuIICl(bpy)2]+ (m/z=449). Ion m/z 449 gives rise to ions m/z 413 (loss of HCl) and m/z 257(loss of HCl and bpy). MS-MS experiments confirm the neutral loss of Cl from the m/z 514 ion, and the formation of the m/z 449 ion via m/z 479 and m/z 514 parents. This pathway was not observed in a prior study for the related complex, [Ru(NO)Cl(dpaH)(dpa)]+ (dpaH=2,2-dipyridylamine), which does not have an external Cl in an ion pair.  相似文献   

2.
3.
Chlorine containing ruthenium bipyridine carbonyl compounds react readily in dilute alkaline solutions under a CO atmosphere affording a poorly soluble and air sensitive product that is suggested to have a polymeric nature. Various analysis methods (MS and TPD) were used in the characterisation of the product. The replacement of the axial chloride ligands in trans(Cl), cis(CO)[Ru(bpy)(CO)2Cl2] and [Ru(bpy)(CO)2Cl]2 is proposed to be the initial step in the polymerisation. The replacement of chlorides in methanolic solution was confirmed by isolating and characterising the dimeric intermediate [Ru(bpy)(CO)2(COOCH3)]2.  相似文献   

4.
Infrared reflection-absorption spectroscopy (IRRAS) of lipid/protein monolayer films in situ at the air/water interface provides unique molecular structure and orientation information from the film constituents. The technique is thus well suited for studies of lipid/protein interaction in a physiologically relevant environment. Initially, the nature of the IRRAS experiment is described and the molecular structure information that may be obtained is recapitulated. Subsequently, several types of applications, including the determination of lipid chain conformation and tilt as well as elucidation of protein secondary structure are reviewed. The current article attempts to provide the reader with an understanding of the current capabilities of IRRAS instrumentation and the type of results that have been achieved to date from IRRAS studies of lipids, proteins, and lipid/protein films of progressively increasing complexity. Finally, possible extensions of the technology are briefly considered.  相似文献   

5.
A new tetracopper(II) complex bridged both by oxamido and carboxylato groups, namely [Cu4(dmaepox)2(bpy)2](NO3)2·2H2O, where H3dmaepox and bpy represent N‐benzoato‐N′‐ (3‐methylaminopropyl)oxamide and 2,2′‐bipyridine, was synthesized, and its structure reveals the presence of a centrosymmetric cyclic tetracopper(II) cation assembled by a pair of cis‐dmaepox3–‐ bridged dicopper(II) units through the carboxylato groups, in which the endo‐ and exo‐copper(II) ions bridged by the oxamido group have a square‐planar and a square‐pyramidal coordination geometries, respectively. The aromatic packing interactions assemble the complex molecules to a two‐dimensional supramolecular structure. The reactivity toward DNA and protein bovine serum albumin (BSA) indicates that the complex can interact with herring sperm DNA through the intercalation mode and the binding affinity is dominated by the hydrophobicity and chelate ring arrangement around copper(II) ions and quenches the intrinsic fluorescence of BSA via a static process. The cytotoxicity of the complex shows selective cancer cell antiproliferative activity.  相似文献   

6.
Two new porphyrins, meso-tris-3,4-dimethoxyphenyl-mono-(4-pyridyl)porphyrin (H2MPy3,4DMPP) and meso-tris-3-methoxy-4-hydroxyphenyl-mono-(4-pyridyl)porphyrin (H2MPy3M4HPP), and their ruthenium analogs obtained by coordination of [Ru(bpy)2Cl]+ groups (where bpy = 2,2′-bipyridine) to the pyridyl nitrogens have been synthesized and studied by electronic absorption spectroscopy, cyclic voltammetry and spectroelectrochemistry. These ruthenated porphyrins couple Ru chromophores to porphyrins containing electroactive meso-substituents. The highest energy electronic absorption for the ruthenated complexes is assigned as a bpy(π) → bpy(π*) intraligand charge transfer while the next lowest energy electronic absorption is assigned as Ru(dπ) → bpy(π*) metal-to-ligand charge transfer (MLCT) transition. The RuIII/II couples occur at approximately 0.95 V versus the SHE reference electrode in acetonitrile solutions. The first oxidation of the porphyrin is localized on the 3,4-dimethoxyphenyl and 3-methoxy-4-hydroxyphenyl substituents, respectively. Electroactive surfaces result from adsorption of these compounds onto glassy carbon electrodes followed by anodic cycling in acidic media.  相似文献   

7.
We report here two new, high purity, high yield, one-step syntheses of cis-[Rh(bpy)2X2][PF6] {X = Cl, Br, I, bpy = 2,2′-bipyridine} directly from the RhX3 · nH2O starting materials - one conventional and one microwave. The key to obtaining the pure complexes appears to be maintaining a 2:1 ratio of bipyridine to rhodium in solution; thus all reactants must be completely dissolved prior to the start of the reaction. Comparison of the two methods is also discussed. These complexes are pure enough for emission spectroscopy after minimal work-up. The complete characterization of all the halide complexes and the first cyclic voltammetry data on the cis-[Rh(bpy)2I2][PF6] complex are reported. The irreversible Rh(III)-Rh(I) redox potential becomes more positive from Cl to I. All three complexes show two reversible redox potentials corresponding to the bipyridine reductions. These data are consistent with the loss of the two halide ligands and formation of [Rh(bpy)2]+ upon reduction of Rh(III) to Rh(I).  相似文献   

8.
We synthesized novel phenylenediamine derivatives and evaluated them as labeling agents to label proteins in close proximity to a single electron transfer catalyst. We found that N’-acyl-N-methylphenylenediamine labels tyrosine effectively in a model experiment using tris(bipyridine)ruthenium (Ru(bpy)32+) as the single electron transfer catalyst. By changing the substituents on the nitrogen atom of the phenylenediamine derivatives, the electrochemical properties of the labeling agent can be drastically changed. On the other hand, horseradish peroxidase (HRP) also catalyzes the reaction with almost the same oxidation potential as Ru(bpy)32+ (~+1.1?V). HRP proximity labeling is applicable to signal amplification in immunohistochemistry. We evaluated the phenylenediamine derivatives as labeling agents for HRP proximity labeling and signal amplification, and found that N’-acyl-N-methylphenylenediamine is a novel and efficient agent for signal amplification using HRP in immunohistochemistry.  相似文献   

9.
《Inorganica chimica acta》1988,148(1):97-100
Six photoproducts were observed in the photolysis of [Ru(bpy)3]2+ in N,N-dimethylformamide (DMF) in the presence of chloride ions. The primary products were cis-[Ru(bpy)2Cl2] and cis-[Ru(bpy)2-(DMF)Cl]+. The remaining ruthenium products, which were thermally unstable to varying degrees, were cis-[Ru(bpy)2Cl2]+, [Ru(bpy)3]+, and a binuclear species we have tentatively identified as [Ru(bpy)2Cl]2n+ (n = 3 or 4).  相似文献   

10.
超高分辨率显微镜成像技术与同位素示踪技术相结合的纳米二次离子质谱技术(NanoSIMS)具有较高的灵敏度和离子传输效率、极高的质量分辨率和空间分辨率(< 50 nm),代表着当今离子探针成像技术的最高水平.利用稳定性或者放射性同位素在原位或者微宇宙条件下示踪目标微生物,然后将样品进行固定、脱水、树脂包埋或者导电镀膜处理,制备成可供二次离子质谱分析的薄片,进一步通过NanoSIMS成像分析,不仅能够在单细胞水平上提供微生物的生理生态特征信息,而且能够准确识别复杂环境样品中的代谢活跃的微生物细胞及其系统分类信息,对于认识微生物介导的元素生物地球化学循环机制具有重要意义.介绍了纳米二次离子质谱技术的工作原理和技术路线,及其与同位素示踪技术、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、荧光原位杂交技术(FISH)、催化报告沉积荧光原位杂交技术(CARD-FISH)、卤素原位杂交技术(Halogen In Situ Hybridization,HISH)等联合使用在微生物生态学研究方面的应用.  相似文献   

11.
Pentamethylcyclopentadienyl rhodium bipyridine ([Cp*Rh(bpy)(H2O)]2+) is a versatile catalyst to promote biocatalytic redox reactions. However, its major drawback lies in the mutual inactivation of [Cp*Rh(bpy)(H2O)]2+ and the biocatalyst. This interaction was investigated using the alcohol dehydrogenase from Thermus sp. ATN1 (TADH) as model enzyme. TADH binds 4 equiv. of [Cp*Rh(bpy)(H2O)]2+ without detectable decrease in catalytic activity and stability. Higher molar ratios lead to time-, temperature-, and concentration-dependent inactivation of the enzyme suggesting [Cp*Rh(bpy)(H2O)]2+ to function as an ‘unfolding catalyst’. This detrimental activity can be circumvented using strongly coordinating buffers (e.g. (NH4)2SO4) while preserving its activity as NAD(P)H regeneration catalyst under electrochemical reaction conditions.  相似文献   

12.
A new oxamido‐bridged bicopper(II) complex, [Cu2(pdpox)(bpy)(CH3OH)](ClO4), where H3pdpox and bpy stand for N‐(2‐hydroxyphenyl)‐N′‐[3‐(diethylamino)propyl]oxamide and 2,2′‐bipyridine, respectively, has been synthesized and characterized by elemental analyses, molar conductivity measurements, infrared and electronic spectra studies, and X‐ray single crystal diffraction. In the crystal structure, the pdpox3? ligand bridges two copper(II) ions as cisoid conformation. The inner copper(II) ion has a {N3O} square‐planar coordination geometry, while the exo‐ one is in a {N2O3} square‐pyramidal environment. There are two sets of interpenetrating two‐dimensional hydrogen bonding networks parallel to the planes (2 1 0) and (), respectively, to form a three‐dimensional supramolecular structure. The bicopper(II) complex exhibits cytotoxic activity against the SMMC7721 and A549 cell lines. The reactivity toward herring sperm DNA and bovine serum albumin revealed that the bicopper(II) complex can interact with the DNA by intercalation mode, and the complex binds to protein BSA responsible for quenching of tryptophan fluorescence by static quenching mechanism. © 2013 Wiley Periodicals, Inc. J BiochemMol Toxicol 27:412‐424, 2013; View this article online at wileyonlinelibrary.com . DOI 10.1002/jbt.21504  相似文献   

13.
A novel “off-On” electrogenerated chemiluminescence (ECL) biosensor has been developed for the detection of mercury(II) based on molecular recognition technology. The ECL mercury(II) biosensor comprises two main parts: an ECL substrate and an ECL intensity switch. The ECL substrate was made by modifying the complex of Ruthenium(II) tris-(bipyridine)(Ru(bpy)32+)/Cyclodextrins-Au nanoparticles(CD-AuNps)/Nafion on the surface of glass carbon electrode (GCE), and the ECL intensity switch is the single hairpin DNA probe designed according to the “molecular recognition” strategy which was functionalized with ferrocene tag at one end and attached to Cyclodextrins (CD) on modified GCE through supramolecular noncovalent interaction. We demonstrated that, in the absence of Hg(II) ion, the probe keeps single hairpin structure and resulted in a quenching of ECL of Ru(bpy)32+. Whereas, in the presence of Hg(II) ion, the probe prefers to form the T-Hg(II)-T complex and lead to an obvious recovery of ECL of Ru(bpy)32+, which provided a sensing platform for the detection of Hg(II) ion. Using this sensing platform, a simple, rapid and selective “off-On” ECL biosensor for the detection of mercury(II) with a detection limit of 0.1 nM has been developed.  相似文献   

14.
Bendiak B  Fang TT 《Carbohydrate research》2010,345(16):2390-2400
Using mass spectrometry in the negative ion mode, m/z 221 ions are frequently observed as product ion substructures derived from reducing disaccharides having 2, 4, or 6 linkages. The ions have been shown to be glycosyl-glycolaldehydes. All 16 stereochemical variants of their pyranosides were prepared and evaluated by infrared photodissociation, in addition to HexNAc-glycolaldehyde variants (m/z 262) of 2-acetamido-2-deoxy-d-glucose and 2-acetamido-2-deoxy-d-galactose. The stereochemistry and anomeric configuration of these ions were differentiated in the gas phase using a Fourier transform ion cyclotron resonance spectrometer with infrared multiphoton dissociation at 10.6 μm. Results were compared to those obtained by collision-induced dissociation. In some cases, differentiation was far preferable using infrared photodissociation; in others, collision-induced dissociation was preferred. Using an instrument that interfaced a linear trap with a Fourier transform ion cyclotron resonance spectrometer, either dissociation technique could be used to optimally discriminate between isomers. With infrared photodissociation, spectral differences were highly statistically significant, even between pairs of isomers having spectra that appeared to be visually somewhat similar (<1 × 10−9, student’s t-test for key discriminatory ions). Comparisons among different instruments suggest that physical standards of the stereochemical variants of these ions will be required for their detailed structural assignments in unknowns, as some variation was observed among instruments, both using infrared photodissociation and collision-induced dissociation.  相似文献   

15.
The discovery that OmpF was related to the transportation of ruthenium complexes through cell membrane was achieved with proteomics technologies. An integral ruthenium complex exists inside the cell as identified by matrix-assisted laser desorption ionization (MALDI) mass spectrometry. An inhibition assay with Escherichia coli was used to demonstrate the relationship between the transportation of the polypyridyl ruthenium complexes and the presence of OmpF (outer membrane protein F). For instance, the amount of [Ru(tpy)(bpy)Cl]+ (tpy: teripyridine; bpy: bipyridine) that entered the cells was determined by inductively coupled plasma optical emission spectroscopy (ICP-OES) of cell extracts and was measured to be approximately 0.55 μM. In the presence of 10% sucrose solution which is known to reduce the OmpF concentration, the ruthenium complex concentration was reduced to approximately 0.28 μM, which is a 50% reduction. These data suggest that OmpF plays a key role in the transportation of positively charged polypyridyl chlororuthenium complexes into E. coli.  相似文献   

16.
The dimethylaminopyridine (DMAP) promoted reaction between [Os(bpy)2(CO)(OTf)]OTf (where ) and methylene chloride is reported. C-Cl bond breaking of a solvent molecule leads to the formation of the [Os(bpy)2(CO)(Cl)]OTf complex. The reactivity and redox properties of [Os(bpy)2(CO)(OTf)]OTf were investigated by means of room- and low-temperature electrochemical experiments. In CH2Cl2, at low temperature, the complex undergoes two 1e electrochemical and chemical reversible reductions (ErEr mechanism), but at room temperature a more complex electrochemical mechanism is observed, leading to the electro-synthesis of [Os(bpy)2(CO)(Cl)]OTf via electrochemical reversible and chemical irreversible reduction processes (ErCi mechanism). The DMAP nucleophilicity was used to produce the new [Os(bpy)2(CO)(Br)]OTf and [Os(bpy)2(CO)(I)]OTf complexes which have been fully characterized.  相似文献   

17.
The reaction of Mn(NO3)2 · 4H2O, 2,2′-bipyridine (bpy) and sodium dicyanamide (dca) in aqueous medium yielded the {[Mn(bpy)3][Mn(dca)3]2}n (1). The single-crystal X-ray analysis of 1 revealed that the anionic part of the complex, [Mn(dca)3], features infinite 2D sheets with a honeycomb-like porous structure having a void space of ca. 12 Å in which [Mn(bpy)3]2+ cations are encapsulated to yield a fascinating molecular assembly. MnII ions possess an octahedral geometry both in the anionic and cationic components of complex 1. In the anionic component, each MnII ion is bridged by three pairs of dicyanamide anions in an end-to-end fashion with two other MnII ions from adjacent [Mn(dca)3] moieties. This type of linking propagates parallel to the bc crystallographic plane to form 2D sheets. [Mn(bpy)3]2+ is found to have somewhat “squeezed” upon encapsulation. No measurable magnetic interaction was evidenced through variable temperature magnetic susceptibility measurements. However, in addition to the broad g ≈ 2 resonance typical of magnetically diluted [Mn(bpy)3]2+ cations, EPR spectroscopy evidenced exchange narrowing of the [Mn(dca)3] resonance at g ≈ 2 thus indicating operation of weak magnetic interactions extended over the whole 2D network through the dca bridges.  相似文献   

18.
High molecular weight poly(ethylene glycol) (PEG) derivatized iron tris(bipyridine) complexes, presenting hydroxyl end groups for further modification as bioconjugates, copolymers, or cross-linking agents, were synthesized via ring-opening anionic polymerization of ethylene oxide from hydroxyl-functionalized bipyridine (bpy) initiators and subsequent chelation to iron(II). Bpy-centered PEG macroligands (bpyPEG(2)) with molecular weights ranging from 4,000 to 17,000 and low polydispersity indices (<1.1) were obtained. Chelation of the bpyPEG(2) macroligands to iron(II) sulfate was studied in aqueous solution by titration and kinetics experiments, which revealed unexpected air sensitivity compared to nonpolymeric iron tris(bipyridine) complexes. Red-violet aqueous solutions of [Fe(bpyPEG(2))(3)](2+) begin to bleach within hours when exposed to air. Enhanced polymer degradation and gel formation of acrylate-modified bpyPEG(2) in the presence of Fe(2+) suggest that radicals may be involved. Under argon, the chromophores are stable. Polymeric iron complexes are slower to form and faster to degrade in air with increasing bpyPEG(2) molecular weight. These studies demonstrate the influence of molecular weight in polymeric iron tris(bipyridine) complex coordination chemistry and reactivity.  相似文献   

19.
Adducts formed by [Mn(2,6-dmb)2(H2O)3]n · nH2O, 2,6-dmb=2,6-dimethoxybenzoate(1-), Mn(2,4-dhb)2 · 8H2O, Mn(2,5-dhb)2 · 4H2O or Mn(2,6-dhb)2 · 8H2O, dhb=dihydroxybenzoate(1-), and 2,2-bipyridine (bpy), 4,4-dimethyl-2,2-bipyridine (Me2bpy) or 4,7-dimethyl-1,10-phenanthroline (Me2phen) were isolated in the solid state and characterised by IR, EPR and thermogravimetry. Two of them, [Mn(2,6-dhb)2(bpy)2] (1) and [Mn2(2,6-dmb)4(Me2Phen)2(H2O)2] · 2EtOH (2), were studied by single crystal X-ray diffraction. The adduct 1 is mononuclear and consists of hexa-co-ordinate manganese(II) ions bound to two bipyridine and two 2,6-dihydroxybenzoate ligands in a cis-octahedral arrangement. The complex 2 exhibits a dinuclear structure in which two manganese(II) ions share two carboxylate groups adopting a rather uncommon single-atom bridging mode. The results allow us to conclude that weak, e.g., hydrogen bonding and stacking interactions govern the type of structure, monomeric or dimeric. The spectral features of the complexes are discussed. In particular, the solid-state EPR features of the complexes are interpreted in terms of D, E and Hmax, the high-field resonance. For the monomeric species, the higher is the D value, the higher is Hmax.  相似文献   

20.
The polymer–cobalt(III) complexes, [Co(bpy)(dien)BPEI]Cl3 · 4H2O (bpy = 2,2′‐bipyridine, dien = diethylentriamine, BPEI = branched polyethyleneimine) were synthesized and characterized. The interaction of these complexes with human serum albumin (HSA) and bovine serum albumin (BSA) was investigated under physiological conditions using various physico‐chemical techniques. The results reveal that the fluorescence quenching of serum albumins by polymer–cobalt(III) complexes took place through static quenching. The binding of these complexes changed the molecular conformation of the protein considerably. The polymer–cobalt(III) complex with x = 0.365 shows antimicrobial activity against several human pathogens. This complex also induces cytotoxicity against MCF‐7 through apoptotic induction. However, further studies are needed to decipher the molecular mode of action of polymer–cobalt(III) complex and for its possible utilization in anticancer therapy. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

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