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161.
Millar AJ Doonan CJ Smith PD Nemykin VN Basu P Young CG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(11):3255-3267
Intermediates in the oxygen atom transfer from Mo(VI) to P(III), [Tp(iPr)MoOX(OPR3)] (Tp(iPr) = hydrotris(3-isopropylpyrazol-1-yl)borate; X = Cl-, phenolates, thiolates), have been isolated from the reactions of [Tp(iPr)MoO2X] with phosphines (PEt3, PMePh2, PPh3). The green, diamagnetic oxomolybdenum(IV) complexes possess local C(1) symmetry (by NMR spectroscopy) and exhibit IR bands assigned to nu(Mo==O) (approximately 950 cm(-1)) and nu(P==O) (1140-1083 cm(-1)) vibrations. The X-ray crystal structures of [Tp(iPr)MoOX(OPEt3)] (X = OC6H4-2-sBu, SnBu), [Tp(iPr)MoO(OPh)(OPMePh2)], and [Tp(iPr)MoOCl(OPPh3)] have been determined. The monomeric complexes exhibit distorted octahedral geometries, with coordination spheres composed of tridentate fac-Tp(iPr) and mutually cis monodentate terminal oxo, phosphoryl (phosphine oxide), and monoanionic X ligands. The electronic structures and stabilities of the complexes have been probed by computational methods, with the three-dimensional energy surfaces confirming the existence of a low-energy steric pocket that restricts the conformational freedom of the phosphoryl ligand and inhibits complete oxygen atom transfer. The reactivity of the complexes is also briefly described. 相似文献
162.
Zhang X Young MA Lyandres O Van Duyne RP 《Journal of the American Chemical Society》2005,127(12):4484-4489
A rapid detection protocol suitable for use by first-responders to detect anthrax spores using a low-cost, battery-powered, portable Raman spectrometer has been developed. Bacillus subtilis spores, harmless simulants for Bacillus anthracis, were studied using surface-enhanced Raman spectroscopy (SERS) on silver film over nanosphere (AgFON) substrates. Calcium dipicolinate (CaDPA), a biomarker for bacillus spores, was efficiently extracted by sonication in nitric acid and rapidly detected by SERS. AgFON surfaces optimized for 750 nm laser excitation have been fabricated and characterized by UV-vis diffuse reflectance spectroscopy and SERS. The SERS signal from extracted CaDPA was measured over the spore concentration range of 10(-14)-10(-12) M to determine the saturation binding capacity of the AgFON surface and to calculate the adsorption constant (Kspore=1.7 x 10(13) M(-1)). At present, an 11 min procedure is capable of achieving a limit of detection (LOD) of approximately 2.6 x 10(3) spores, below the anthrax infectious dose of 10(4) spores. The data presented herein also demonstrate that the shelf life of prefabricated AgFON substrates can be as long as 40 days prior to use. Finally, these sensing capabilities have been successfully transitioned from a laboratory spectrometer to a field-portable instrument. Using this technology, 10(4) bacillus spores were detected with a 5 s data acquisition period on a 1 month old AgFON substrate. The speed and sensitivity of this SERS sensor indicate that this technology can be used as a viable option for the field analysis of potentially harmful environmental samples. 相似文献
163.
A new bismaleimide (BMI) resin was synthesized to formulate epoxy(tetraglycidyl diaminodiphenyl methane; TGDDM) – bismaleimide thermoset blends for composite matrix applications. 4,4′-diaminodiphenyl methane (DDM) was used as an amine curing agent for the TGDDM. A Fourier transform infrared (FTIR) spectroscopy was employed to characterize the new BMI resin. Cure behavior of the epoxy–BMI blends was studied using a differential scanning calorimeter (DSC). DSC thermograms of the thermoset blends indicated two exothermic peaks. The glass transition temperature of the thermoset blends decreased with BMI content. Thermogravimetric analysis (TGA) was carried out to investigate thermal degradation behavior of the cured epoxy–BMI thermoset blends. The new BMI resin reacted partially with the DDM and weak intercrosslinking polymer networks were formed during cure of the thermoset blends. 相似文献
164.
The preparations and spectroscopic characteristics are reported of a series of (trimethylgermyl)methyl- and (trimethylstannyl)methylplatinum(II) complexes with diene and P-donor ancillary ligands, cis-Pt(CH2GeMe3)2L2 (L = PPh3 or PPh2Me; L2 = dppe or cod) and cis-Pt(CH2SnMe3)2L2 (L = PPh3; L2 =cod). Thermolysis of toluene solutions of cis-Pt(CH2GeMe3)2(PPh3)2 leads to cis-Pt(Me)(CH2GeMe2CH2GeMe3)(PPh3)2 via β-alkyl migration, after (non-rate-limiting) phosphine dissociation. Estimated activation parameters (ΔH298 K‡ = 126 ± 3 kJ mol−1, ΔS‡ = + 17 ± 7 J mol−1 K−1 and hence Δ298 K‡ = 121 ± 5 kJ mol−1) suggest that this system is more migration labile than its silicon analogue, primarily as a result of a lower activation enthalpy. While cis-Pt(CH2GeMe3)2(PPh2Me)2 reacts similarly but less readily, Pt(CH2GeMe3)2(dppe)2 is inert at operable temperatures. Thermolysis of Pt(CH2GeMe3)2(cod) generates 1,1,3,3,-tetramethyldi-1,3-germacyclobutane as the major organogermanium product, while from cis-Pt(CH2SnMe3)2(PPh3)2, 1,1,3,3-tetramethyldi-1,3-stannacyclobutane predominates. Mechanistic implications are discussed. 相似文献
165.
Some photosensitive molecules, such as p-N,N′-dimethylaminobenzoic acid (DMABA), Nile Red, heteropolytungstic acid (H3PW12O40, HPA) and metalloporphyrins, have been entrapped onto nano-scale pores or channels of TiO2-modified Y-Zeolite (TiO2-Y-Zeolite) and MCM41 (TiO2-MCM41) and their excited-state intermediates have been characterized in terms of the excited-state dynamics by using laser spectroscopic techniques. Through these studies, it has been found that the photo-induced electrons are generated from the intramolecular charge transfer (ICT) state of DMABA, Nile Red or metalloporphyrin (MnTPP(Cl)), followed by transferring to the TiO2-Y-Zeolite or TiO2-MCM41 more efficiently as compared to the bulk TiO2, NaY-Zeolite or MCM41. The efficient photoinduced interfacial electron transfer causes the rapid formation of radicals of those photosensitive molecules (a few tens ps). It has been also found that these photophysical properties can be applied to develop the new photocatalyst as observed by the efficient photocatalytic activities of the DMABA or Nile Red-entrapped TiO2-Y-Zeolites for the photoreduction of an azo-dye such as Methyl Orange in water. On the other hand, in case of HPA-entrapped TiO2-Y-zeolite, the electron generated from the excited-state TiO2 is transferred to HPA, followed by formation of the reduction product, heteropoly blue (HPB) which is also generated by UV irradiation of HPA. This electron transfer is analogous to the Z-scheme mechanism of plant photosynthetic systems showing two photon reactions. Because of this photoelectron transfer mechanism, the HPA-entrapped TiO2-Y-zeolite has demonstrated the synergistic enhancement of the photocatalytic decomposition of Methyl Orange and hydrogen generation from photolysis of water. 相似文献
166.
Anthraquinone-2-sulfonate (AQS) photosensitizes pyrimidine dimer splitting. Electron abstraction from the dimer is thought to induce dimer splitting, but direct evidence for the existence and intermediacy of dimer radical cations has been lacking. By employing photochemically induced dynamic nuclear polarization, we have found emission signals in the NMR spectra of dimers upon photolysis of dimers in the presence of anthraquinone-2-sulfonate. The two dimers employed were cis, syn-thymine dimer in which the N(1)-positions were linked by a three-carbon bridge and the N(3), N(3')-dimethyl derivative of that compound. The anthraquinone-2-sulfonate sensitized photochemically induced dynamic nuclear polarization spectrum of the methylated derivative exhibited an emission signal from the dimer-C(6) hydrogens. This result implied the existence of a dimer radical cation (mD+.) formed by electron abstraction by excited anthraquinone-2-sulfonate and nuclear spin sorting within a solvent caged radical ion pair [mD+. AQS-.]. Product pyrimidine photochemically induced dynamic nuclear polarization signals were also seen [enhanced absorption by C(6)-hydrogens and emission by C(5)-methyl groups]. Nuclear spin polarization in the product resulted from spin sorting in one or more of its precursors, including mD+. The results support the conclusion that dimer radical cations not only exist but are intermediates in the photosensitized splitting of pyrimidine dimers by anthraquinonesulfonate. 相似文献
167.
Novak P Young MM Schoeniger JS Kruppa GH 《European journal of mass spectrometry (Chichester, England)》2003,9(6):623-631
In a preliminary communication we described a top-down approach to the determination of chemical cross-link location in proteins using Fourier transform mass spectrometry (FT-MS). We have since extended the approach to use a series of homobifunctional cross-linkers with the same reactive functional groups, but different cross-linker arm lengths. Correlating cross-linking data across a series of related linkers allows the distance constraint derived from a cross-link between two reactive side chains to be determined more accurately and increases the confidence in the assignment of the cross-links. In ubiquitin, there are seven lysines with primary amino groups and the amino terminus. Disuccinimidyl suberate (DSS, cross-linker arm length = 11.4 A), disuccinimidyl glutarate (DSG, cross-linker arm length = 7.5 A) and disuccinimidyl tartrate (DST, cross- linker arm length = 5.8 A) are homobifunctional cross-linking reagents that react specifically with primary amines. Using tandem mass spectrometry (MS/MS) on the singly, internally cross-linked precursor ion of ubiquitin, we found cross-links with DSS and DSG between the amino terminus and Lys 6, between Lys 6 and Lys 11, and between Lys 63 and Lys 48. Using disuccinimidyl tartrate (DST), the shortest cross-linker in the series, only the cross-links between the amino terminus and Lys 6, and between Lys 6 and Lys 11 were observed. The observed cross-links are consistent with the crystal structure of ubiquitin, if the lysine side chains and the amino terminus are assumed to have considerable flexibility. In a separate study, we probed the reactivity of the primary amino groups in ubiquitin using the amino acetylating reagent, N-hydroxy succinimidyl acetate (NHSAc), and a top-down approach to localize the acetylated lysine residues. The reactivity order obtained in that study (M1 approximate, equals K6 approximate, equals K48 approximate, equals K63) > K33 > K11 > (K27, K29), shows that the cross-link first formed in ubiquitin by reaction with DSS and DSG occurs between the most reactive residues. 相似文献
168.
Ahn YH Park EJ Cho K Kim JY Ha SH Ryu SH Yoo JS 《Rapid communications in mass spectrometry : RCM》2004,18(20):2495-2501
The enrichment of phosphopeptides using immobilized metal ion affinity chromatography (IMAC) and subsequent mass spectrometric analysis is a powerful protocol for detecting phosphopeptides and analyzing their phosphorylation state. However, nonspecific binding peptides, such as acidic, nonphosphorylated peptides, often coelute and make analyses of mass spectra difficult. This study used a partial chemical tagging reaction of a phosphopeptide mixture, enriched by IMAC and contaminated with nonspecific binding peptides, following a modified beta-elimination/Michael addition method, and dynamic mass analysis of the resulting peptide pool. Mercaptoethanol was used as a chemical tag and nitrilotriacetic acid (NTA) immobilized on Sepharose beads was used for IMAC enrichment. The time-dependent dynamic mass analysis of the partially tagged reaction mixture detected intact phosphopeptides and their mercaptoethanol-tagged derivatives simultaneously by their mass difference (-20 Da for each phosphorylation site). The number of new peaks appearing with the mass shift gave the number of multiply phosphorylated sites in a phosphopeptide. Therefore, this partial chemical tagging/dynamic mass analysis method can be a powerful tool for rapid and efficient phosphopeptide identification and analysis of the phosphorylation state concurrently using only MS analysis data. 相似文献
169.
Ka Young Lee 《Tetrahedron letters》2004,45(26):5043-5046
The reaction of arylacetylenes 1 and N,N-dimethylformamide dimethylacetal (2a, DMF-DMA) afforded the corresponding arylpropargyl aldehydes 3 in moderate yields. Similarly, the reaction of 1 and N,N-dimethylacetamide dimethylacetal (2b, DMA-DMA) gave 4-aryl-3-butyn-2-ones 4. 相似文献
170.
Won Young Jung Seung Hee Baek Seong Soo Park Gun-Dae Lee Euh Duck Jeong Hyun Gyu Kim Seong-Soo Hong 《Reaction Kinetics and Catalysis Letters》2007,91(2):233-240
The nanosized titania and TiO2/SiO2 particles were prepared by the microwave-hydrothermal method. The effect of physical properties TTIP/TEOS ratio and calcination
temperature has been investigated. The major phase of the pure TiO2 particle is of the anatase structure, and a rutile peak was observed above 800°C. In TiO2/SiO2 particles, however, no significant rutile phase was observed, although the calcination temperature was 900°C. No peaks for
the silica crystal phase were observed at either silica/titania ratio. The crystallite size of TiO2/SiO2 particles decreases as compared to pure TiO2 at high calcination temperatures. The TiO2/SiO2 particles show higher activity on the photocatalytic decomposition of orange II as compared to pure TiO2 particles. 相似文献