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991.
Arnold PL Edworthy IS Carmichael CD Blake AJ Wilson C 《Dalton transactions (Cambridge, England : 2003)》2008,(28):3739-3746
Magnesium dications bind strongly to a tridentate anionic dicarbene ligand L = [N{CH(2)CH(2)(CNCHCHNMes)}(2)] forming dinuclear and trinuclear Mg complexes with some particularly short Mg-C bonds. Treatment of the proligand H(4)LCl(3) with three equivalents of methyl magnesium chloride or benzyl magnesium chloride affords Mg(3)(HL)Cl(6) in high yield. A suspension of in thf was heated to 80 degrees C for 2 h to afford Mg(2)(L)Cl(3), consistent with the loss of one equivalent of MgCl(2), and the deprotonation of the remaining acidic NH, lost as HCl gas. Treatment of Mg(3)(HL)Cl(6) with one equivalent of KC(8) results in deprotonation of the ligand amine NH to afford Mg(3)(L)Cl(5); treatment with a second equivalent forms the radical anion of the complex, K[Mg(3)(L)Cl(5)], which decomposes upon storage, precluding its structural characterisation. The acidic NH proton of the ligand in Mg(3)(HL)Cl(6) can also be removed by deprotonation with Li{N(SiMe(3))(2)}; additional equivalents of which also exchange the magnesium-bound chlorides for silylamido ligands, affording Mg(2)(L)Cl(2)N' and Mg(2)(L)Cl(N')(2), which have both been characterised by single-crystal X-ray diffraction studies. 相似文献
992.
Manik Pavan Maheswaram Dhruthiman Mantheni Indika Perera Hareesha Venumuddala Alan Riga Kenneth Alexander 《Journal of Thermal Analysis and Calorimetry》2013,111(3):1987-1997
Morphological and thermodynamic transitions in drugs as well as their amorphous and crystalline content in the solid state have been distinguished by thermal analytical techniques, which include dielectric analysis (DEA), differential scanning calorimetry (DSC), and macro-photomicrography. These techniques were used successfully to establish a structure versus property relationship with the United States Pharmacopeia standard set of active pharmaceutical ingredient (API) drugs. A distinguishing method is the DSC determination of the amorphous and crystalline content which is based on the fusion properties of the specific drug and its recrystallization. The DSC technique to determine the crystalline and amorphous content is based on a series of heat and cool cycles to evaluate the drugs ability to recrystallize. To enhance the amorphous portion, the API is heated above its melting temperature and cooled with liquid nitrogen to ?120 °C (153 K). Alternatively a sample is program heated and cooled by DSC at a rate of 10 °C min?1. DEA measures the crystalline solid and amorphous liquid API electrical ionic conductivity. The DEA ionic conductivity is repeatable and differentiates the solid crystalline drug with a low conductivity level (10?2 pS cm?1) and a high conductivity level associated with the amorphous liquid (106 pS cm?1). The DSC sets the analytical transition temperature range from melting to recrystallization. However, analysis of the DEA ionic conductivity cycle establishes the quantitative amorphous and crystalline content in the solid state at frequencies of 0.10–1.00 Hz and to greater than 30 °C below the melting transition as the peak melting temperature. This describes the “activation energy method.” An Arrhenius plot, log ionic conductivity versus reciprocal temperature (K?1), of the pre-melt DEA transition yields frequency dependent activation energy (E a, J mol?1) for the complex charging in the solid state. The amorphous content is inversely proportional to the E a where the E a for the crystalline form is higher and lower for the amorphous form with a standard deviation of ±2%. There was a good agreement between the DSC crystalline melting, recrystallization, and the solid state DEA conductivity method with relevant microscopic evaluation. An alternate technique to determine amorphous and crystalline content has been established for the drugs of interest based on an obvious amorphous and crystalline state identified by macro-photomicrography and compared to the conductivity variations. This second “empirical method” correlates well with the “activation energy” method. 相似文献
993.
A new polymorph of the iminophosphorane Ph2P(CH2Py)(NSiMe3), ( 1 ), is compared to a just recently published. The reaction of the starting material, the phosphane Ph2P(CH2Py) with N3SiMe3 in the presence of water gives [Ph2P(CH2Py)(NH2)][N3], ( 2 ). A comparison of the structural and NMR parameters of 2 with previously reported derivatives of 1 , suggests that 2 is best described as a phosphonium salt in which the negatively charged imino nitrogen atom is protonated, according to [Ph2(CH2Py)P+—NH2][N3]—, rather than as an iminiumphosphane salt [Ph2(CH2Py)P=+NH2][N3]—. 相似文献
994.
The reaction of AgC(6)F(5) with monomeric iminophosphanes of Mes*-N═P-X (X = Cl, I) in CH(2)Cl(2) at ambient temperature gives imino(pentafluorophenyl)phosphane, Mes*N═P(C(6)F(5)) (1), in almost quantitative yield (96%), which could be isolated as a highly viscous blue oil. The same reaction with LiC(6)F(5) results in the formation of imino(amino)phosphane (C(6)F(5))(2)P-N(Mes*)-P═NMes* (2) (yield 93%). In the second series of experiments the analogous reaction of MC(6)F(5) (M = Ag, Li) with dimeric [Cl-P(μ-N-Dipp)](2) was studied, leading to the formation of [R-P(μ-N-Dipp)](2) (R = C(6)F(5)) (3) for M = Ag, while only decomposition products such as P(C(6)F(5))(3) were observed in the reaction with the Li salt. Highly labile Mes*-N═P-C(6)F(5) (1) decomposes at ambient temperatures, forming among other products the diphosphane (C(6)F(5))(2)P-P(C(6)F(5))(2) (4). Reaction of 1 with Fe(2)(CO)(9) yields the iron carbonyl complexes Mes*-N═P(C(6)F(5))·Fe(CO)(4) (5) and [Mes*-N═P(C(6)F(5))](2)·Fe(CO)(3) (6). The structure, bonding, and potential energy surface are discussed on the basis of B3LYP/6-31G(d,p) computations. According to time-dependent B3LYP calculations, the blue color of 1 arises from an n → π* electronic transition. 相似文献
995.
Boron as a Powerful Reductant: Synthesis of a Stable Boron‐Centered Radical‐Anion Radical‐Cation Pair 下载免费PDF全文
Dr. Philipp Bissinger Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Christian Hörl Dr. Ivo Krummenacher Dr. Thomas Kupfer 《Angewandte Chemie (International ed. in English)》2015,54(1):359-362
Despite the fundamental importance of radical‐anion radical‐cation pairs in single‐electron transfer (SET) reactions, such species are still very rare and transient in nature. Since diborenes have highly electron‐rich B? B double bonds, which makes them strong neutral reductants, we envisaged a possible realization of a boron‐centered radical‐anion radical‐cation pair by SET from a diborene to a borole species, which are known to form stable radical anions upon one‐electron reduction. However, since the reduction potentials of all know diborenes (E1/2=?1.05/?1.55 V) were not sufficiently negative to reduce MesBC4Ph4 (E1/2=?1.69 V), a suitable diborene, IiPr?(iPr)B?B(iPr)?IiPr, was tailor‐made to comply with these requirements. With a halfwave potential of E1/2=?1.95 V, this diborene ranks amongst the most powerful neutral organic reductants known and readily reacted with MesBC4Ph4 by SET to afford a stable boron‐centered radical‐anion radical‐cation pair. 相似文献
996.
Franziska Doll Annette Buntz Anne‐Katrin Späte Verena F. Schart Alexander Timper Waldemar Schrimpf Prof. Dr. Christof R. Hauck Prof. Dr. Andreas Zumbusch Prof. Dr. Valentin Wittmann 《Angewandte Chemie (International ed. in English)》2016,55(6):2262-2266
Protein glycosylation is a ubiquitous post‐translational modification that is involved in the regulation of many aspects of protein function. In order to uncover the biological roles of this modification, imaging the glycosylation state of specific proteins within living cells would be of fundamental importance. To date, however, this has not been achieved. Herein, we demonstrate protein‐specific detection of the glycosylation of the intracellular proteins OGT, Foxo1, p53, and Akt1 in living cells. Our generally applicable approach relies on Diels–Alder chemistry to fluorescently label intracellular carbohydrates through metabolic engineering. The target proteins are tagged with enhanced green fluorescent protein (EGFP). Förster resonance energy transfer (FRET) between the EGFP and the glycan‐anchored fluorophore is detected with high contrast even in presence of a large excess of acceptor fluorophores by fluorescence lifetime imaging microscopy (FLIM). 相似文献
997.
A PCP Pincer Ligand for Coordination Polymers with Versatile Chemical Reactivity: Selective Activation of CO2 Gas over CO Gas in the Solid State 下载免费PDF全文
Junpeng He Nolan W. Waggoner Samuel G. Dunning Dr. Alexander Steiner Dr. Vincent M. Lynch Prof. Simon M. Humphrey 《Angewandte Chemie (International ed. in English)》2016,55(40):12351-12355
A tetra(carboxylated) PCP pincer ligand has been synthesized as a building block for porous coordination polymers (PCPs). The air‐ and moisture‐stable PCP metalloligands are rigid tetratopic linkers that are geometrically akin to ligands used in the synthesis of robust metal–organic frameworks (MOFs). Here, the design principle is demonstrated by cyclometalation with PdIICl and subsequent use of the metalloligand to prepare a crystalline 3D MOF by direct reaction with CoII ions and structural resolution by single crystal X‐ray diffraction. The Pd?Cl groups inside the pores are accessible to post‐synthetic modifications that facilitate chemical reactions previously unobserved in MOFs: a Pd?CH3 activated material undergoes rapid insertion of CO2 gas to give Pd?OC(O)CH3 at 1 atm and 298 K. However, since the material is highly selective for the adsorption of CO2 over CO, a Pd?N3 modified version resists CO insertion under the same conditions. 相似文献
998.
Site‐Specific Isotope‐Labeling of Inosine Phosphoramidites and NMR Analysis of an Inosine‐Containing RNA Duplex 下载免费PDF全文
999.
Alexander G. Ramm Alexandra B. Smirnova Angelo Favini 《Annali di Matematica Pura ed Applicata》2003,182(1):37-52
A nonlinear operator equation F(x)=0, F:H→H, in a Hilbert space is considered. Continuous Newton’s-type procedures based on a construction of a dynamical system with
the trajectory starting at some initial point x
0 and becoming asymptotically close to a solution of F(x)=0 as t→+∞ are discussed. Well-posed and ill-posed problems are investigated.
Received: June 29, 2001; in final form: February 26, 2002?Published online: February 20, 2003
This paper was finished when AGR was visiting Institute for Theoretical Physics, University of Giessen. The author thanks
DAAD for support 相似文献
1000.
Stefan Jaschke Claudia Klüppelberg Alexander Lindner 《Journal of multivariate analysis》2004,88(2):252-273
We derive results on the asymptotic behavior of tails and quantiles of quadratic forms of Gaussian vectors. They appear in particular in delta–gamma models in financial risk management approximating portfolio returns. Quantile estimation corresponds to the estimation of the Value-at-Risk, which is a serious problem in high dimension. 相似文献