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11.
Poverenov E Gandelman M Shimon LJ Rozenberg H Ben-David Y Milstein D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(19):4673-4684
Novel anionic dialkyl, diaryl, and dihydride platinum(II) complexes based on the new "long-arm" hemilabile PCN-type ligand C6H4[CH2P(tBu)2](CH2)2N(CH3)2 with the general formula Li+[Pt(PCN)(R)2]- (R=Me (4), Ph (6) and H (9)) were prepared by reaction of [Pt(PCN)(R)] complexes (obtained from the corresponding chlorides) with an equivalent of RLi, as a result of the opening of the chelate ring. Alkylating agents based on other metals produce less stable products. These anionic d8 complexes are thermally stable although they bear no stabilizing pi acceptors. They were characterized by 1H, 31P[1H], 13C, and 7Li NMR spectroscopy; complex 9 was also characterized by single crystal X-ray crystallography, showing that the Li+ ion is coordinated to the nitrogen atom of the open amine arm and to the hydride ligand (trans to the P atom) of a neighboring molecule (H--Li=2.15 A), resulting in a dimeric structure. Complexes 4 and 9 exhibit high nucleophilic reactivity, upon which the pincer complex is regenerated. Reaction of 4 with water, methyl iodide, and iodobenzene resulted in the neutral complex [Pt(PCN)(CH3)] (3) and methane, ethane, or toluene, respectively. Labeling studies indicate that the reaction proceeds by direct electrophilic attack on the metal center, rather than attack on the alkyl ligand. The anionic dihydride complex 9 reacted with water and methyl iodide to yield [Pt(PCN)(H)] (8) and H2 or methane, respectively. 相似文献
12.
S. E. Morozova A. V. Komissarov K. A. Esikov V. Yu. Zubarev A. A. Malin V. A. Ostrovskii 《Russian Journal of Organic Chemistry》2004,40(10):1532-1538
Linear polynuclear tetrazole-containing compounds were synthesized. Alkylation of 5-[-(5-phenyl-2-tetrazolyl)alkyl]tetrazoles with ethyl bromoacetate and chloroacetamide gave the corresponding esters and amides. Treatment of the latter with tetrachlorosilane-sodium azide afforded compounds containing three tetrazole rings linked through polymethylene bridges. Acid ionization constants of the products possessing an NH-tetrazole ring (pK
a = 2.9–3.2) and the corresponding carboxylic acids (pK
a = 2.9–3.1) in aqueous methanol were determined by potentiometric titration.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1580–1586.Original Russian Text Copyright © 2004 by Morozova, Komissarov, Esikov, Zubarev, Malin, Ostrovskii. 相似文献
13.
Rybtchinski B Konstantinovsky L Shimon LJ Vigalok A Milstein D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(17):3287-3292
Reaction of the complex [Rh(coe)2(solv)n]BF4 (coe=cyclooctene) with the phosphane 1-di-tert-butylphosphinomethyl-2,4,6-trimethylbenzene (1) results in selective C-H bond activation, yielding the spectroscopically characterized solvento complexes [(solv)nRhH(CH2C6H2(CH3)2[CH2P(tBu)2]]]BF4 (solv = acetone, 2a; THF, 2b; methanol, 2c). The stability of these complexes is solvent dependent, alcohols providing significant stabilization. Although cis-alkylrhodium hydride complexes containing labile ligands are generally unstable, 2a-c are stable at room temperature. Complex [ (acetone)(ketol)RhH[CH2C6H2(CH3)2[CH2P(t-Bu)2]]]BF4 (2d, ketol 4-hydroxy-4-methyl-2-pentanone, the product of acetone aldol condensation), crystallized from a solution of 2a in acetone and was structurally characterized. Unusual solvent- and temperature-dependent selectivity in reversible C-H bond elimination of these complexes, most probably controlled by a special mode of strong agostic interactions, is observed by spin saturation transfer experiments. 相似文献
14.
Shimon?Tanaka Hideya?Kawasaki Masao?Suzuki Masahiko?Annaka Norio?Nemoto Mats?Almgren Hiroshi?MaedaEmail author 《Colloid and polymer science》2004,282(10):1140-1145
Vesicle formation in a mixture of oleyldimethylamine oxide (OleylDMAO) and sodium oleate (NaOl) was investigated by viscoelastic measurements and cryoscopic transmission electron micrograph (cryo-TEM) observations. The viscoelastic properties changed with increasing mole fraction of NaOl (X
NaOl) from the Maxwell behavior of OleylDMAO solutions (X
NaOl=0) suggesting a transient network of long flexible chains. For X
NaOl=0.2 and 0.4 mixtures, both the shear storage modulus G and the shear loss modulus G showed weak dependences on angular frequency with a relation G>G. From cryo-TEM observations, vesicles coexisted with threadlike micelles in mixtures of X
NaOl=0.2 and 0.3. As X
NaOl increased further (X
NaOl=0.5 and 0.6), threadlike micelles disappeared and the coexistence of vesicles and globular micelles was observed. At X
NaOl=0.5, the viscosity decreased remarkably, which was consistent with the disappearance of threadlike micelles. The results indicated that vesicles were formed by the addition of NaOl to OleylDMAO solutions, contrary to the expectation of a decrease of the packing parameter with the introduction of electric charges. 相似文献
15.
Mid infrared spectroscopy is a non-destructive technique that can provide detailed information on important, molecule-specific features such as the conformation and functional groups of a large range of compounds. Infrared spectroscopy is now an established and frequently used technique for qualitative analysis, i.e. the identification of chemical constituents in a sample. In addition, its use for quantitative purposes has grown dramatically in recent years. It is important to realise that the analytical problem defines the mode of operation and implementation of the FTIR technique. This Highlight article focuses on the advantages and scope of on-line FTIR detection strategies. However, in common with all techniques, on-line FTIR detection has a number of potential shortcomings, which are also discussed. 相似文献
16.
Johansson A Abrahamsson M Magnuson A Huang P Mårtensson J Styring S Hammarström L Sun L Akermark B 《Inorganic chemistry》2003,42(23):7502-7511
The preparation of donor (D)-photosensitizer (S) arrays, consisting of a manganese complex as D and a ruthenium tris(bipyridyl) complex as S has been pursued. Two new ruthenium complexes containing coordinating sites for one (2a) and two manganese ions (3a) were prepared in order to provide models for the donor side of photosystem II in green plants. The manganese coordinating site consists of bridging and terminal phenolate as well as terminal pyridyl ligands. The corresponding ruthenium-manganese complexes, a manganese monomer 2b and dimer 3b, were obtained. For the dimer 3b, our data suggest that intramolecular electron transfer from manganese to photogenerated ruthenium(III) is fast, k(ET) > 5 x 10(7) s(-)(1). 相似文献
17.
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
18.
A. A. Malin E. V. Korchevskaya M. B. Shcherbinin V. A. Ostrovskii 《Russian Journal of Organic Chemistry》2001,37(12):1767-1770
The reaction of 5'-O-benzoyl-2,3'-anhydrothymidine with triethylammonium tetrazolide in DMF at 100-120°C is described by a second-order kinetic equation, following the first-order kinetics in each of the reactants. On the basis of the experimental activatin parameters, H298 = 80 kJ/mol, S = -116 J× mol-
1 K-
1, a mechanism was proposed, according to which in the rate-determining stage of SN2 reaction triethylammonium tetrazolide attacks the C3
' atom of 5'-O-benzoyl-2,3'-anhydrothymidine with simultaneous loosening of the C3
'ÄO2 anhydro bond. 相似文献
19.
20.
Novel rapid liquid chromatography tandem masspectrometry method for vemurafenib and metabolites in human plasma,including metabolite concentrations at steady state
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Svante Vikingsson Malin Strömqvist Anna Svedberg Johan Hansson Veronica Höiom Henrik Gréen 《Biomedical chromatography : BMC》2016,30(8):1234-1239
A novel, rapid and sensitive liquid chromatography tandem–mass spectrometry method for quantification of vemurafenib in human plasma, that also for the first time allows for metabolite semi‐quantification, was developed and validated to support clinical trials and therapeutic drug monitoring. Vemurafenib was analysed by precipitation with methanol followed by a 1.9 min isocratic liquid chromatography tandem masspectrometry analysis using an Acquity BEH C18 column with methanol and formic acid using isotope labelled internal standards. Analytes were detected in multireaction monitoring mode on a Xevo TQ. Semi‐quantification of vemurafenib metabolites was performed using the same analytical system and sample preparation with gradient elution. The vemurafenib method was successfully validated in the range 0.5–100 μg/mL according to international guidelines. The metabolite method was partially validated owing to the lack of commercially available reference materials. For the first time concentration levels at steady state for melanoma patients treated with vemurafenib is presented. The low abundance of vemurafenib metabolites suggests that they lack clinical significance. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献