全文获取类型
收费全文 | 398篇 |
免费 | 13篇 |
国内免费 | 2篇 |
专业分类
化学 | 333篇 |
力学 | 1篇 |
数学 | 28篇 |
物理学 | 51篇 |
出版年
2023年 | 1篇 |
2022年 | 8篇 |
2021年 | 7篇 |
2020年 | 7篇 |
2019年 | 5篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 15篇 |
2015年 | 6篇 |
2014年 | 11篇 |
2013年 | 16篇 |
2012年 | 20篇 |
2011年 | 34篇 |
2010年 | 22篇 |
2009年 | 5篇 |
2008年 | 32篇 |
2007年 | 20篇 |
2006年 | 31篇 |
2005年 | 24篇 |
2004年 | 20篇 |
2003年 | 22篇 |
2002年 | 15篇 |
2001年 | 11篇 |
2000年 | 5篇 |
1999年 | 1篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1971年 | 1篇 |
1939年 | 2篇 |
1934年 | 1篇 |
排序方式: 共有413条查询结果,搜索用时 0 毫秒
131.
Wang W Cuyckens F Van den Heuvel H Apers S Pieters L Steenkamp V Stewart MJ Luyckx VA Claeys M 《Rapid communications in mass spectrometry : RCM》2003,17(1):49-55
Two novel compounds, 8-C-D-glucopyranosyl-7-hydroxy-5-methylchromone-2-carboxylic acid and a 2-O'-p-coumaroyl derivative thereof, were identified in a herbal tea that caused severe vomiting in a South African patient who had taken the traditional remedy to clean his stomach. For structural characterization, electrospray (ES) ionization in combination with collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS) were used, as well as UV and nuclear magnetic resonance (NMR) spectroscopy. Specific ions or neutral losses generated under conditions of ES-MS/CID/MS permitted the establishment of structural features such as the free carboxyl group, the C-hexosidic part and the p-coumaroyl group. NMR spectroscopy was necessary to support the structure of the chromone-type aglycone and the glucosidic parts. Since the compounds are structurally related to aloesin and aloeresin A, which are chemotaxonomic markers of Aloe species, and have not been previously reported, we propose that they were formed by oxidative degradation during preparation of the herbal tea from an Aloe species or during its storage. 相似文献
132.
133.
Smalley RE Li Y Moore VC Price BK Colorado R Schmidt HK Hauge RH Barron AR Tour JM 《Journal of the American Chemical Society》2006,128(49):15824-15829
With the desire to mass produce any specific n,m type of single wall carbon nanotube (SWNT) from a small sample of the same material, we disclose here the preliminary work directed toward that goal. The ultimate protocol would involve taking a single n,m-type nanotube sample, cutting the nanotubes in that sample into many short nanotubes, using each of those short nanotubes as a template for growing much longer nanotubes of the same type, and then repeating the process. The result would be an amplification of the original tube type: a parent SWNT serving as the prolific progenitor of future identical SWNT types. As a proof-of-concept, we use here a short SWNT seed as a template for vapor liquid solid (VLS) amplification growth of an individual long SWNT. The original short SWNT seed was a polymer-wrapped SWNT, end-carboxylated, and further tethered with Fe salts at its ends. The Fe salts were to act as the growth catalysts upon subsequent reductive activation. Deposition of the short SWNT-Fe tipped species upon an oxide surface was followed by heating in air to consume the polymer wrappers, then reducing the Fe salts to Fe(0) under a H2-rich atmosphere. During this heating, the Fe(0) can etch back into the short SWNT so that the short SWNT acts as a template for new growth to a long SWNT that occurs upon introduction of C2H4 as a carbon source. Analysis indicated that the templated VLS-grown long SWNT had the same diameter and surface orientation as the original short SWNT seed, although amplifying the original n,m type remains to be proven. This study could pave the way for an amplified growth process of SWNTs en route to any n,m tube type synthesis from a starting sample of pure nanotubes. 相似文献
134.
Valerie Paprocki Peter Hrobrik Katie L. M. Harriman Martin S. Luff Thomas Kupfer Martin Kaupp Muralee Murugesu Holger Braunschweig 《Angewandte Chemie (International ed. in English)》2020,59(31):13109-13115
The π coordination of arene and anionic heteroarene ligands is a ubiquitous bonding motif in the organometallic chemistry of d‐block and f‐block elements. By contrast, related π interactions of neutral heteroarenes including neutral bora‐π‐aromatics are less prevalent particularly for the f‐block, due to less effective metal‐to‐ligand backbonding. In fact, π complexes with neutral heteroarene ligands are essentially unknown for the actinides. We have now overcome these limitations by exploiting the exceptionally strong π donor capabilities of a neutral 1,4‐diborabenzene. A series of remarkably robust, π‐coordinated thorium(IV) and uranium(IV) half‐sandwich complexes were synthesized by simply combining the bora‐π‐aromatic with ThCl4(dme)2 or UCl4, representing the first examples of actinide complexes with a neutral boracycle as sandwich‐type ligand. Experimental and computational studies showed that the strong actinide–heteroarene interactions are predominately electrostatic in nature with distinct ligand‐to‐metal π donation and without significant π/δ backbonding contributions. 相似文献
135.
136.
Rodriguez-Garcia V Yagi K Hirao K Iwata S Hirata S 《The Journal of chemical physics》2006,125(1):014109
Franck-Condon (FC) integrals of polyatomic molecules are computed on the basis of vibrational self-consistent-field (VSCF) or configuration-interaction (VCI) calculations capable of including vibrational anharmonicity to any desired extent (within certain molecular size limits). The anharmonic vibrational wave functions of the initial and final states are expanded unambiguously by harmonic oscillator basis functions of normal coordinates of the respective electronic states. The anharmonic FC integrals are then obtained as linear combinations of harmonic counterparts, which can, in turn, be evaluated by established techniques taking account of the Duschinsky rotations, geometry displacements, and frequency changes. Alternatively, anharmonic wave functions of both states are expanded by basis functions of just one electronic state, permitting the FC integral to be evaluated directly by the Gauss-Hermite quadrature used in the VSCF and VCI steps [Bowman et al., Mol. Phys. 104, 33 (2006)]. These methods in conjunction with the VCI and coupled-cluster with singles, doubles, and perturbative triples [CCSD(T)] method have predicted the peak positions and intensities of the vibrational manifold in the X 2B1 photoelectron band of H2O with quantitative accuracy. It has revealed that two weakly visible peaks are the result of intensity borrowing from nearby states through anharmonic couplings, an effect explained qualitatively by VSCF and quantitatively by VCI, but not by the harmonic approximation. The X 2B2 photoelectron band of H2CO is less accurately reproduced by this method, likely because of the inability of CCSD(T)/cc-pVTZ to describe the potential energy surface of open-shell H2CO+ with the same high accuracy as in H2O+. 相似文献
137.
Antifreeze proteins (AFPs) are found in different species from polar, alpine, and subarctic regions where they serve to inhibit ice crystal growth by adsorption to ice surfaces. Computational methods have the power to investigate the antifreeze mechanism in atomic detail. Molecular dynamics simulations of water under different conditions have been carried out to test our water model for simulations of biological macromolecules in extreme conditions: very low temperatures (200 K) and at the ice/liquid water interface. We show that the flexible F3C water model reproduces properties of water in the solid phase (ice I(h)), the supercooled liquid phase, and at the ice/liquid water interface. Additionally, the hydration of the type III AFP from ocean pout was studied as a function of temperature. Hydration waters on the ice-binding surface of the AFP were less distorted and more tetrahedral than elsewhere on the surface. More ice-like hydrating water structures formed on the ice-binding surface of the protein such that it created an ice-like structure in water within its first hydration layer but not beyond, suggesting that this portion of the protein has high affinity for ice surfaces. 相似文献
138.
The kinetics of the equilibrium reaction between [Ni(SC(6)H(4)R-4)(2)(dppe)] (R= MeO, Me, H, Cl, or NO(2); dppe = Ph(2)PCH(2)CH(2)PPh(2)) and mixtures of [lutH](+) and lut (lut = 2,6-dimethylpyridine) in MeCN to form [Ni(SHC(6)H(4)R-4)(SC(6)H(4)R-4)(dppe)](+) have been studied using stopped-flow spectrophotometry. The kinetics for the reactions with R = MeO, Me, H, or Cl are consistent with a single-step equilibrium reaction. Investigation of the temperature dependence of the reactions shows that DeltaG = 13.6 +/- 0.3 kcal mol(-)(1) for all the derivatives but the values of DeltaH and DeltaS vary with R (R = MeO, DeltaH() = 8.5 kcal mol(-)(1), DeltaS = -16 cal K(-)(1) mol(-)(1); R = Me, DeltaH() = 10.8 kcal mol(-)(1), DeltaS = -9.5 cal K(-)(1) mol(-)(1); R = Cl, DeltaH = 23.7 kcal mol(-)(1), DeltaS = +33 cal K(-)(1) mol(-)(1)). With [Ni(SC(6)H(4)NO(2)-4)(2)(dppe)] a more complicated rate law is observed consistent with a mechanism in which initial hydrogen-bonding of [lutH](+) to the complex precedes intramolecular proton transfer. It seems likely that all the derivatives operate by this mechanism, but only with R = NO(2) (the most electron-withdrawing substituent) does the intramolecular proton transfer step become sufficiently slow to result in the change in kinetics. Studies with [lutD](+) show that the rates of proton transfer to [Ni(SC(6)H(4)R-4)(2)(dppe)] (R = Me or Cl) are associated with negligible kinetic isotope effect. The possible reasons for this are discussed. The rates of proton transfer to [Ni(SC(6)H(4)R-4)(2)(dppe)] vary with the 4-R-substituent, and the Hammett plot is markedly nonlinear. This unusual behavior is attributable to the electronic influence of R which affects the electron density at the sulfur. 相似文献
139.
Valerie R. Kempf Kazumasa Wakamatsu Shosuke Ito John D. Simon 《Photochemistry and photobiology》2010,86(4):765-771
The morphological and chemical changes associated with the exposure of melanosomes to methyl iodide are assessed by a variety of analytical, imaging and spectroscopic methods. Scanning electron microscopy, light scattering and N2 adsorption measurements all indicate significant changes in the morphology of the pigment following methylation. Solid-state nuclear magnetic resonance (SS-NMR) spectroscopy and chemical degradation analysis reveals the methylation results in the introduction of ester groups into the pigment structures. Amino acid analysis further reveals that Arg, Cys, His, Ser and Tyr undergo methylation; the SS-NMR data provide additional evidence for the methylation of the sulfur of Cys. Methylation results in increased solubility of the melanosome; the absorption properties of the dissolved material are characterized by an absorption maximum at 225 nm, with a long tail throughout the UV-A and UV-B, indicating that the solubilized material is a combination of protein and pigment. The methylation-induced decomposition of the melanosomes provides new insights into both the observed increase in O-methyl derivatives of the indolic precursor to eumelanin in the urine of melanoma patients and how increased levels of biologic methylating agents in the brain induce symptoms that resemble Parkinson’s disease. 相似文献
140.
Huber V Sengupta S Würthner F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(26):7791-7807
A series of zinc 3(1)-hydroxymethyl chlorins 10 a-e and zinc 3(1)-hydroxyethyl chlorins 17 with varied structural features were synthesized by modifying naturally occurring chlorophyll a. Solvent-, temperature-, and concentration-dependent UV/Vis and CD spectroscopic methods as well as microscopic investigations were performed to explore the importance of particular functional groups and steric effects on the self-assembly behavior of these zinc chlorins. Semisynthetic zinc chlorins 10 a-e possess the three functional units relevant for self-assembly found in their natural bacteriochlorophyll (BChl) counterparts, namely, the 3(1)-OH group, a central metal ion, and the 13(1) C==O moiety along the Q(y) axis, and they contain various 17(2)-substituents. Depending on whether the zinc chlorins have 17(2)-hydrophobic or hydrophilic side chains, they self-assemble in nonpolar organic solvents or in aqueous media, respectively. Zinc chlorins possessing at least two long side chains provide soluble self-aggregates that are stable in solution for a prolonged time, thus facilitating elucidation of their properties by optical spectroscopy. The morphology of the zinc chlorin aggregates was elucidated by atomic force microscopy (AFM) studies, revealing well-defined nanoscale rod structures for zinc chlorin 10 b with a height of about 6 nm. It is worth noting that this size is in good accordance with a tubular arrangement of the dyes similar to that observed in their natural BChl counterparts in the light-harvesting chlorosomes of green bacteria. Furthermore, for the epimeric 3(1)-hydroxyethyl zinc chlorins 17 with hydrophobic side chains, the influence of the chirality center at the 3(1)-position on the aggregation behavior was studied in detail by UV/Vis and CD spectroscopy. Unlike zinc chlorins 10, the 3(1)-hydroxyethyl zinc chlorins 17 formed only small oligomers and not higher rod aggregate structures, which can be attributed to the steric effect imposed by the additional methyl group at the 3(1)-position. 相似文献