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61.
The new ligand‐deficient chain polymer [Hg(μ‐Br)2(3,5‐Br2py)]∞ has been obtained in form of single crystals by thermolysis of the ligand‐rich [Hg(μ‐Br)2(3,5‐Br2py)2]∞ at 180 °C at ambient pressure. From this reaction, high quality crystals of the product are directly accessible. The title compound features HgII cations in a distorted square‐pyramidal coordination; their metal centers aggregate via edge‐sharing with asymmetric halide bridges to chains in which all apical N donor ligands are oriented to the same side of the [Hg(μ‐Br)2]∞ backbone. The new polymer cannot be prepared by stoichiometric reaction in solution. 相似文献
62.
Carina E. Cannizzaro Inge M. E. Thiel Norma B. D'Accorso 《Journal of heterocyclic chemistry》1998,35(2):481-484
The synthesis of 2-(p-chlorophenyl)-5-[1′,2′,3′,4′,5′-penta-O-benzoyl-D-galactopentitol-1-yl]-1,3,4-oxadiazole is described. Its debenzoylation gave an equilibrium mixture of the 1,3,4-oxadiazole derivative without protection of the hydroxyl group and the N-benzoyl-D-galactono-1,4-lactonehydrazone. A similar equilibrium was observed by debenzoylation of 2-phenyl-5-[1′,2′,3′,4′,5′-penta-O-benzoyl-D-galactopentitol-1-yl]-1,3,4-oxadiazole. The 1H, 13C nmr and ms spectra of these compounds are presented. 相似文献
63.
The magnitude of the stabilizing interaction between an aliphatic C[bond]H bond attached to an ammonium nitrogen and a carbonyl oxygen was evaluated by ab initio calculations at the MP2/6-311++G** level of theory. Attractive R(3)N(+)-C-H...O[double bond]C interactions play an important role in supramolecular recognition and various types of stereoselective catalysis. Our calculations show that R(3)N(+)-C-H...O[double bond]C is the strongest hydrogen bond of the C-H...O type known to date. Such hydrogen bonds remain as stabilizing interactions even in water for amide acceptors. 相似文献
64.
Débora de Oliveira Marco Di Luccio Carina Faccio Clarissa Dalla Rosa João Paulo Bender Nádia Lipke Silvana Menoncin Cristiana Amroginski José Vladimir de Oliveira 《Applied biochemistry and biotechnology》2004,115(1-3):771-780
We studied the production of fatty acid ethyl esters from castor oil using n-hexane as solvent and two commercial lipases, Novozym 435 and Lipozyme IM, as catalysts. For this purpose, a Taguchi experimental
design was adopted considering the following variables: temperature (35–65°C), water (0–10 wt/wt%), and enzyme (5–20 wt/wt%)
concentrations and oil-to-ethanol molar ratio (1∶3 to 1∶10). An empirical model was then built so as to assess the main and
cross-variable effects on the reaction conversion and also to maximize biodiesel production for each enzyme. For the system
containing Novozym 435 as tatalyst the maximum conversion obtained was 81.4% at 65°C, enzyme concentration of 20 wt/wt%, water
concentration of 0 wt/wt%, and oil-to-ethanol molar ratio of 1∶10. When the catalyst was Lipozyme IM, a conversion as high
as 98% was obtained at 65°C, enzyme concentration of 20 wt/wt%, water concentration of 0 wt/wt%, and oil-to-ethanol molar
ratio of 1∶3. 相似文献
65.
In 1989, Larsen et al. at Merck discovered that the addition of chiral alcohols to ketenes provided enantiomerically enriched aryl propionic acids, compounds valued for their therapeutic antiinflammatory properties. The high 1,4-asymmetric induction observed (>99:1 dr in the addition, and up to 99% ee after hydrolysis to the acid) is rare. A quantitative model based on B3LYP density functional theory calculations accounts for the stereoselectivity in the addition of (S)-methyl lactate, (S)-3-methyl-2-butanol, and (S)-pantolactone to methylphenylketene. The conformational processes of the intermediates can impact the stereoselectivity of the process, and either the addition step, or the protonation of the enolate intermediate, may be stereoselectivity determining. 相似文献
66.
We classify all the quasifinite highest-weight modules over the central extension of the Lie algebra of matrix quantum pseudo-differential operators, and obtain them in terms of representation theory of the Lie algebra
(, R
m
) of infinite matrices with only finitely many nonzero diagonals over the algebra R
m
=
[t]/(t
m+1). We also classify the unitary ones. 相似文献
67.
Distinctive MS/MS Fragmentation Pathways of Glycopeptide‐Generated Oxonium Ions Provide Evidence of the Glycan Structure 下载免费PDF全文
Jin Yu Manuel Schorlemer Alejandro Gomez Toledo Christian Pett Dr. Carina Sihlbom Prof. Göran Larson Dr. Ulrika Westerlind Dr. Jonas Nilsson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(3):1114-1124
Post‐translational glycosylation of proteins play key roles in cellular processes and the site‐specific characterisation of glycan structures is critical to understanding these events. Given the challenges regarding identification of glycan isomers, glycoproteomic studies generally rely on the assumption of conserved biosynthetic pathways. However, in a recent study, we found characteristically different HexNAc oxonium ion fragmentation patterns that depend on glycan structure. Such patterns could be used to distinguish between glycopeptide structural isomers. To acquire a mechanistic insight, deuterium‐labelled glycopeptides were prepared and analysed. We found that the HexNAc‐derived m/z 126 and 144 oxonium ions, differing in mass by H2O, had completely different structures and that high‐mannose N‐glycopeptides generated abundant Hex‐derived oxonium ions. We describe the oxonium ion decomposition mechanisms and the relative abundance of oxonium ions as a function of collision energy for a number of well‐defined glycan structures, which provide important information for future glycoproteomic studies. 相似文献
68.
Vrančić C Fomichova A Gretz N Herrmann C Neudecker S Pucci A Petrich W 《The Analyst》2011,136(6):1192-1198
The continuous surveillance of glucose concentration reduces short-term risks and long-term complications for people with diabetes mellitus, a disorder of glucose metabolism. As a first step towards the continuous monitoring of glucose, reagent-free transmission spectroscopy in the mid-infrared region has been carried out in vitro using a quantum cascade laser and an optical silver halide fiber. A 30 μm gap in the fiber allowed for transmission spectroscopy of aqueous glucose solutions at a wavelength of 9.69 μm, which is specific to a molecular vibration of glucose. A noise-equivalent concentration as low as 4 mg/dL was achieved at an average power of 1.8 mW and an integration time of 50 s. This is among the most precise of glucose measurements using mid-infrared spectroscopy. Even with the very low average laser power of 0.07 mW the sensitivity of previous results (using a fiber optical evanescent field analysis) has been improved upon by almost one order of magnitude. Finally, the impact of potentially interfering substances such as other carbohydrates was analyzed. 相似文献
69.
Carina M. M. Machado Georgina M. S. Alves Isabel S. S. Pinto Stephanie Scheerlinck Steven Van Acker Helena M. V. M. Soares 《Journal of solution chemistry》2013,42(8):1602-1619
The complexation behavior of four systems involving cadmium(II) or zinc(II) in aqueous solutions with the biological buffers 3-[N,N-bis(2-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid (DIPSO), and [(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)amino]-1-propanesulfonic acid (TAPS) was studied by direct current polarography (DCP) and glass electrode potentiometry (GEP), at 25.0 ± 0.1 °C and ionic strength 0.1 mol·dm?3 KNO3. Except for the Cd–TAPS system, for which full characterization of the system was possible either by DCP or GEP, full characterization of the other metal-buffer systems (Zn–DIPSO, Zn–TAPS and Cd–DIPSO) was only possible using DCP. For Zn-buffers systems, ZnL+ and $ {\text{ZnL(OH)}}_{2}^{ - } $ ZnL(OH) 2 ? (where L stands for buffer) were identified. For the Zn–DIPSO system, the overall stability constant values (as log10 β) are 2.1 ± 0.2 and 13.4 ± 0.2, respectively. For the Zn–TAPS system, the overall stability constants values (as log10 β) are 2.4 ± 0.1 and 12.9 ± 0.3, respectively. For the Cd–DIPSO system, the overall stability constants values (as log10 β) of CdL+ and CdL(OH) are 2.9 ± 0.1 and 6.9 ± 0.3, respectively. For the Cd–TAPS system, only the species CdL+ was identified with log10 β = 2.5 ± 0.1. 相似文献
70.
Åsa Östlund Alexander Idström Carina Olsson Per Tomas Larsson Lars Nordstierna 《Cellulose (London, England)》2013,20(4):1657-1667
In this study the effects of altering the coagulation medium during regeneration of cellulose dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate, were investigated using solid-state NMR spectroscopy and NMR cryoporometry. In addition, the influence of drying procedure on the structure of regenerated cellulose was studied. Complete conversion of the starting material into regenerated cellulose was seen regardless of the choice of coagulation medium. Coagulation in water predominantly formed cellulose II, whereas coagulation in alcohols mainly generated non-crystalline structures. Subsequent drying of the regenerated cellulose films, induced hornification effects in the form of irreversible aggregation. This was indicated by solid-state NMR as an increase in signal intensity originating from crystalline structures accompanied by a decrease of signal intensity originating from cellulose surfaces. This phenomenon was observed for all used coagulants in this study, but to various degrees with regard to the polarity of the coagulant. From NMR cryoporometry, it was concluded that drying induced hornification generates an increase of nano-sized pores. A bimodal pore size distribution with pore radius maxima of a few nanometers was observed, and this pattern increased as a function of drying. Additionally, cyclic drying and rewetting generated a narrow monomodal pore size pattern. This study implies that the porosity and crystallinity of regenerated cellulose can be manipulated by the choice of drying condition. 相似文献