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101.
Engineering the Donor Selectivity of D‐Fructose‐6‐Phosphate Aldolase for Biocatalytic Asymmetric Cross‐Aldol Additions of Glycolaldehyde
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Dr. Anna Szekrenyi Anna Soler Dr. Xavier Garrabou Dr. Christine Guérard‐Hélaine Dr. Teodor Parella Dr. Jesús Joglar Prof. Dr. Marielle Lemaire Dr. Jordi Bujons Prof. Dr. Pere Clapés 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12572-12583
D ‐Fructose‐6‐phosphate aldolase (FSA) is a unique catalyst for asymmetric cross‐aldol additions of glycolaldehyde. A combination of a structure‐guided approach of saturation mutagenesis, site‐directed mutagenesis, and computational modeling was applied to construct a set of FSA variants that improved the catalytic efficiency towards glycolaldehyde dimerization up to 1800‐fold. A combination of mutations in positions L107, A129, and A165 provided a toolbox of FSA variants that expand the synthetic possibilities towards the preparation of aldose‐like carbohydrate compounds. The new FSA variants were applied as highly efficient catalysts for cross‐aldol additions of glycolaldehyde to N‐carbobenzyloxyaminoaldehydes to furnish between 80–98 % aldol adduct under optimized reaction conditions. Donor competition experiments showed high selectivity for glycolaldehyde relative to dihydroxyacetone or hydroxyacetone. These results demonstrate the exceptional malleability of the active site in FSA, which can be remodeled to accept a wide spectrum of donor and acceptor substrates with high efficiency and selectivity. 相似文献
102.
103.
Pere Castell Angels Serra Marina Gali Marta Giamberini Cossimo Carfagna 《Journal of polymer science. Part A, Polymer chemistry》2003,41(1):1-12
Novel epoxy‐terminated monomers based on imine groups were synthesized and their mesogenic properties studied. Aliphatic spacers of different lengths were introduced between the rigid unit and the glycidylic group, and their liquid‐crystalline behavior was examined. They were reacted with primary aromatic diamines inside a magnetic field so that the formation of anisotropic networks could be investigated. The influence of curing conditions and the structure of monomers and amines on the formation of liquid‐crystal thermosets were investigated. Thermosets with locked nematic textures were obtained in all cases. The influence of a 7.1 T magnetic field on the macroscopic orientation of these materials was studied, and mechanical properties of the resulting networks were evaluated by dynamic mechanical analysis. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1–12, 2003 相似文献
104.
105.
The Flanders Theorem relates the matrices AB and BA and provides a necessary and sufficient condition for the consistency of the matrix system P = ABQ = BA In this paper, we generalize the Flanders condition for several matrices. 相似文献
106.
107.
Barrios LA Aromí G Frontera A Quiñonero D Deyà PM Gamez P Roubeau O Shotton EJ Teat SJ 《Inorganic chemistry》2008,47(13):5873-5881
The polydentate ligand 2,4,6-tris(dipyridin-2-ylamino)-1,3,5-triazine (dpyatriz) in combination with the Cu(ClO 4) 2/CuX 2 salt mixtures (X (-) = Cl (-), Br (-), or N 3 (-)) leads to the formation of molecular coordination aggregates with formulas [Cu 3Cl 3(dpyatriz) 2](ClO 4) 3 ( 2), [Cu 3Br 3(dpyatriz) 2](ClO 4) 3 ( 3), and [Cu 4(N 3) 4(dpyatriz) 2(DMF) 4(ClO 4) 2](ClO 4) 2 ( 4). These complexes consist of two dpyatriz ligands bridged via coordination to Cu (II) and disposed either face-to-face in an eclipsed manner ( 2 and 3) or parallel and mutually shifted in one direction. The copper ions complete their coordination positions with Cl (-) ( 2), Br (-) ( 3), or N 3 (-), ClO 4 (-), and N, N-dimethylformamide (DMF) ( 4) ligands. All complexes crystallize together with noncoordinate ClO 4 (-) groups that display anion...pi interactions with the triazine rings. These interactions have been studied by means of high level ab initio calculations and the MIPp partition scheme. These calculations have proven the ClO 4 (-)...[C 3N 3] interactions to be favorable and have revealed a synergistic effect from the combined occurrence of pi-pi stacking of triazine rings and the interaction of these moieties with perchlorate ions, as observed in the experimental systems. 相似文献
108.
Hoyer D Frank B Götze C Stein PK Zebrowski JJ Baranowski R Palacios M Vallverdú M Caminal P Bayés de Luna A Schmidt G Schmidt H 《Chaos (Woodbury, N.Y.)》2007,17(1):015110
The cardiovascular system incorporates several controlling mechanisms acting as feedback loops over different time horizons. Because of their complex interrelationships, information-based methods such as autonomic information flow (AIF) functions promise to be useful in identifying normal and pathological behavior. Optimal adjustment between those controllers is necessary for healthy global behavior of the organism. We investigated the question as to whether there are typical relationships between short-term and long-term AIF by means of a meta-analysis of several of our own clinical studies of the mortality of patients with multiple organ dysfunction syndrome, heart failure, idiopathic dilated cardiomyopathy, and the length of stay in hospital after abdominal aorta surgery. We found a fundamental association of increased short-term randomness (decreased AIF) and decreased long-term randomness (increased AIF) due to pathology. A systems theoretic validation of this fundamental type of association was done by an appropriate mathematical model using a dissipative system with two feedback loops over different time horizons. The systematic simulation of an increasing collapse of the short feedback loop confirmed the inverse association between short-term and long-term information flow as a fundamental, system inherent type of readjustment that occurs under pathological conditions. 相似文献
109.
Engineered L‐Serine Hydroxymethyltransferase from Streptococcus thermophilus for the Synthesis of α,α‐Dialkyl‐α‐Amino Acids
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Karel Hernandez Igor Zelen Giovanna Petrillo Prof. Dr. Isabel Usón Claudia M. Wandtke Dr. Jordi Bujons Dr. Jesús Joglar Dr. Teodor Parella Prof. Dr. Pere Clapés 《Angewandte Chemie (International ed. in English)》2015,54(10):3013-3017
α,α‐Disubstituted α‐amino acids are central to biotechnological and biomedical chemical processes for their own sake and as substructures of biologically active molecules for diverse biomedical applications. Structurally, these compounds contain a quaternary stereocenter, which is particularly challenging for stereoselective synthesis. The pyridoxal‐5′‐phosphate (PLP)‐dependent L ‐serine hydroxymethyltransferase from Streptococcus thermophilus (SHMTSth; EC 2.1.2.1) was engineered to achieve the stereoselective synthesis of a broad structural variety of α,α‐dialkyl‐α‐amino acids. This was accomplished by the formation of quaternary stereocenters through aldol addition of the amino acids D ‐Ala and D ‐Ser to a wide acceptor scope catalyzed by the minimalist SHMTSth Y55T variant overcoming the limitation of the native enzyme for Gly. The SHMTSth Y55T variant tolerates aromatic and aliphatic aldehydes as well as hydroxy‐ and nitrogen‐containing aldehydes as acceptors. 相似文献
110.
A density functional theory study of the two-leg spin ladder (C(5)H(12)N)(2)CuBr(4) reveals antiferromagnetic interactions through the rungs and legs, although the latter are significantly smaller. Our work suggests interest in manipulating the physical behavior of this prototypical system by doping or chemical modifications. 相似文献