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121.
This paper serves as an introductory review of Brownian Dynamics (BD), Molecular Dynamics (MD), and Monte Carlo (MC) modeling techniques. These three simulation methods have proven to be exceptional investigative solutions for probing discrete molecular, ionic, and colloidal motions at their basic microscopic levels. The review offers a general study of the classical theories and algorithms that are foundational to Brownian Dynamics, Molecular Dynamics, and Monte Carlo simulations. Important topics of interest include fundamental theories that govern Brownian motion, the Langevin equation, the Verlet algorithm, and the Metropolis method. Brownian Dynamics demonstrates advantages over Molecular Dynamics as pertaining to the issue of time-scale separation. Monte Carlo methods exhibit strengths in terms of ease of implementation. Hybrid techniques that combine these methods and draw from these efficacies are also presented. With their rigorous microscopic approach, Brownian Dynamics, Molecular Dynamics, and Monte Carlo methods prove to be especially viable modeling methods for problems with challenging complexities such as high-level particle concentration and multiple particle interactions. These methods hold promising potential for effective modeling of transport in colloidal systems. 相似文献
122.
Burghard Grüning Gerhard Holze Albert Gossauer Ludger Ernst 《Helvetica chimica acta》1985,68(6):1771-1781
The transformation of the c-acetic-acid chain of hexamethyl Coα, Coβ-dicyanocobyrinate into an ethyl group (→ 2 ) as well as the synthesis of the pentadecaalkyl-cobalticorrin 6d from commercial cyanocobalamin are described. On reaction of 2 or 6d with O2 in the presence of ascorbic acid, migration of the CH3 group at C(5) to the vicinal position C(6) takes place concomitantly with the introduction of a carbonyl group at C(5). 相似文献
123.
Abstract— Kinetic studies of the hematoporphyrin–sensitized photooxidation of l -tryptophan and tryptamine at pH 10 in either homogeneous aqueous solutions or in aqueous dispersions of Triton X–100 and cetyltrimethylammonium bromide micelles indicate that the indole substrates are attacked via a mixed type I (electron transfer from triplet dye)/type II (1 O2 -involving) mechanism. Both reactive intermediates, generated by micelle-solubilized hematoporphyrin, can diffuse to attack substrate molecules located in either the bulk aqueous phase or a different micelle. In particular, incorporation of the substrate into a micelle has only minor effects on its reactivity toward1 O2 , although the 1 O2 —indole interaction appears to be more efficient in cationic micelles owing to a favourable orientation of the target with respect to the attacking species. On the other hand, the electron transfer from triplet porphyrin to a micellized substrate is virtually non-operative when the latter is located in an anionic micelle, whereas in neutral or cationic micelles, the efficiency of the process is again controlled by the substrate orientation. Studies of tryptamine photooxidation sensitized by meso-tetra-(4-sulfonato-phenyl) porphine in the presence of sodium dodecylsulphate micelles lend further support to the abovementioned conclusions. 相似文献
124.
The rhodium(II)-catalyzed cyclization/cycloaddition cascade of a o-carbomethoxyaryl diazo dione is described as a potential route to the oxatricyclo[6.3.1.0(0,0)]dodecane substructure of the icetexane diterpene komaroviquinone. The initially formed carbonyl ylide dipole prefers to cyclize to an epoxide at 25 degrees C but can be induced to undergo cycloaddition across the tethered pi-bond at higher temperatures. [reaction: see text] 相似文献
125.
Several new methods for the synthesis of differently substituted 2-amidofurans are described. The thermolysis of furan-2-carbonyl azide results in a Curtius rearrangement and the resulting furanyl isocyanate was trapped with various organometallic reagents. A second method consists of a C-N cross-coupling reaction of a bromo-substituted furan with various amides, carbamates, and lactams. The CuI-catalyzed cross-coupling reaction between furanyl bromides and amides furnished 2- and 3-substituted amidofurans in 45-95% yield. The third protocol used involves the reaction of cyclic carbinol amides with triflic anhydride. The reaction proceeds under very mild conditions to provide alpha-(trifluoromethyl)sulfonamido-substituted furans in high yield. The resulting iminium ion derived from the reaction of the hydroxy pyrrolidinone with Tf(2)O undergoes a facile ring opening as a consequence of the adjacent hydroxyl group to produce an imino triflate intermediate. Subsequent cyclization of this highly electrophilic imine with the oxygen atom of the adjacent carbonyl group leads to an imino dihydrofuran that reacts further with another equivalent of Tf(2)O to give the observed product. 相似文献
126.
A simple and efficient palladium-catalyzed carbon-oxygen bond formation is reported. The palladium-tri-tert-butylphosphine complex was found to be effective in converting haloarenes to corresponding substituted phenols. This methodology offers a direct transformation of aryl halides to phenols, as well as the straightforward application to generate a wide variety of diaryl or alkyl/aryl ethers. 相似文献
127.
An application of automated on-line HPLC-HRGC is described for direct analysis of edible oils for migrated polymer additives. The sample preparation, separating the additive from the oil triglycerides, is carried out using normal phase HPLC. The fraction of the eluent containing the additive is automatically transferred to a HRGC where a second and final separation of the additive from minor oil components takes place. The method compares well with off-line separation methods. Migration data for Tinuvin 1577 from PET and PC polymers as well as an unspecified experimental polymer is given. The advantages and disadvantages of using different edible oils as food simulants are discussed. 相似文献
128.
The reaction of NaEt3BH with Nb2(-SMe2)3Cl6 results in the transfer of a hydride ion to dimethylthioether with concomitant production of methane. Further reaction with potassium di-p-tolylformamidinate, KDTolF, yields Nb2(-SMe)2(-DTolF)22-DTolF:)2.2 toluene, 1. In the latter, two thiomethoxide ions and two DTolF groups bridge the trivalent niobium atoms. Each of the other two DTolF groups chelate a metal atom to give the molecule an edge-sharing bioctahedral structure, The niobium-niobium distance of 2.655(2) A is consistent with the presence of a double bond between the metal atoms. 相似文献
129.
[reaction: see text] The first total synthesis of (+/-)-jamtine (4), a tetrahydroisoquinoline alkaloid reputed for its therapeutic properties, is described. The key step involves a tandem thionium/N-acyliminium ion cyclization from enamido sulfoxide 13. The cascade process takes place with high diastereoselectivity and in excellent yield. 相似文献
130.
Roland K. Robins Ganapathi R. Revankar Darrell E. O'Brien Robert H. Springer Thomas Novinson Anthony Albert Keitaro Senga Jon P. Miller David G. Streeter 《Journal of heterocyclic chemistry》1985,22(3):601-634
A number of new hypoxanthine analogs have been prepared as substrate inhibitors of xanthine oxidase. Most noteworthy inhibitory new hypoxanthine analogs are 3-(m-tolyl)pyrazolo[1,5-a]pyrimidin-7-one ( 47 ), ID50 0.06 μM and 3-phenylpyrazolo[1,5-a]pyrimidin-7-one ( 46 ), ID50 0.40 μM. 5-(p-Chlorophenyl)pyrazolo[1,5-a]pyrimidin-7-one ( 63 ) and the corresponding 5-nitrophenyl derivative 64 exhibited an ID50 of 0.21 and 0.23 μM, respectively. 7-Phenylpyrazolo[1,5-a]-s-triazin-4-one ( 40 ) is shown to exhibit an ID50 of 0.047 μM. The structure-activity relationships of these new phenyl substituted hypoxanthine analogs are discussed and compared with the xanthine analogs 3-m-tolyl- and 3-phenyl-7-hydroxypyrazolo[1,5-a]pyrimidin-5-ones ( 90 ) and ( 91 ), previously reported from our laboratory to have ID50 of 0.025 and 0.038 μM, respectively. The presence of the phenyl and substitutedphenyl groups contribute directly to the substrate binding of these potent inhibitors. This work presents an updated study of structure-activity relationships and binding to xanthine oxidase. In view of the recent elucidation of the pterin cofactor and the proposed binding of this factor to the molybdenum ion in xanthine oxidase, a detailed mechanism of xanthine oxidase oxidation of hypoxanthine and xanthine is proposed. Three types of substrate binding are viewed for xanthine oxidase. The binding of xanthine to xanthine oxidase is termed Type I binding. The binding of hypoxanthine is termed Type II binding and the specific binding of alloxanthine is assigned as Type III binding. These three types of substrate binding are analyzed relative to the most potent compounds known to inhibit xanthine oxidase and these inhibitors have been classified as to the type of inhibitor binding most likely to be associated with specific enzyme inhibition. The structural requirements for each type of binding can be clearly seen to correlate with the inhibitory activity observed. The chemical syntheses of the new 3-phenyl- and 3-substituted phenylpyrazolo[1,5-a]pyrimidines with various substituents are reported. The syntheses of various 8-phenyl-2-substituted pyrazolo-[1,5-a]-s-triazines, certain s-triazolo[1,5-a]-s-triazines and s-triazolo[1,5-a]pyrimidine derivatives prepared in connection with the present study are also described. 相似文献