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81.
82.
Permyakov Sergei E.; Cherskaya Alexandra M.; Senin Ivan I.; Zargarov Aminullah A.; Shulga-Morskoy Sergey V.; Alekseev Andrey M.; Zinchenko Dmitry V.; Lipkin Valery M.; Philippov Pavel P.; Uversky Vladimir N.; Permyakov Eugene A. 《Protein engineering, design & selection : PEDS》2000,13(11):783-790
A molecule of the photoreceptor Ca2+-binding protein recoverincontains four potential EF-hand Ca2+-binding sites, of whichonly two, the second and the third, are capable of binding calciumions. We have studied the effects of substitutions in the second,third and fourth EF-hand sites of recoverin on its Ca2+-bindingproperties and some other characteristics, using intrinsic fluorescence,circular dichroism spectroscopy and differential scanning microcalorimetry.The interaction of the two operating binding sites of wild-typerecoverin with calcium increases the protein's thermal stability,but makes the environment around the tryptophan residues moreflexible. The amino acid substitution in the EF-hand 3 (E121Q)totally abolishes the high calcium affinity of recoverin, whilethe mutation in the EF-hand 2 (E85Q) causes only a moderatedecrease in calcium binding. Based on this evidence, we suggestthat the binding of calcium ions to recoverin is a sequentialprocess with the EF-hand 3 being filled first. Estimation ofCa2+-binding constants according to the sequential binding schemegave the values 3.7 x 106 and 3.1 x 105 M1 for thirdand second EF-hands, respectively. The substitutions in theEF-hand 2 or 3 (or in both the sites simultaneously) do notdisturb significantly either tertiary or secondary structureof the apo-protein. Amino acid substitutions, which have beendesigned to restore the calcium affinity of the EF-hand 4 (G160D,K161E, K162N, D165G and K166Q), increase the calcium capacityand affinity of recoverin but also perturb the protein structureand decrease the thermostability of its apo-form. 相似文献
83.
Sergey N. Rashkeev Daniel M. Ginosar Lucia M. Petkovic Helen H. Farrell 《Catalysis Today》2009,139(4):291
Production of hydrogen by splitting of water in the thermochemical sulfur-based cycles that employs the catalytic decomposition of sulfuric acid into SO2 and O2 is of considerable interest. However, all of the known catalytic systems studied to date that consist of metal particles on oxide substrates deactivate with time on stream. To develop an understanding of the factors that are responsible for catalyst activity, we investigate the fresh activity of several platinum group metals (PGM) catalysts, including Pd, Pt, Rh, Ir, and Ru supported on titania at 850 °C and perform an extensive theoretical study (density-functional-theory-based first-principles calculations and computer simulations) of the activity of the PGM nanoparticles of different size and shape positioned on TiO2 (rutile and anatase) and Al2O3 (γ- and η-alumina) surfaces. The activity and deactivation of the catalytic systems are defined by (i) the energy barrier for the detachment of O atoms from the SOn (n = 1, 2, 3) species, and (ii) the removal rate of the products of the sulfuric acid decomposition (atomic O, S, and the SOn species) from metal nanoparticles. We show that these two nanoscale features collectively result in the observed experimental behavior. The removal rate of the reaction products is always lower than the SOn decomposition rates. The relation between these two rates explains why the “softer” PGM nanoparticles (Pd and Pt) exhibit the highest initial catalytic activity. 相似文献
84.
Dmitry N. Kaluzhny Dr. Victor V. Tatarskiy Jr. Lyubov G. Dezhenkova Dr. Irina L. Plikhtyak Dr. Tatyana D. Miniker Dr. Anna K. Shchyolkina Dr. Sergey A. Strel'tsov Dr. Ghermes G. Chilov Dr. Fedor N. Novikov Dr. Irina Yu. Kubasova Dr. Zoya S. Smirnova Dr. Stalina Ya. Mel'nik Dr. Mikhail A. Livshits Dr. Olga F. Borisova Dr. Alexander A. Shtil Dr. 《ChemMedChem》2009,4(10):1641-1648
Novel indolocarbazole derivative 12‐(α‐L ‐arabinopyranosyl)indolo[2,3‐α]pyrrolo[3,4‐c]carbazole‐5,7‐dione (AIC) demonstrated high potency (at submicromolar concentrations) against the NCI panel of human tumor cell lines and transplanted tumors in vivo. In search of tentative targets for AIC, we found that the drug formed high affinity intercalative complexes with d(AT)20, d(GC)20 and calf thymus DNA (binding constants (1.6×106) M ?1≤Ka≤(3.3×106) M ?1). The drug intercalated preferentially into GC pairs of the duplex. Importantly, the concentrations at which AIC formed the intercalative complexes with DNA (C≤1 μM ) were identical to the concentrations that triggered p53‐dependent gene reporter transactivation, the replication block, the inhibition of topoisomerase I‐mediated DNA relaxation and death of HCT116 human colon carcinoma cells. We conclude that the formation of high affinity intercalative complexes with DNA is an important factor for anticancer efficacy of AIC. 相似文献
85.
Raman, UV and XRD studies have been performed to characterize the structures of differently prepared samples of poly(methyl-n-propylsilane). The results demonstrate polymorphism of this polymer between Tc and Tg. At room temperature the polymer can exist in up to four modifications which comprise one amorphous disordered phase and three more ordered modifications, differing in the interchain organization and in the silicon backbone conformations. The latter are considered to be deviant, transoid and all-anti, respectively. The number of the modifications present and relative amount of each strongly depends on the preparation method and thermal history of the sample as well as on the molecular weight. 相似文献
86.
Sergey Y. Nechaev Alexei V. Lutay Valentin V. Vlassov Marina A. Zenkova 《International journal of molecular sciences》2009,10(4):1788-1807
RNA non-enzymatic recombination reactions are of great interest within the hypothesis of the “RNA world”, which argues that at some stage of prebiotic life development proteins were not yet engaged in biochemical reactions and RNA carried out both the information storage task and the full range of catalytic roles necessary in primitive self-replicating systems. Here we report on the study of recombination reaction occuring between two 96 nucleotides (nts) fragments of RNAs under physiological conditions and governed by a short oligodeoxyribonucleotide template, partially complementary to sequences within each of the RNAs. Analysis of recombination products shows that ligation is predominantly template-directed, and occurs within the complementary complex with the template in “butt-to-butt” manner, in 1- or 3- nts bulges or in 2–3 nts internal loops. Minor recombination products formed in the template-independent manner are detected as well. 相似文献
87.
Sergey Lapshin Sarat K. Swain Avraam I. Isayev 《Polymer Engineering and Science》2008,48(8):1584-1591
A continuous ultrasound assisted process using a single screw compounding extruder with an ultrasonic attachment was developed to prepare polyolefin/clay nanocomposites. High‐density polyethylene and isotactic polypropylene were compared. The feed rate that controls the residence time of the polymer in the ultrasonic treatment zone was varied. Die pressure and power consumption were measured. Rheological properties, morphology, and mechanical properties of the untreated and ultrasonically treated nanocomposites were studied. Similarities and differences of obtained nanocomposites are discussed based on their properties and structural characteristics. The modified Halpin‐Tsai theory of composite materials has been employed in order to predict the effect of incomplete exfoliation of clay platelets on the Young's modulus of the nanocomposites. A good agreement between experimental and theoretical data has been observed when reduction of the reinforcement efficiency of clay had been incorporated through the reduced aspect ratio of elementary clay platelets. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers 相似文献
88.
Dmitry V. Orekhov Oleg A. Kazantsev Sergey V. Orekhov Alexey P. Sivokhin Denis M. Kamorin Alexander S. Simagin Maria V. Savinova Evgeniya A. Bolshakova Michail S. Korotaev 《应用聚合物科学杂志》2021,138(38):50982
Thermoresponsive PEG-based (PEG stands polyethylene glycol) polymers are unique for use in medicine because of their low toxicity, good biocompatibility and biodegradability, but usually more hydrophobic and more toxic comonomers are used to adjust lower critical solution temperature (LCST). A convenient way to overcome this problem and to finely tune LCST is to use alkoxy oligo(ethylene glycol)- or alkoxy oligo(propylene glycol) (meth)acrylates as starting comonomers. Here we report on the conditions for the simple and affordable synthesis of methoxy oligo(propylene glycol) (meth)acrylate- and methoxy oligo(propylene glycol)-block-oligo(ethylene glycol) (meth)acrylate-based macromonomers with high yields (80%–98.7%) by the acid-catalyzed esterification of (meth)acrylic acid with alkoxy oligo(alkylene glycols) containing oligo(ethylene glycol) (OEG) and/or oligo(propylene glycol) (OPG) blocks. p-Toluene sulphonic acid (pTSA), alkyl(C12–C14)benzene sulfonic acid (ABSA) and H2SO4 were used as catalysts. It has been shown that pTSA and ABSA are practically the same in catalytic activity and are superior to sulfuric acid. The reaction orders with respect to catalyst was found to be close to 1 in all cases. It has been shown that the reaction is actually insensitive to the lengths of OEG and OPG blocks, as well as to the structure of the terminal alkyl group, while the esterification of acrylic acid (AA) proceeds much faster compared to methacrylic acid (MAA) one under the same conditions. The influence of temperature on the equilibrium conversions of alcohols was determined, which were found to be 89%–93% for the esterification of AA and 61%–86% for MAA in the temperature range of 60–120°C. A further increase in conversion was achieved by introducing an azeotropic agent (toluene), its optimal concentration was found to be 10%–15%. 相似文献
89.
90.
管道是二氧化碳捕集、利用和封存(carbon capture, utilization, and storage,CCUS)技术产业链中输运大量二氧化碳(CO2)的最优方式,但其在运行中具有意外泄漏风险。本文从实验和计算机模拟两个方面综述了国内外开展CO2管道泄漏减压、断裂扩展的研究进展,分析了相态、管材、埋地条件等初始状态对裂纹扩展规律的影响。阐述了状态方程、杂质因素、理论模型对开展实验和模拟计算研究的影响。归纳了适用于建立减压波预测模型的状态方程,开展流固耦合研究的理论方法和模拟仿真软件,设计CO2输运管道参考的技术文档。总结了当前CO2管道泄漏减压、断裂扩展控制研究方面需深入研究的科学问题,展望了亟待开展的研究内容,包括构建多元混合物状态方程在三相点、相间线的计算模型;探究裂纹裂间处CO2热物性质与裂纹断裂扩展的耦合关系;建立管道止裂准则,开发、优化CO2输运管道专用止裂器。 相似文献