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61.
Carboxymethyl starch (CMS) was prepared in a completely heterogeneous procedure in a methanol/water slurry activated with aqueous sodium hydroxide (45%, w/v) using monochloroacetic acid as the etherifying agent. The influence of the reaction conditions and the type of starting starch (amylose content and preactivation) was evaluated in regard to the formation of the main repeating units (i.e., unfunctionalized and mono‐, di‐, tri‐, and tetra‐O‐carboxymethylated) and the pattern of functionalization within the anhydroglucose units (AGU). The reproducible synthesis gave products with a maximal degree of substitution of CM groups (DSCM) of 0.66, which was reached in a one‐step synthesis. Repeated carboxymethylation led to products with a DSCM of 0.88. As revealed by means of HPLC analysis after complete acidic depolymerization, in any sample the mono‐O‐carboxymethylated glucose (mono‐O‐CMglc) was preferably present while the di‐O‐CMglc was formed to a very low extent only. The tri‐O‐CMglc was found in some samples while tetra‐O‐CMglc was not detected. The mole fractions determined did not follow the simple Spurlin statistic as shown for CM cellulose synthesized under comparable conditions. Within the carboxymethylated AGUs a preferred functionalization at position 2 was analyzed by means of 1H‐NMR spectroscopy after hydrolytic chain degradation. Consequently, the CMS samples synthesized contained mainly 2‐mono‐O‐CM‐AGU. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2036–2044, 2001 相似文献
62.
Comparative Assessment of Complex Stabilities of Radiocopper Chelating Agents by a Combination of Complex Challenge and in vivo Experiments 下载免费PDF全文
Shanna Litau Dr. Uwe Seibold Alicia Vall‐Sagarra Prof. Dr. Gert Fricker Prof. Dr. Björn Wängler Priv.‐Doz. Dr. Carmen Wängler 《ChemMedChem》2015,10(7):1200-1208
For 64Cu radiolabeling of biomolecules to be used as in vivo positron emission tomography (PET) imaging agents, various chelators are commonly applied. It has not yet been determined which of the most potent chelators—NODA‐GA ((1,4,7‐triazacyclononane‐4,7‐diyl)diacetic acid‐1‐glutaric acid), CB‐TE2A (2,2′‐(1,4,8,11‐tetraazabicyclo[6.6.2]hexadecane‐4,11‐diyl)diacetic acid), or CB‐TE1A‐GA (1,4,8,11‐tetraazabicyclo[6.6.2]hexadecane‐4,11‐diyl‐8‐acetic acid‐1‐glutaric acid)—forms the most stable complexes resulting in PET images of highest quality. We determined the 64Cu complex stabilities for these three chelators by a combination of complex challenge and an in vivo approach. For this purpose, bioconjugates of the chelating agents with the gastrin‐releasing peptide receptor (GRPR)‐affine peptide PESIN and an integrin αvβ3‐affine c(RGDfC) tetramer were synthesized and radiolabeled with 64Cu in excellent yields and specific activities. The 64Cu‐labeled biomolecules were evaluated for their complex stabilities in vitro by conducting a challenge experiment with the respective other chelators as challengers. The in vivo stabilities of the complexes were also determined, showing the highest stability for the 64Cu–CB‐TE1A‐GA complex in both experimental setups. Therefore, CB‐TE1A‐GA is the most appropriate chelating agent for *Cu‐labeled radiotracers and in vivo imaging applications. 相似文献
63.
Katharina Zorn Elke Vorndran Uwe Gbureck Frank A. Müller 《Journal of the American Ceramic Society》2015,98(12):4028-4035
Self‐setting resorbable phosphate cements are characterized by an excellent biocompatibility and bioactivity. However, poor mechanical properties restrict their application. Most studies which characterize phosphate cements mechanically focus on strength measurements. Examinations of mechanical reliability and facture toughness were hardly performed. In this study, calcium phosphate whisker‐reinforced magnesium‐ammonium‐phosphate (struvite) cements were examined at the whisker–matrix interface and the measured strength, reliability and toughness values were correlated to these observations. Moreover, the toughening mechanisms were evaluated. It was shown that whisker incorporation is not beneficial for material strength. It led to a strength decrease from 29.8 to 21.8 MPa by the incorporation of 15 vol% calcium‐deficient hydroxyapatite (CDHA) whiskers compared to the pure struvite cement. Weibull statistics and microstructural observations revealed that this is caused by the whisker–matrix interface, which acts as a flaw. In contrast with that, the reliability increases upon whisker incorporation. Furthermore, the critical stress intensity factor KIC as well as the work‐of‐fracture γwof increase from 0.52 to 0.60 MPam1/2 and from 9.5 to 12.9 J/m² by the addition of 15 vol% CDHA whiskers compared to the original struvite cement. It was shown that whisker pull‐out and crack deflection are the main mechanisms responsible for this increase. 相似文献
64.
Summary: The dicationic [(dppp)Pd(NCCH3)2](BF4)2 catalyst (dppp = 1,3‐bis(diphenylphosphino)propane) was applied in a liquid monomer, two phase process for the CO/propene copolymerization reaction. For the first time it was possible to synthesize propene/CO copolymers with an activity up to 7 500 g/(mol · h) and molecular weights of 500 000 g/mol. Activities up to 40 000 g/(mol · h) could be obtained with the use of the unsymmetric catalyst [(CF3‐dppp)Pd(NCCH3)](BF4)2 (CF3‐dppp = 1‐diphenylphosphino‐3‐bis[3,5‐di(trifluormethyl)phenyl]phosphinopropane) in homogeneous liquid propene solution.
65.
Radiation‐induced graft copolymerization of hydroxyethyl methacrylate with hydroxyethyl acrylate, acrylic acid or glycidyl methacrylate on ethylene tetrafluoroethylene (ETFE) films allow for tailor‐made synthesis of membranes for high and low temperature fuel cell applications. According to the operating temperatures proton conductivity may be achieved via doping with phosphoric acid or a two‐step sulfonation of the functional monomers. Fuel cell tests provide power densities and internal resistances, which indicate that the membranes are suitable for high and low temperature fuel cells. 相似文献
66.
Lars Steinberg Ravisankar Naraparaju Mirko Heckert Christoph Mikulla Uwe Schulz Christoph Leyens 《Journal of the European Ceramic Society》2018,38(15):5101-5112
Aero-engines operating in dust-laden environments often encounter a lot of dust/sand that causes a severe problem to the TBCs by means of erosion. As the turbine entry temperatures are rising, molten sand is also a big concern to the life-time of TBCs.This paper deals with the TBC behavior under the combined influence of erosion and corrosion attack. Variations in TBC morphology, CMAS infiltration time and CMAS composition and their influence on the erosion resistance at room temperature were investigated. Two different EB-PVD 7YSZ morphologies consisting of a different porosity arrangement were tested in the erosion/corrosion regime. The more ‘Feathery’ structure has a better resistance to erosion compared to a more columnar ‘Normal’ structure, which leads to less degradation of the TBC. However, under the influence of CMAS infiltration the effect was found to be reversed. In general, CMAS-infiltrated EB-PVD TBCs exhibit a higher erosion resistance than the non-infiltrated ones. 相似文献
67.
Williams CC Thang SH Hantke T Vogel U Seeberger PH Tsanaktsidis J Lepenies B 《ChemMedChem》2012,7(2):281-291
A series of well‐defined polymer–drug conjugates were prepared in order to modify the physical properties of a known cytotoxic drug, 7‐ethyl‐10‐hydroxycamptothecin (SN‐38), the active metabolite of irinotecan (CPT‐11). Reversible addition–fragmentation chain transfer (RAFT) polymerisation was used to covalently and site‐specifically append a defined N‐(2‐hydroxypropyl)methacrylamide (HPMA) polymer to SN‐38 using a graft‐from process. These poly‐HPMA–SN‐38 conjugates displayed excellent aqueous solubility and stability, whilst retaining the cytotoxic activity of the parent SN‐38. In vitro co‐culture assays containing both cancer and noncancer cell lines demonstrated the specificity of RAFT‐derived poly‐HPMA–SN‐38 conjugates for cancerous cells. The concept of post‐optimisation modification of small‐molecule drugs through a graft‐from polymer conjugation method is introduced. 相似文献
68.
Protein Engineering of the Progesterone Hydroxylating P450‐Monooxygenase CYP17A1 Alters Its Regioselectivity 下载免费PDF全文
Lisa K. Morlock Sascha Grobe Dr. Kathleen Balke Dr. Stephan Mauersberger Dr. Dominique Böttcher Prof. Dr. Uwe T. Bornscheuer 《Chembiochem : a European journal of chemical biology》2018,19(18):1954-1958
The CYP171 enzyme is known to catalyse a key step in the steroidogenesis of mammals. The substrates progesterone and pregnenolone are first hydroxylated at the C17 position, and this is followed by cleavage of the C17?C20 bond to yield important precursors for glucosteroids and androgens. In this study, we focused on the reaction of the bovine CYP17A1 enzyme with progesterone as a substrate. On the basis of a created homology model, active‐site residues were identified and systematically mutated to alanine. In whole‐cell biotransformations, the importance of the N202, R239, G297 and E305 residues for substrate conversion was confirmed. Additionally, mutation of the L206, V366 and V483 residues enhanced the formation of the 16α‐hydroxyprogesterone side product up to 40 % of the total product formation. Furthermore, residue L105 was found not to be involved in this side activity, which contradicts a previous study with the human enzyme. 相似文献
69.
Andreas Zehnsdorf Anja Scherber Steffen Schmidt Anna Theresia Ebersbach Katy Bernhard Daniel Jentzsch Uwe Schlenker 《化学,工程师,技术》2018,90(3):333-339
A mobile root‐zone wastewater treatment system with a reaction zone consisting solely of reed roots as the growth surface for microorganisms was tested for temporary applications in the treatment of municipal wastewater. Pretreated municipal wastewater from a large‐scale wastewater treatment plant was fed to this system during the 2016 vegetation period. The outlet limit values for chemical oxygen demand and biochemical oxygen demand were adhered to reliably at an inlet volumetric flow rate of 1200 L d?1. Short‐term loading peaks of up to 1800 L d?1 did not lead to overloading of the system. 相似文献
70.