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51.
Saeed Raoufmoghaddam Eite Drent Elisabeth Bouwman 《Advanced Synthesis \u0026amp; Catalysis》2013,355(4):717-733
The catalytic reductive amidation of an aldehyde (hexanal) with an amide (acetamide) is reported. Apart from the desired N‐hexylacetamide, the two isomeric unsaturated intermediates as well as hexanol are produced together with higher mass products that arise from aldol condensation and diamide coupling of the aldehyde. Screening of different catalyst precursor salts, ligands and reaction conditions led to the finding that the catalytic system based on the (cyclooctadiene)rhodium chloride dimer, [Rh(cod)Cl]2, in combination with the ligand xantphos and an acid co‐catalyst results in high selectivity for the desired product. Under optimized conditions nearly full conversion is reached with high selectivity to the desired N‐alkylamide and with a very high N ‐ alkylamide/alcohol ratio, while producing only small amounts of by‐products. The scope of the reaction has been investigated using different amides as well as aldehydes; the results show the general applicability of this novel reaction, but with electron‐withdrawing amides the selectivity to N‐alkylamide is lower. NMR studies showed that the nucleophilic addition of acetamide to hexanal is acid catalyzed, forming N‐(1‐hydroxyhexyl)acetamide in equilibrium with both hexanal and the dehydrated unsaturated imides. A catalytic mechanism is proposed in which a strong acid such as HOTs acts as a co‐catalyst by establishing a rapid chemical equilibrium between the aldehyde, acetamide and the intermediates. Furthermore, it is proposed that the presence of acid causes a change in catalytic species, enabling a cationic Rh/xantphos hydrogenation catalyst to selectively hydrogenate the intermediates to N‐hexylacetamide in the presence of hexanal. 相似文献
52.
Benedict M.B. Grant Elisabeth M. Francis Joao Quinta da Fonseca Mark R. Daymond Michael Preuss 《Acta Materialia》2012,60(19):6829-6841
Deformation mechanisms under tensile loading at room temperature have been studied in a polycrystalline nickel-based superalloy containing close to 50 vol.% γ′. In order to identify the effect of γ′ particle size on deformation mechanisms, model microstructures with unimodal γ′ size distributions were developed. The investigations were carried out by combining in situ loading experiments using neutron diffraction and two-site elasto-plastic self-consistent plasticity modelling with detailed post-mortem electron microscopy. The microscopy work also includes results for samples strained at 500 °C. During early plastic deformation, the diffraction data demonstrate that γ and γ′ display the same elastic strain response, indicating that at this stage γ′ is cut by dislocations regardless of the γ′ particle size. Scanning electron microscopy studies showed an abundance of shearing processes in all three microstructures, hence supporting the conclusions drawn from the diffraction experiment. As the material is further deformed, elastic load transfer from γ to γ′ was observed in the medium (130 nm) and coarse (230 nm) γ′ microstructures but not in the fine (90 nm) γ′ microstructure. The load transfer can be explained by assuming that Orowan looping becomes an additional operative deformation mode. Transmission electron microscopy confirmed that in the fine γ′ microstructure deformation takes place by strongly coupled dislocations cutting the γ′, while the medium and coarse γ′ microstructures showed additional signs of Orowan looping. 相似文献
53.
Lars Blankenburg Martin D. Hager Stephan Sell Steffi Sensfuss Elisabeth Klemm 《应用聚合物科学杂志》2009,111(4):1850-1861
A series of phenyleneethynylene copolymers with triphenylamine units as hole‐transporting moieties (TPA‐PPEs) were synthesized by the palladium‐catalyzed cross‐coupling polycondensation of diethynyltriphenylamines and selected dihalogen comonomers, for instance substituted benzene, thiophene, benzothiadiazole, or anthracene. Incorporation of the electron‐rich amino group into the PPE backbone does not interrupt the main chain conjugation. Furthermore, it has a decreasing effect on the oxidation potential, thus makes these polymers interesting as hole‐injection/hole‐transporting materials. The chemical structure of the new alternating copolymers was confirmed by 1H and 13C NMR spectroscopy and elemental analysis and gel‐permeation chromatography (GPC; THF, Mn ≈ 15,000–30,000 g/mol) was conducted. Furthermore, their optical properties were investigated by UV/vis spectroscopy. The TPA‐PPEs exhibit absorption maxima at around 400 nm (π‐π*), except anthracene containing copolymer 3f (λmax = 514 nm in THF) and benzothiadiazole containing one 3g (λmax = 503 nm in THF). The TPA copolymers have oxidation potentials about 1.1 V (Ag/AgCl). They are good photoconducting materials ( 3a : IPhoto = 4 × 10?10 A at 425 nm (400 V), 3g : IPhoto = 1.3 × 10?11 A at λmax = 500 nm (20 V)) and show emission after excitation at around 450 nm (560 nm 3f ). Their application in nonoptimized polymer solar cells (bulk heterojunction) led to power conversion efficiencies of around 1–1.8% after illumination with 100 mW/cm2 of AM1.5. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
54.
Florina Stefanoiu Laure Candy Carlos Vaca‐Garcia Elisabeth Borredon 《European Journal of Lipid Science and Technology》2008,110(5):441-447
Alkenyl succinic anhydrides (ASA) were obtained by reaction between maleic anhydride and high‐oleic sunflower oil (HOSO) esters. A kinetics study of the maleinization of alkyl esters indicated that the maleinization reaction was second order overall and first order with respect to the individual reactants, and the activation energy was 77.2 ± 3.3 kJ/mol in the investigated temperature range (185–225 °C). These results showed that the cis configuration and the central position of the double bond in HOSO esters facilitate the maleinization of the latter. On the contrary, the length of the linear ester moiety had no influence on the course of the maleinization reaction. Moreover, new evidence demonstrates that there are two different reaction mechanisms: ene‐reaction and addition in allylic position with a 2 : 1 ratio, respectively. This ratio was constant throughout the reaction, thus indicating that these mechanisms are independent. 相似文献
55.
Liubov Shtykova Mariam Masuda Carina Eriksson Kristina Sjödin Elisabeth Marling Fredrik Schlyter Magnus Nydén 《Progress in Organic Coatings》2008
Latex-based coatings for protection of tree seedlings against pest insect feeding are evaluated with respect to surface-, mechanical-, and release properties and antifeedant activity. The latex dispersion Eudragit copolymer (EC) was used to form the coatings, 2,6-di-tert-butyl-4-methylphenol (BHT) and cis-dihydropinidine (Alk) as antifeedants, and a thickener and a alkylglucoside based nonionic surfactant were used as additives to optimize the release- and mechanical properties of coatings. Coating characterization was performed with respect to surface morphology (atomic force microscopy, AFM) and surface wetting (contact angle), as well as to mechanical (tensile stress- and tensile strain at break) properties. Surface smoothness and wettability as well as elasticity increased with addition of the surfactant. The optimized coatings were found to be elastic and water resistant at 3–6 wt.% of BHT and 3 wt.% of surfactant. BHT was released into SDS/water at very low rates. Several formulations of BHT and Alk were efficient in preventing the feeding on conifer bark by a pine insect, Hylobius abietis both in laboratory (no-choice) and in field (3 months) tests. 相似文献
56.
Elisabeth Antic-Fidancev Fabien Serpaggi Grard Frey 《Journal of Alloys and Compounds》2002,340(1-2):88-94
Praseodymium dicarboxylate, [Pr(H2O)]2[O2C(CH2)3CO2]3.4H2O]–glutarate, Pr[glut], is synthesized by hydrothermal techniques. The title compound crystallizes in the monoclinic space group C2/c (No. 15). The rare earth cation is coordinated by nine oxygen atoms, eight oxygen atoms from the carboxylate groups and one from the water molecule. The local symmetry of Pr site is low, Cs. The absorption spectra of Pr[glut] are recorded from the visible to the far IR domain at 300, 77 and 9 K. Under various Ar+ laser excitations no emission is detected from 3P0 and 1D2 excited levels of Pr3+ ion. In the low temperature absorption spectra only one electronic line is recorded for 3H4→3P0 transition. It confirms a unique local environment for the rare earth ion in Pr[glut]. The utility of the ‘barycenter curves’ in the attribution of electronic lines is demonstrated. Energy level scheme of 36 Stark components is deduced from the absorption spectra. The parametric calculation was performed on the whole 4f2 (Pr3+) configuration with the starting set of crystal field parameters obtained previously for the Eu3+ ion in the isostructural compound. Eight free ion and nine phenomenological crystal field parameters in C2v symmetry reproduce quite well several electronic levels of Pr3+ ion experimentally observed in Pr[glut]. A good r.m.s. standard deviation of 14.8 cm−1 is obtained. 相似文献
57.
Dr. Anders Højgaard Hansen Henriette B. Christensen Dr. Sunil K. Pandey Dr. Eugenia Sergeev Alice Valentini Julia Dunlop Domonkos Dedeo Simone Fratta Dr. Brian D. Hudson Prof. Graeme Milligan Prof. Trond Ulven Prof. Elisabeth Rexen Ulven 《ChemMedChem》2021,16(21):3326-3341
Free fatty acid receptor 2 (FFA2) is a sensor for short-chain fatty acids that has been identified as an interesting potential drug target for treatment of metabolic and inflammatory diseases. Although several ligand series are known for the receptor, there is still a need for improved compounds. One of the most potent and frequently used antagonists is the amide-substituted phenylbutanoic acid known as CATPB ( 1 ). We here report the structure-activity relationship exploration of this compound, leading to the identification of homologues with increased potency. The preferred compound 37 (TUG-1958) was found, besides improved potency, to have high solubility and favorable pharmacokinetic properties. 相似文献
58.
Application of Polyimide-based Microfluidic Devices on Acid-catalyzed Hydrolysis of Dimethoxypropane
Microfluidic devices intensify transport phenomena and can improve chemical processes. New manufacturing processes and materials are perpetually developed due to constantly growing interest in process intensification. In this contribution, the authors present the design and application of polyimide-foil-based microfluidic mixing devices manufactured by reactive ion etching. As appropriate model reaction system, acid-catalyzed 2,2-dimethoxypropane (DMP) hydrolysis was chosen and investigated in three different mixing structure with varying flow rate. Energy dissipation rates were calculated to estimate mixing performances. The results show good mixing quality for Reynolds numbers between 10 and 100 and similar mixing times scales for all investigated microstructured mixers. 相似文献
59.
The increased use of carbon fiber reinforced thermosets generates more waste and end-of-life products. However, an efficient recycling method for the expensive carbon fibers has not yet been developed. The selective decomposition of amine-cured epoxy resin under mild conditions is presented. A two-step method was investigated to decompose the epoxy resin. The optimum parameters were initially determined using a model compound. By analysis of the reaction products, a cleavage of the C–N bond according to the Cope elimination could be proven. Therefore, the Cope elimination is suggested as the main step of the decomposition of amine-cured epoxy resins in presence of hydrogen peroxide. By dissolving the resin, it is possible to recover resin-free fibers with unimpaired mechanical properties. 相似文献
60.
Patricia A. Miguez Stephen A. Tuin Adam G. Robinson Joyce Belcher Prapaporn Jongwattanapisan Kimberly Perley Vinicius de Paiva Gon«alves Arash Hanifi Nancy Pleshko Elisabeth R. Barton 《International journal of molecular sciences》2021,22(6)
This study evaluated the direct effect of a phytochemical, hesperidin, on pre-osteoblast cell function as well as osteogenesis and collagen matrix quality, as there is little known about hesperidin’s influence in mineralized tissue formation and regeneration. Hesperidin was added to a culture of MC3T3-E1 cells at various concentrations. Cell proliferation, viability, osteogenic gene expression and deposited collagen matrix analyses were performed. Treatment with hesperidin showed significant upregulation of osteogenic markers, particularly with lower doses. Mature and compact collagen fibrils in hesperidin-treated cultures were observed by picrosirius red staining (PSR), although a thinner matrix layer was present for the higher dose of hesperidin compared to osteogenic media alone. Fourier-transform infrared spectroscopy indicated a better mineral-to-matrix ratio and matrix distribution in cultures exposed to hesperidin and confirmed less collagen deposited with the 100-µM dose of hesperidin. In vivo, hesperidin combined with a suboptimal dose of bone morphogenetic protein 2 (BMP2) (dose unable to promote healing of a rat mandible critical-sized bone defect) in a collagenous scaffold promoted a well-controlled (not ectopic) pattern of bone formation as compared to a large dose of BMP2 (previously defined as optimal in healing the critical-sized defect, although of ectopic nature). PSR staining of newly formed bone demonstrated that hesperidin can promote maturation of bone organic matrix. Our findings show, for the first time, that hesperidin has a modulatory role in mineralized tissue formation via not only osteoblast cell differentiation but also matrix organization and matrix-to-mineral ratio and could be a potential adjunct in regenerative bone therapies. 相似文献