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Products of the Dimerisation of Unsaturated Fatty Acids IX: Kinetic Studies about the Dimerisation of Linoleic Acid To clarify the dimerisation process of linoleic acid, we investigated samples taken in different time intervals. The first reaction step is a water addition at double bonds of the starting material and not double bond isomerisation as previously assumed. The resulting unsaturated monohydroxy fatty acids can cyclize with the second double bond in an intramolecular reaction forming 2,5-disubstituted tetrahydrofuran respectively 2,6-disubstituted tetrahydropyran derivates. Linolenic acid, present nearly always in small amounts in linoleic acid, reacts to first dimerisation products with linoleic acid by formation of a C-C-bond. The aliphatic dimers cyclize in an intramolecular reaction to mono-cyclic compounds. No dimeric acids, which would result from a Diels-Alder-reaction, could be identified. Bicyclic and aromatic dimeric acids can also be found in the early phase of the dimerisation. In the further progress of the reaction isomerisations, hydrogenations and dehydrogenations of the primary reaction products occur, thus the content of aromatic substances increases steadily. 相似文献
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An aerosol dynamics model, AERO2, is presented, which describes the formation of H2SO4-H2O aerosol in a smog chamber. The model is used to analyse how the uncertainties on four input parameters are propagated through an aerosol dynamics model. The input parameters are: the rate of the reaction between SO2 and OH (k1), the ratio between the nucleation rate used in AERO2 and that derived from classical nucleation theory (tn), the H2SO4 mass accommodation coefficient () and a measure of the turbulence intensity in the reactor (ke). Uncertainties for these parameters are taken from the literature. One of the results of the analysis is that AERO2 and aerosol dynamics models in general can only predict upper bounds for the total number (Ntot) and total volume (Vtot) concentrations of the particles. The uncertainties on Ntot and Vtot are mainly due to the uncertainties on k1, and tn. An uncertainty factor of 20–100 still remains when the uncertainty on k1, is reduced to ±5%. Aerosol measurements from three smog chamber experiments have therefore been used, in an attempt to reduce the uncertainty on k1 and tn. Values for k1 are obtained in the reduced range 7.8 × 10−13 to 1.0 × 10−12 cm3 s−1, which is within the range found in the literature. For tn, values in the range 104–107 are obtained, which is close to the upper bound of the range in literature. These values for tn are in marked contrast with a recent set of experiments on nucleation in H2SO4-H2O mixtures, which suggests a value for tn of at most 10−5. 相似文献
4.
G. Y. Kim L. M. He J. D. Meyer W. Y. Lee A. Quintero J. A. Haynes 《Metallurgical and Materials Transactions A》2004,35(11):3581-3593
A laboratory-scale chemical vapor deposition (CVD) reactor was used to perform “continuous” Hf doping experiments while the
surface of a single-crystal Ni alloy was being aluminized to form an aluminide (β-NiAl) coating matrix for 45 minutes at 1150 °C. The continuous doping procedure, in which HfCl4 and AlCl3 were simultaneously introduced with H2, required a high HfCl4/AlCl3 ratio (>∼0.6) to cause the precipitation of Hf-rich particles (∼0.1 μm) at grain boundaries of the coating layer, with the overall Hf concentration of ∼0.05 to 0.25 wt pct measured in the coating
layer by glow-discharge mass spectroscopy (GDMS). Below this ratio, Hf did not incorporate as a dopant into the growing coating
layer from the gas phase, as the coating matrix appeared to be “saturated” with other refractory elements partitioned from
the alloy substrate. In comparison, the Hf concentration in the aluminide coating layer formed on pure Ni was in the range
of ∼0.1 wt pct, which was close to the solubility of Hf estimated for bulk NiAl. Interestingly, the segregation of Hf and
the formation of a thin γ′-Ni3Al layer (∼0.5 μm) at the coating surface were consistently observed for both the alloy and pure-Ni substrates. The formation of the thin
γ′-Ni3Al layer was attributed to an increase in the elastic strain of the β-NiAl phase, associated with the segregation of Hf as well as other refractory alloying elements at the coating surface. This
phenomenon also implied that the coating layer was actually growing at the interface between the γ′-Ni3Al layer and the β-NiAl coating matrix, not at the gas/coating interface, during the early stage of the coating growth. 相似文献
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Sara Oliveira Tamaeh Monteiro-Alfredo Rita Henriques Carlos Fontes Ribeiro Raquel Seia Teresa Cruz Clia Cabral Rosa Fernandes Ftima Piedade Maria Paula Robalo Paulo Matafome Snia Silva 《International journal of molecular sciences》2022,23(10)
Curcumin has been suggested as a promising treatment for metabolic diseases, but the high doses required limit its therapeutic use. In this study, a new curcuminoid is synthesised to increase curcumin anti-inflammatory and antioxidant potential and to achieve hypoglycaemic and protective vascular effects in type 2 diabetic rats in a lower dose. In vitro, the anti-inflammatory effect was determined through the Griess reaction, and the antioxidant activity through ABTS and TBARS assays. In vivo, Goto-Kakizaki rats were treated for 2 weeks with the equimolar dose of curcumin (40 mg/kg/day) or curcuminoid (52.4 mg/kg/day). Fasting glycaemia, insulin tolerance, plasma insulin, insulin signalling, serum FFA, endothelial function and several markers of oxidative stress were evaluated. Both compounds presented a significant anti-inflammatory effect. Moreover, the curcuminoid had a marked hypoglycaemic effect, accompanied by higher GLUT4 levels in adipose tissue. Both compounds increased NO-dependent vasorelaxation, but only the curcuminoid exacerbated the response to ascorbic acid, consistent with a higher decrease in vascular oxidative and nitrosative stress. SOD1 and GLO1 levels were increased in EAT and heart, respectively. Altogether, these data suggest that the curcuminoid developed here has more pronounced effects than curcumin in low doses, improving the oxidative stress, endothelial function and glycaemic profile in type 2 diabetes. 相似文献
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Sandra Brasil Mariateresa Allocca Salvador C. M. Magrinho Inês Santos Madalena Raposo Rita Francisco Carlota Pascoal Tiago Martins Paula A. Videira Florbela Pereira Giuseppina Andreotti Jaak Jaeken Kristin A. Kantautas Ethan O. Perlstein Vanessa dos Reis Ferreira 《International journal of molecular sciences》2022,23(15)
Advances in research have boosted therapy development for congenital disorders of glycosylation (CDG), a group of rare genetic disorders affecting protein and lipid glycosylation and glycosylphosphatidylinositol anchor biosynthesis. The (re)use of known drugs for novel medical purposes, known as drug repositioning, is growing for both common and rare disorders. The latest innovation concerns the rational search for repositioned molecules which also benefits from artificial intelligence (AI). Compared to traditional methods, drug repositioning accelerates the overall drug discovery process while saving costs. This is particularly valuable for rare diseases. AI tools have proven their worth in diagnosis, in disease classification and characterization, and ultimately in therapy discovery in rare diseases. The availability of biomarkers and reliable disease models is critical for research and development of new drugs, especially for rare and heterogeneous diseases such as CDG. This work reviews the literature related to repositioned drugs for CDG, discovered by serendipity or through a systemic approach. Recent advances in biomarkers and disease models are also outlined as well as stakeholders’ views on AI for therapy discovery in CDG. 相似文献
9.
Elisa Boschetti Leonardo Caporali Roberto DAngelo Carolina Malagelada Anna Accarino Maria Teresa Dotti Roberta Costa Giovanna Cenacchi Loris Pironi Rita Rinaldi Vincenzo Stanghellini Stefano Ratti Lucia Manzoli Valerio Carelli Roberto De Giorgio 《International journal of molecular sciences》2022,23(15)
mitochondrial neuro-gastrointestinal encephalomyopathy (MNGIE) is a rare genetic disorder characterized by thymidine phosphorylase (TP) enzyme defect. The absence of TP activity induces the imbalance of mitochondrial nucleotide pool, leading to impaired mitochondrial DNA (mtDNA) replication and depletion. Since mtDNA is required to ensure oxidative phosphorylation, metabolically active tissues may not achieve sufficient energy production. The only effective life-saving approach in MNGIE has been the permanent replacement of TP via allogeneic hematopoietic stem cell or liver transplantation. However, the follow-up of transplanted patients showed that gut tissue changes do not revert and fatal complications, such as massive gastrointestinal bleeding, can occur. The purpose of this study was to clarify whether the reintroduction of TP after transplant can recover mtDNA copy number in a normal range. Using laser capture microdissection and droplet-digital-PCR, we assessed the mtDNA copy number in each layer of full-thickness ileal samples of a naive MNGIE cohort vs. controls and in a patient pre- and post-TP replacement. The treatment led to a significant recovery of gut tissue mtDNA amount, thus showing its efficacy. Our results indicate that a timely TP replacement is needed to maximize therapeutic success before irreversible degenerative tissue changes occur in MNGIE. 相似文献
10.