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871.
For screening early-stage gastric malignancies, the existing serum biomarkers have limited sensitivity and specificity. Gastric juice biomarkers are scarce and require further investigation. We divided this study on searching potential biomarkers into four parts: (1) detection of differential fluorescence spectrum and peaks in the gastric juice from patients using fluorescence spectroscopy and HPLC, (2) identification and validation of differential peaks using LC/MS and NMR, (3) quantification of potential biomarkers, and (4) establishment of diagnostic detection. The fluorescence intensity (FI), tyrosine, phenylalanine, tryptophan and total protein content were significantly higher in the gastric juice of patients with gastric malignancies (all P<0.01). With all P<0.001, the areas under the receiver operating characteristic curves of the biomarkers were tyrosine, 0.838; phenylalanine, 0.856; and tryptophan, 0.816. At a specificity of 79.4%, the sensitivity for gastric malignancy detection with phenylalanine was 87.9% only. Aromatic amino acids in gastric juices could be used as potential diagnostic biomarkers to screen gastric malignancies. It is a less-invasive and economical method compared to gastric biopsy. 相似文献
872.
Protein kinases transfer phosphate groups from ATP to substrate proteins, they are known to be involved in diverse cellular processes. They are also important therapeutic targets in pharmaceutical design. Previous studies indicated that multiple post-translational modifications (PTMs) exist in kinases in addition to phosphorylation, and these PTMs play an important role in regulating kinases activities. Nevertheless, a comprehensive analysis for PTMs of kinases is insufficient due to technical limitations, which prevent us from better understanding their functional regulation. Here, we have developed a novel strategy that combines glutathione S-transferase tag affinity enrichment with nano-liquid chromatography coupled with tandem mass spectrometry analysis and non-restrictive protein sequence alignment for identification of diverse PTMs in four yeast kinases. The method allows us to enrich and analyze the entire protein isomers and to minimize the loss of all isomers of protein sample during protein purification. In our study, nineteen phosphorylation sites and several other types of PTMs sites were localized in 4 protein kinases. In addition, we found that some interesting mass shifts can not match those of the known PTMs. It suggested the existence of some undescribed PTMs in the proteins. Accordingly, this study showed that the novel strategy holds a great potential for identification of full-spectrum PTMs in proteins. Our data serves as a stepping stone for future functional studies. 相似文献
873.
Three new citrinin derivatives, penicitrinols C, D, and E (1-3), along with two known compounds, citrinin (4) and decarboxydihydrocitrinone (5), were isolated from Penicillium citrinum. Their structures were determined by spectroscopic methods and X-ray diffraction analysis. Compounds 1 and 3 demonstrated weak cytotoxicity against the HL-60 cell line. 相似文献
874.
Ping‐Tsung Huang Cheng‐Wei Chou Mei‐Ying Chang Wen‐Yao Huang Chih‐Chien Lee Yu‐Kai Han Shun‐Wei Liu 《中国化学会会志》2011,58(3):326-331
The performance of a blue polymer light‐emitting diodes (PLED) was significantly improved by doping a controlled amount (<1%) of a hole transport molecule N,N′‐bis‐(1‐naphthyl)‐N,N′‐diphenyl‐1,1′‐biphenyl‐4,4″‐diamine (NPB) into the emitting layer. Hole carrier mobility of the blue emitting polymer, BP105 (trade name of The Dow Chemicals Co.), increased from 5.27 × 10‐7 cm‐2/Vs of the pristine BP105 to 1.80 × 10‐6 cm‐2/Vs with the addition of 1% NPB in BP105. The enhanced carrier mobility greatly promoted performance of a blue PLED device with a device structure of ITO/PEDOT:PSS/BP105+x% NPB/LiF/Ca/Al. Luminance increased from 573 cd/m2 to 2,720 cd/m2 at 6V and efficiency increased from 1.1 lm/W to 1.6 lm/W at 1,000 cd/m2 with 1% NPB in BP105. The most important improvement was an increase in the lifetime of the blue device from 80 to 120 hours at an initial luminance of 400 cd/m2. We found that by choosing the appropriate dopant with good energy alignment and controlled dopant concentration, the performance of a blue PLED device could be greatly improved. 相似文献
875.
On-chip fraction collection for multiple selected ssDNA fragments using isolated extraction channels
Li Z Sun K Sunayama M Matsuo Y Mizeikis V Araki R Ueno K Abe M Misawa H 《Journal of chromatography. A》2011,1218(7):997-1003
High efficiency and high-purity fraction collection is highly sought in analysis of fragments-of-interest from selective polymerase chain reaction (PCR) products generated by High Coverage Gene Expression Profiling (HiCEP) methods. Here we demonstrate a new electrophoretic chip device enabling automatic high-efficient fractionation of multiple ssDNA target fragments during a run of separation. We used thoroughly isolated extraction channels for each selected target to reduce the risk of cross-contamination between targets due to cross-talk of extraction channels. Fragments of 35, 108 and 138 b, were successfully isolated, then the recovery was PCR-amplified and assessed by capillary electrophoresis (CE) analysis. Total impurity level of the targets due to unwanted fragments of 0.7%, 2% and 6% respectively, was estimated. Difficulties in collecting multiple target factions are due to band diffusion and DNA adsorption to the walls for the fragments in the separation channel, which is generated by transferring the DNA target fraction from the extraction section to the target reservoir. Therefore, we have carefully measured band broadening and analyzed its influence on the separation resolution due to the delay. 相似文献
876.
Ishizaki T Teshima K Masuda Y Sakamoto M 《Journal of colloid and interface science》2011,360(1):280-288
Alkyl- and perfluoro-phosphonic acid derived SAMs were successfully formed on Mg alloy by liquid phase method for the first time. The chemical and anticorrosive properties of the prepared SAMs on magnesium alloys were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and electrochemical measurements. Water contact angle measurements revealed that the maximum advancing/receding water contact angles of n-octyl (OP: CH(3)(CH(2))(7)PO(OH)(2)), n-dodecyl (DP: CH(3)(CH(2))(11)PO(OH)(2)), n-octadecyl (ODP: CH(3)(CH(2))(17)PO(OH)(2)) phosphonic acid, and 2-(perfluorohexyl)ethyl (PFEP: CF(3)(CF(2))(5)CH(2)CH(2)PO(OH)(2)) phosphonic acid were 105.1/64.7°, 108.3/69.6°, 111.9/75.2°, and 115.2/67.4° respectively. In the case of alkylphosphonic acid SAMs (OP, DP, and ODP), the advancing and receding water contact angles increased with an increase in the preparation time. The angle-resolved XPS (AR-XPS) data revealed that the film thicknesses of the OP, DP, ODP, PFEP on Mg alloy were estimated to be 0.8, 1.2, 1.7, and 1.1 nm, respectively. The XPS O 1s data support that the phosphonic acid derived SAM is covalently bound to the oxide or hydroxide surface of the Mg alloy in a monodenate or bidenate manner. Chemical stability of the alkyl- and perfluoro-phosphonic acid modified Mg alloy surfaces was investigated using aqueous solutions at pH=4.0, 7.0, and 10.0. The contact angles of OP, DP, and PFEP modified Mg surface decreased rapidly within the first 5 min after immersion in all the aqueous solutions and were less than 20°. On the other hand, the contact angles of the ODP modified Mg alloy after immersion in aqueous solutions at pH 4, 7 and 10 for 5 min were 45.1°, 89.3,° and 85.5°, respectively. The ODP modified Mg alloy had highest chemical stability in four types of the phosphonic acid derived SAMs used in this study, indicating that the molecular density of ODP on Mg alloy would be higher than those of OP, DP, PFEP on Mg alloy. The corrosion resistance of ODP modified Mg alloy was investigated by potentiodynamic polarization curve measurements. The ODP modified Mg alloy exhibits protective properties in a solution containing Cl(-) ions compared to unmodified Mg alloy. 相似文献
877.
Comprehensive computational modeling of coordination structures, thermodynamic stabilities, and luminescence spectra of uranyl-glycine-water complexes [UO(2)(Gly)(n)aq(m)](2+) (Gly = glycine, aq = H(2)O, n = 0-2, m = 0-5) in aqueous solution has been carried out using relativistic density functional approaches. The solvent is approximated by a dielectric continuum model and additional explicit water molecules. Detailed pictures are obtained by synergic combination of experimental and theoretical data. The optimal equatorial coordination numbers of uranyl are determined to be five. The energies of several complex conformations are competitively close to each other. In non-basic solution the most probable complex forms are those with two water ligands replaced by the bidentate carboxyl groups of zwitterionic glycine. The N,O-chelation in non-basic solution is neither entropically nor enthalpically favored. The symmetric and antisymmetric stretch vibrations of the nearly linear O-U-O unit determine the luminescence features. The shapes of the vibrationally resolved experimental solution spectra are reproduced theoretically with an empirically fitted overall line-width parameter. The calculated luminescence origins correspond to thermally populated, near-degenerate groups of the lowest electronically excited states of (3)Δ(g) and (3)Φ(g) character, originating from (U-O)σ(u) → (U-5f)δ(u),?(u) configurations of the linear [OUO](2+) unit. The intensity distributions of the vibrational progressions are consistent with U-O bond-length changes around 5 1/2 pm. The unusually high intensity of the short wavelength foot is explained by near-degeneracy of vibrationally and electronically excited states, and by intensity enhancement through the asymmetric O-U-O stretch mode. The combination of contemporary computational chemistry and experimental techniques leads to a detailed understanding of structures, thermodynamics, and luminescence of actinide compounds, including those with bioligands. 相似文献
878.
An efficient strategy for the total synthesis of (+)-przewalskin B is reported. The key steps feature an intermolecular S(N)2' substitution of iodoallylic phosphate with organocupper reagent, a diastereoselective organocatalytic aldol cyclization, as well as a Rh(2)(OAc)(4)-mediated intramolecular carbene insertion to the tertiary C-H bond. 相似文献
879.
A sweeping structural revision of the sarcodonin natural product family (published structures 1a-13a) is proposed after extensive studies aimed at their chemical synthesis. Key features of revised structure 1b include replacement of the N,N-dioxide moiety with an oxime, ring-opening of the central diketopiperazine, and transposition of the terphenyl wing from the 1β-2β position of 1a to the 2β-3β position of 1b. This structure revision arose from the serendipitous synthesis of a benzodioxane aminal (44) whose structure was unambiguously determined by X-ray crystallography and whose spectral properties bore considerable resemblance to the published data for the sarcodonins. A versatile new method for O-arylation of hydroxamic acids is also reported herein, as well as a manganese(III)-mediated α-oxidation of hydroxamic acids to aminals. 相似文献
880.
Lambrecht DS Brandhorst K Miller WH McCurdy CW Head-Gordon M 《The journal of physical chemistry. A》2011,115(13):2794-2801
A kinetic-energy-based fitting metric for application in the context of resolution of the identity second-order M?ller-Plesset perturbation theory is presented, which is derived from the Poisson equation. Preliminary tests of the applicability include the evaluation of the error in the correlation energy, compared to standard M?ller-Plesset perturbation theory, with respect to the auxiliary basis set employed. We comment on the potential merits of this fitting metric, compared to standard resolution of the identity second-order M?ller-Plesset perturbation theory, and discuss its scaling behavior in the limit of large molecules. 相似文献