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821.
Yun-Yun Tang Hou-Yu Wang Lu Chen Si Li Chen-Gang Guo Hui-Zhi Fan Cheng-Xi Cao Liu-Yin Fan 《Analytical and bioanalytical chemistry》2013,405(26):8587-8595
We developed a novel polyacrylamide gel electrophoresis (PAGE) method to stack and separate human hemoglobins (Hbs) based on the concept of moving reaction boundary (MRB). This differs from the classic isotachophoresis (ITP)-based stacking PAGE in the aspect of buffer composition, including the electrode buffer (pH 8.62 Tris–Gly), sample buffer (pH 6.78 Tris–Gly), and separation buffer (pH 8.52 Tris–Gly). In the MRB-PAGE system, a transient MRB was formed between alkaline electrode buffer and acidic sample buffer, being designed to move toward the anode. Hbs carried partial positive charges in the sample buffer due to its pH below pI values of Hbs, resulting in electromigrating to the cathode. Hbs would carry negative charges quickly when migrated into the alkaline electrode buffer and be transported to the anode until meeting the sample buffer again. Thus, Hbs were stacked within a MRB until the transient MRB reached the separation buffer and then separated by zone electrophoresis with molecular sieve effect of the gel. The experimental results demonstrated that there were three clear and sharp protein zones of Hbs (HbA1c, HbA0, and HbA2) in MRB-PAGE, in contrast to only one protein zone (HbA0) in ITP-PAGE for large-volume loading (≥15 μl), indicating high stacking efficiency, separation resolution, and good sensitivity of MRB-PAGE. In addition, MRB-PAGE was performed in a conventional slab PAGE device, requiring no special device. Thus, it could be widely used in separation and analysis of diluted protein in a standard laboratory. Figure
Diagram of MRB-induced stacking in a slab PAGE. (A) arrangement of separation buffer (pH 8.01–9.55 Tris–Gly), sample buffer (pH 6.37–7.22 Tris–Gly), and electrode buffer (pH 8.21–9.05 Tris–Gly); (B) initial MRB formed between electrode and sample buffers for stacking of low-content Hbs in sample buffer under electric field; (C) MRB moving toward the anode and partly stacking of Hbs within the MRB; (D) quasi-complete stacking of Hbs via MRB closing to the separating gel; (E) separation of Hbs in a zone electrophoresis mode 相似文献
822.
823.
A concise enantioselective synthesis of malyngamide W (1) and its 2'-epimer was described. The strategy was based on three key steps: (1) ozonolysis of compound 11 which was derived from (R)-(-)-carvone 8, followed by copper-iron-catalyzed rearrangement to give the key cyclohex-2-enone intermediate 5, (2) Nozaki-Hiyama-Kishi coupling reaction between aldehyde 4 and iodide 14 to afford alcohol 3, and (3) asymmetric (R)-CBS reduction of the ketone functionality in compound 21 to establish the C-2' chiral center in the target compound 1. The absolute configuration of malyngamide W (1) was thus confirmed via the synthesis of 1 and 2'-epi-1. 相似文献
824.
Fragmentation pathways of a series of pentacoordinated bisaminoacylspirophosphoranes were elucidated by electrospray ionization multistage mass spectrometry (ESI-MS(n)) in negative mode. The deprotonated ions of pentacoordinated bisaminoacylspirophosphoranes tend to eliminate a corresponding amino acid to form base peak. The hydrogen/deuterium exchange experiment, the high-resolution mass spectrometry, (13)C stable isotope labeling experiment and theoretical calculations were used to rationalize the proposed fragmentation pathways and to verify the differences between the fragmentation pathways. The results indicate that the negative molecular ions of pentacoordinated bisaminoacylspirophosphoranes dissociate through its open-chain tricoordinated tautomers. The relative Gibbs free energies (ΔG) of the product ions and proposed fragmentation pathways were estimated using the B3LYP/6-31 + + G(d, p) model. The results have some potential applications in the identification structures of similar spirophosphorane compounds by ESI-MS(n). 相似文献
825.
826.
In the present paper, different electronic structure methods have been used to determine stationary and intersection structures on the ground (S(0)) and (1)ππ? (S(2)) states of 4-methylpyridine, which is followed by adiabatic and nonadiabatic dynamics simulations to explore the mechanistic photoisomerization of 4-methylpyridine. Photoisomerization starts from the S(2)((1)ππ?) state and overcomes a small barrier, leading to formation of the prefulvene isomer in the S(0) state via a S(2)∕S(0) conical intersection. The ultrafast S(2) → S(0) nonradiative decay and low quantum yield for the photoisomerization reaction were well reproduced by the combined electronic structure calculation and dynamics simulation. The prefulvene isomer was assigned as a long-lived intermediate and suggested to isomerize to 4-methylpyridine directly in the previous study, which is not supported by the present calculation. The nonadiabatic dynamics simulation and electronic structure calculation reveal that the prefulvene isomer is a short-lived intermediate and isomerizes to benzvalene form very easily. The benzvalene form was predicted as the stable isomer in the present study and is probably the long-lived intermediate observed experimentally. A consecutive light and thermal isomerization cycle via Dewar isomer was determined and this cycle mechanism is different from that reported in the previous study. It should be pointed out that formation of Dewar isomer from the S(2)((1)ππ?) state is not in competition with the isomerization to the prefulvene form. The Dewar structure observed experimentally may originate from other excited states. 相似文献
827.
Efficient white light emitting polymers were synthesized based on poly(9,9-dioctylfluorene-co-dibenzothiophene-S,S-dioxide) as blue emitter and a bisphenylamine functionalized 2,1,3-benzothiadiazole (DPABT) as red emitter. It was found that the incorporation of hole-transporting carbazole moiety into polymer main chain could effectively reduce the hole injection barriers, which can lead to distinctly improved charge balance in the emissive layer. Additionally, the hole-transporting carbazole units may form efficient bipolar host with electron-transporting dibenzothiophene-S,S-dioxide units. The white light emitting diodes based on single polymer PFSOCzDPABT showed the maximum luminous efficiency of 3.3 cd/A with the maximum luminance of 10282 cd/m2 , and the luminous efficiency showed only 24% roll off at current density of 400 mA/cm2 . These Commission Internationale d’Enclairage (CIE) coordinates of the devices changed slightly with the driving voltages increasing from 8 V to 12 V, and were very close to National Television System Committee (NTSC) standard white light emission of (0.33, 0.33). The results indicated that the incorporating bipolar host and low band gap DPABT unit was a promising way to achieve efficient single white light emitting copolymers. 相似文献
828.
One-dimensional (1D) homochiral nickel coordination polymers [Ni(3)(bpdc)(RR-L)(2)·(DMF)](n) (2R, RR-L = (R,R)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene), bpdc = 4,4'-biphenyldicarboxylic acid) and [Ni(3)(bpdc)(SS-L)(2)·(DMF)](n) (2S, SS-L = (S,S)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene) based on enantiopure pyridyl-functionalized salen(Ni) metalloligand units NiL ((1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene))Ni(II)) have been synthesized and characterized by microanalysis, IR spectroscopy, solid-state UV-vis spectroscopy, thermogravimetric analysis (TGA), circular dichroism (CD) spectroscopy, cyclic voltammetric measurement, and powder and single crystal X-ray diffraction. Each NiL as unbridging pendant metalloligand uses one terminal pyridyl group to coordinate achiral unit (nickel and bpdc(2-)) building a helical chain, while the other pyridyl group remains uncoordinated. Both 2R and 2S contain left- and right-handed helical chains made of the achiral building blocks, while the NiL as remote external chiral source is perpendicular to the backbone of the helices. The nickel coordination polymers 2R and 2S containing unsaturated active nickel center in metalloligand NiL can be used as self-supported heterogeneous catalysts. They show catalytic activity comparable with their homogeneous counterpart in alkene epoxidation and exhibit great potential as recyclable catalysts. 相似文献
829.
Hua Li Siwang Wang Qian Yang Yanhua Xie Wei Cao Bangle Zhang Jianbo Wang Jiepin Wang Meng Wang 《Chromatographia》2011,73(5-6):495-500
Paeonol, an important constituent of the traditional Chinese medicine Cortex Moutan, has a variety of bioactivity. A simple and sensitive HPLC?CUV method has been developed for analysis of paeonol in different rat tissue (heart, liver, spleen, lung, kidney, and brain). Bio-samples were prepared by simple protein precipitation, and separation of paeonol was achieved on a C18 column with methanol?C2% glacial acetic acid solution 70:30 (v/v) as mobile phase at a flow rate of 1.0 mL min?1. UV detection was at 274 nm and the column temperature was 30 °C. Linearity was good between 0.025 and 5.0 ??g mL?1 (r 2 ?? 0.9990) for tissue samples. Inter-day and intra-day accuracy (as relative error, RE) and precision (as relative standard deviation, RSD) were <5.94 and 6.05%, respectively. The limit of detection was 0.025 ??g mL?1 and extraction recovery for all samples was ??85.86%. The method was successfully applied to a tissue-distribution study after oral administration of 40 mg kg?1 paeonol to healthy Sprague?CDawley rats. The study showed that paeonol was quickly distributed and eliminated after oral administration; liver and kidney were the major distribution tissues of paeonol in rats, and paeonol quickly passed through the blood?Cbrain barrier. It was also found there was no long-term accumulation of paeonol in rat tissues. 相似文献
830.
Matiullah Khan Junna Xu Ning Chen Wenbin Cao Asadullah Zahid Usman D. F. Khan 《Research on Chemical Intermediates》2013,39(4):1633-1644
The electronic and optical properties of pure and Ag-doped anatase TiO2 have been calculated by spin-polarized density functional theory. Ag-doped TiO2 with different Ag doping concentrations ranging from 2.08 to 8.33 % was investigated, and the electronic and optical properties evaluated. Substitutional Ag doped at Ti sites introduced Ag 4d states just above the valence-band maximum, which may help in shifting visible-light excited electrons to the conduction band. Our results show that increasing the doping concentration will enhance visible-light absorption up to Ag doping concentration of 6.25 %; however, further increase of the doping concentration leads to a decrease in visible-light absorption. These results indicate the possibility of tailoring the band gap and optical absorption of TiO2 doped with Ag by varying the doping concentration. The enhanced visible-light absorption for Ag-doped TiO2 with doping concentration of 6.25 % may be due to the existence of widely distributed Ag 4d states above the valence-band maximum and the optimal doping concentration. Ag doping shifted the absorption edge of TiO2 towards visible light, consistent with recent experimental results. Our calculation results provide a reasonable explanation for the experimental findings. 相似文献