全文获取类型
收费全文 | 4917篇 |
免费 | 184篇 |
国内免费 | 22篇 |
专业分类
化学 | 3641篇 |
晶体学 | 45篇 |
力学 | 107篇 |
数学 | 676篇 |
物理学 | 654篇 |
出版年
2023年 | 33篇 |
2022年 | 59篇 |
2021年 | 83篇 |
2020年 | 104篇 |
2019年 | 81篇 |
2018年 | 83篇 |
2017年 | 80篇 |
2016年 | 143篇 |
2015年 | 133篇 |
2014年 | 167篇 |
2013年 | 312篇 |
2012年 | 329篇 |
2011年 | 370篇 |
2010年 | 222篇 |
2009年 | 171篇 |
2008年 | 309篇 |
2007年 | 312篇 |
2006年 | 258篇 |
2005年 | 268篇 |
2004年 | 263篇 |
2003年 | 187篇 |
2002年 | 170篇 |
2001年 | 59篇 |
2000年 | 47篇 |
1999年 | 47篇 |
1998年 | 40篇 |
1997年 | 32篇 |
1996年 | 53篇 |
1995年 | 27篇 |
1994年 | 35篇 |
1993年 | 38篇 |
1992年 | 31篇 |
1991年 | 39篇 |
1990年 | 32篇 |
1989年 | 24篇 |
1988年 | 23篇 |
1987年 | 26篇 |
1986年 | 16篇 |
1985年 | 31篇 |
1984年 | 41篇 |
1983年 | 20篇 |
1982年 | 37篇 |
1981年 | 28篇 |
1980年 | 29篇 |
1979年 | 30篇 |
1978年 | 21篇 |
1977年 | 20篇 |
1976年 | 20篇 |
1975年 | 23篇 |
1973年 | 17篇 |
排序方式: 共有5123条查询结果,搜索用时 15 毫秒
41.
For use in micro-patterned scaffolds in tissue engineering, novel diacrylated triblock macromers (PLA-b-PCL-b-PLA, PGA-b-PCL-b-PGA and PCL-b-PEO-b-PCL) were synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and gel permeation chromatography (GPC). All diacrylated polymers were designed as triblock copolymers and involved biodegradable blocks of relatively non-polar epsilon-caprolactone (CL) and polar monomers such as glycolide (GA), lactide (LA) or ethylene oxide (EO). All triblock polymers were prepared in molecular weights of a few kilo daltons via the anionic ring-opening polymerization (ROP) of the corresponding lactide, glycolide or caprolactone using stannous octoate [Sn(Oct)(2)] as catalyst. The polymers had low polydispersity indices, ranging from 1.23 to 1.56. Biodegradable polymeric networks were prepared with conversions of 72-84% via photopolymerization of the triblock diacrylated polymers with 2,2-dimethoxy-2-phenylacetophenone (DMPA) as photoinitiator. PLA-b-PCL-b-PLA copolymers crumbled easily and were not suitable for micro-patterning. PGA-b-PCL-b-PGA copolymers had higher water contact angles than PCL-b-PEO-b-PCL and were also cytocompatible with Fibroblasts 3T3. 相似文献
42.
Gary W Caldwell John A Masucci Mary Evangelisto Robert White 《Journal of chromatography. A》1998,800(2):1071-169
Chromatographic retention factors (k′) of a series of eight β-adrenoceptor antagonist compounds (β-adrenolytic drugs) were determined employing an immobilized artificial membrane column (IAM.PC.DD). The influence of mobile phase pH, ionic strength, and organic modifier composition was studied in order to examine column performance. After the IAM.PC.DD columns were exposed to approximately 7000 column volumes of a 0.01 M PBS mobile phase, five out of six columns tested showed significant peak broadening and decreased k′ values indicative of premature column failure. The data suggested that the immobilized phospholipids stationary phase was removed by the 0.01 M PBS mobile phase. The β-adrenolytic drug's log k′IAM values obtained with an IAM.PC.DD column were compared to an esterIAM.PC.MG column for predicting drug membrane interactions. For the linear regression analysis between log k′IAM and the logarithm of the n-octanol–water partition coefficients (rIAM.PC.DD=0.8710 vs. rIAM.PC.MG=0.9538), the C18 HPLC retention factors (rIAM.PC.DD=0.8408 vs. rIAM.PC.MG=0.9380), the liposome partition coefficients (rIAM.PC.DD=0.8887 vs. rIAM.PC.MG=0.9187), and various pharmacokinetic parameters, significantly better correlations were obtained with the esterIAM.PC.MG column than the IAM.PC.DD column. 相似文献
43.
Hoteling AJ Kawaoka K Goodberlet MC Yu WM Owens KG 《Rapid communications in mass spectrometry : RCM》2003,17(14):1671-1676
Details of the optimization of the collision-induced dissociation (CID) process, using a collision cell on a matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometer, are described using poly(ethylene glycol) 1000 (PEG 1000) as a model analyte. The effects of collision gas identity (helium, air, and argon), as well as collision gas pressure, on the resulting MS/MS data were investigated. With PEG 1000, helium was found to give the best results with respect to signal-to-noise (S/N) ratio. The optimum pressure for each gas was found to be in the range where the precursor ion signal was attenuated to approximately 30-50% for helium and 40-60% for argon. The effect of cation choice (Li, Na, and K) on the CID of PEG was also studied. CID spectra were produced for each, but PEG cationized with lithium was found to produce the spectra with the highest S/N ratio. The MALDI-TOF CID spectra that were generated for PEG were compared with the high-energy and low-energy MS/MS spectra obtained from a sector mass spectrometer and from a triple quadrupole mass spectrometer, respectively. The results observed for PEG confirm that CID on a MALDI-TOF mass spectrometer is a high-energy MS/MS technique. 相似文献
44.
Thompson M Wilkins SJ Compton RG Viles HA 《Journal of colloid and interface science》2003,259(2):338-345
The dissolution kinetics of surface-pretreated and weathered calcite was investigated in dilute acid using a channel flow cell with microdisk detection. Two pretreatments were studied, polymaleic acid and phosphoric acid. Treatment with polymaleic acid was shown to significantly passivate calcite but to a lesser extent than the phosphoric acid and the former coating was found to be less effective for protection of calcite from acid attack. However, treatment of calcite with phosphoric acid resulted in the passivation of calcite from acid attack which strongly inhibited dissolution, an effect that was enhanced even further after exposure to the environment. 相似文献
45.
Jo E Sanna MG Gonzalez-Cabrera PJ Thangada S Tigyi G Osborne DA Hla T Parrill AL Rosen H 《Chemistry & biology》2005,12(6):703-715
The essential role of the sphingosine 1-phosphate (S1P) receptor S1P(1) in regulating lymphocyte trafficking was demonstrated with the S1P(1)-selective nanomolar agonist, SEW2871. Despite its lack of charged headgroup, the tetraaromatic compound SEW2871 binds and activates S1P(1) through a combination of hydrophobic and ion-dipole interactions. Both S1P and SEW2871 activated ERK, Akt, and Rac signaling pathways and induced S1P(1) internalization and recycling, unlike FTY720-phosphate, which induces receptor degradation. Agonism with receptor recycling is sufficient for alteration of lymphocyte trafficking by S1P and SEW2871. S1P(1) modeling and mutagenesis studies revealed that residues binding the S1P headgroup are required for kinase activation by both S1P and SEW2871. Therefore, SEW2871 recapitulates the action of S1P in all the signaling pathways examined and overlaps in interactions with key headgroup binding receptor residues, presumably replacing salt-bridge interactions with ion-dipole interactions. 相似文献
46.
Liu Y Vinje J Pacifico C Natile G Sletten E 《Journal of the American Chemical Society》2002,124(43):12854-12862
The reactions of the anticancer complex trans-[PtCl2{(E)-HN=C(OMe)Me}2] (trans-EE) with a series of ribo and deoxyribodinucleotides have been studied by HPLC and 2D [1H, 15N] HMQC NMR spectroscopy and compared with those of the inactive trans isomer of cisplatin, trans-[PtCl2(NH3)2] (trans-DDP). Reactions of trans-EE with r(ApG) and d(ApG) take place through solvolysis of the starting substrate and subsequent formation of trans G-N7/monochloro and G-N7/monoaqua adducts. Slowly, the monofunctional adducts evolve to a bifunctional adduct forming an unprecedented and unexpected A-N3/G-N7 platinum cross-link spanning two trans positions. For stereochemical reasons, trans platinum complexes cannot form N7/N7 cross-links between adjacent purines in di- or polynucleotides. For the reverse sequence r(GpA), no chelate structure was formed even after a two-week reaction. The reaction of trans-DDP with r(ApG) produces many more products than the analogous reaction with trans-EE. One of these products was identified as the A-N3/G-N7 trans-chelate. 相似文献
47.
Rhodium(I) complexes trans-[RhCl(CO)(PR(2)[NC(4)H(3)C(O)Me-2])(2)] (R = Ph, NC(4)H(4)) react with water to give the diphosphoxane-bridged dimers [Rh(2)Cl(2)(CO)(2)(mu-PR(2)OPR(2))(2)] following cleavage of the P-N bonds to the 2-acetyl-N-pyrrolyl groups. The two dimers have been crystallographically characterized and show a number of structural differences, with the PPh(2)OPPh(2) compound possessing semibridging chloride and carbonyl ligands whereas the P(NC(4)H(4))(2)OP(NC(4)H(4))(2) compound contains only terminal chlorides and carbonyls. No evidence for cleavage of the P-N bonds involving the unfunctionalized N-pyrrolyl groups in trans-[RhCl(CO)(P[NC(4)H(4)](2)[NC(4)H(3)C(O)Me-2])(2)] was observed. 相似文献
48.
Amidines can be prepared on a solid support by reducing polymer-bound amidoximes with SnCl2·2H2O. The method has proved to be straightforward and highly efficient. Amidoximes attached to the solid support are readily available by treating resin-bound nitriles with hydroxylamine. 相似文献
49.
The reaction of epibromohydrin with hydroxyquinazolin-2-(1H)one derivatives. Novel oxazine formation
Mary Lou Cotter Victor Bandurco Elizabeth Wong Zoltan G. Hajos 《Journal of heterocyclic chemistry》1979,16(3):623-624
Epibromohydrin was found to react with 7-hydroxy-2-methylpyrrolo[1,2-c]quinazolin-5(6H)-one ( 4 ) in the presence of sodium hydroxide to form the novel oxazine 5 . The structure of compound 5 was proven by cmr and pmr analysis. 相似文献
50.
Toward a microchip-based solid-phase extraction method for isolation of nucleic acids 总被引:7,自引:0,他引:7
Wolfe KA Breadmore MC Ferrance JP Power ME Conroy JF Norris PM Landers JP 《Electrophoresis》2002,23(5):727-733
A silica-based solid-phase extraction system suitable for incorporation into a microchip platform (nu-total analytical system; nu-TAS) would find utility in a variety of genetic analysis protocols, including DNA sequencing. The extraction procedure utilized is based on adsorption of the DNA onto bare silica. The procedure involves three steps: (i) DNA adsorption in the presence of a chaotropic salt, (ii) removal of contaminants with an alcohol/water solution, and (iii) elution of the adsorbed DNA in a small volume of buffer suitable for polymerase chain reaction (PCR) amplification. Multiple approaches for incorporation of this protocol into a microchip were examined with regard to extraction efficiency, reproducibility, stability, and the potential to provide PCR-amplifiable DNA. These included packing microchannels with silica beads only, generating a continuous silica network via sol-gel chemistry, and combinations of these. The optimal approach was found to involve immobilizing silica beads packed into the channel using a sol-gel network. This method allowed for successful extraction and elution of nanogram quantities of DNA in less than 25 min, with the DNA obtained in the elution buffer fraction. Evaluation of the eluted DNA indicated that it was of suitable quality for subsequent amplification by PCR. 相似文献