全文获取类型
收费全文 | 6012篇 |
免费 | 262篇 |
国内免费 | 1444篇 |
专业分类
化学 | 7174篇 |
晶体学 | 31篇 |
力学 | 35篇 |
综合类 | 28篇 |
数学 | 16篇 |
物理学 | 434篇 |
出版年
2024年 | 6篇 |
2023年 | 27篇 |
2022年 | 63篇 |
2021年 | 78篇 |
2020年 | 152篇 |
2019年 | 134篇 |
2018年 | 135篇 |
2017年 | 205篇 |
2016年 | 235篇 |
2015年 | 172篇 |
2014年 | 217篇 |
2013年 | 627篇 |
2012年 | 318篇 |
2011年 | 290篇 |
2010年 | 313篇 |
2009年 | 383篇 |
2008年 | 402篇 |
2007年 | 378篇 |
2006年 | 374篇 |
2005年 | 361篇 |
2004年 | 328篇 |
2003年 | 265篇 |
2002年 | 267篇 |
2001年 | 233篇 |
2000年 | 213篇 |
1999年 | 203篇 |
1998年 | 175篇 |
1997年 | 162篇 |
1996年 | 165篇 |
1995年 | 143篇 |
1994年 | 161篇 |
1993年 | 134篇 |
1992年 | 120篇 |
1991年 | 70篇 |
1990年 | 53篇 |
1989年 | 39篇 |
1988年 | 38篇 |
1987年 | 21篇 |
1986年 | 11篇 |
1985年 | 8篇 |
1984年 | 8篇 |
1983年 | 4篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 1篇 |
1979年 | 6篇 |
1978年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有7718条查询结果,搜索用时 187 毫秒
971.
《Macromolecular bioscience》2018,18(7)
The cyclic brush polymers, due to the unique topological structure, have shown in the previous studies higher delivery efficacy than the bottlebrush analogues as carriers for drug and gene transfer. However, to the best of knowledge, the preparation of reduction‐sensitive cyclic brush polymers for drug delivery applications remains unexplored. For this purpose, a reduction‐sensitive amphiphilic cyclic brush copolymer, poly(2‐hydroxyethyl methacrylate‐g‐poly(ε‐caprolactone)‐disulfide link‐poly(oligoethyleneglycol methacrylate)) (P(HEMA‐g‐PCL‐SS‐POEGMA)) with reducible block junctions bridging the hydrophobic PCL middle layer and the hydrophilic POEGMA outer corona is designed and synthesized successfully in this study via a “grafting from” approach using sequential ring‐opening polymerization (ROP) and atom transfer free radical polymerization (ATRP) from a cyclic multimacroinitiator PHEMA. The resulting self‐assembled unimolecular core–shell–corona (CSC) micelles show sufficient salt stability and efficient destabilization in the intracellular reducing environment for a promoted drug release toward a greater therapeutic efficacy relative to the reduction‐insensitive analogues. The overall results demonstrate the reducible cyclic brush copolymers developed herein provides an elegant solution to the tradeoff between extracellular stability and intracellular high therapeutic efficacy toward efficient anticancer drug delivery. 相似文献
972.
Pan H Liu J Dong Y Sima M Kopecková P Brandi ML Kopecek J 《Macromolecular bioscience》2008,8(7):599-605
Bone-targeting N-(2-hydroxypropyl)methacrylamide (HPMA) copolymer-PGE(1) conjugates, containing cathepsin K sensitive spacers, were incubated with induced osteoclasts and osteoblasts, their precursors, and control non-skeletal cells. The release of PGE(1) was monitored by an HPLC assay. In both murine and human cell lines, osteoclasts appeared to be the most active cells in the cleavage (PGE(1) release). Incubation with osteoblasts also resulted in fast PGE(1) release, whereas precursor and control cells released PGE(1) with a substantially slower rate than bone cells (apparently through ester bond cleavage). Experiments in the presence of inhibitors revealed that other enzymes, in addition to cathepsin K, were participating in the cleavage of the conjugate. Confocal fluorescence studies exposed internalization of the conjugate by endocytosis with ultimate localization in the lysosomal/endosomal compartment. 相似文献
973.
A novel IPN hydrogel designed to recognize MMTCA is prepared by applying the molecular-imprinting method. The IPN is characterized by FT-IR, DSC, and SEM. Langmuir analysis shows that an equal class of adsorption is formed in the hydrogel. The adsorption equilibrium constant and the maximum adsorption capacity are evaluated, and the effect of the pH on MMTCA adsorption is discussed. The selectivity of the imprinted polymer for MMTCA is studied in aqueous solutions of MMTCA/aspirin/riboflavin. The results suggest that the MMTCA-imprinted polymer shows superior selectivity for MMTCA as compared to riboflavin and aspirin. The reproducibility of the imprinted polymer to MMTCA is also studied. 相似文献
974.
M. Dolores Fernández M. Jesús Fernández 《Journal of Thermal Analysis and Calorimetry》2008,92(3):829-837
The thermal degradation of poly(vinyl acetate) (PVA), poly(vinyl alcohol) (PVAL), vinyl acetate-vinyl alcohol (VAVAL), vinyl
acetate-vinyl-3,5-dinitrobenzoate (VAVDNB) and vinyl alcohol-3,5-dinitrobenzoate (VALVDNB) copolymers have been studied using
differential thermal analysis (DTA) and thermogravimetry (TG) under isothermal and dynamic conditions in nitrogen. Thermal
analysis indicates that PVA and PVAL are thermally more stable than VAVAL copolymers, being PVAL the most stable polymer.
The presence of small amounts of vinyl-3,5-dinitrobenzoate (VDNB) in PVA or PVAL produces a marked decrease in the thermal
stability of both homopolymers, being VALVDNB copolymers the less stable materials. The apparent activation energy of the
degradative process was determined by the Kissinger and Flynn-Wall methods which agree well. 相似文献
975.
Bakr F. Abdel-Wahab Salwa F. Mohamed Abd El-Galil E. Amr Mohamed M. Abdalla 《Monatshefte für Chemie / Chemical Monthly》2008,139(9):1083-1090
Methyl 2-(thiazol-2-ylcarbamoyl)acetate was synthesized and used as starting material. It was treated with hydrazine hydrate
to afford the hydrazide, which was reacted with nitromethane and formaldehyde to give the saturated nitropyrimidine. The hydrazide
was reacted with phenyl isothiocyanate to afford the thiosemicarbazide, which was cyclized with ethyl bromoacetate, sodium
hydroxide, or sulfuric acid to afford N-phenylthiazolidinone, N-phenyltriazole, and thiadiazolyl derivatives. The methyl 2-(thiazol-2-ylcarbamoyl)acetate was coupled with diazonium salts
of aniline, 4-chloroaniline, 4-bromoaniline, or 4-aminobenzenesulfonamide to afford the carbamoyl acetates, which were reacted
with 2-aminobenzimidazole, 1,2,4,5-tetrachlorophthalic anhydride, and hydrazine hydrate to afford the corresponding thiazolylmalonamide,
tetrachloroisoindolylimide, and tri-azole derivatives. Schiff bases and imides are newly synthesized candidates obtained via simple condensation of the hydrazide with aldehydes, 2,3-pyridinedicarboxylic anhydride, or 1,8-naphthalenedicarboxylic anhydride.
The pharmacological screening showed that many of these compounds have good antihypertensive α-blocking activity and low toxicity.
Correspondence: Abd El-Galil E. Amr, National Research Center, Applied Organic Chemistry, Dokki, Cairo, Egypt. 相似文献
976.
Thermal events encountered throughout the heat treatment of praseodymium acetate, Pr(CH3COO)3·H2O, were studied in nitrogen and air atmospheres. The samples calcined at the 300–700 °C temperature range were characterized using XRD, IR and N2 adsorption. Moreover, in situ electrical conductivity was employed to follow up the formation of the different decomposition intermediates. The results indicated that the anhydrous salt decomposes to the final product, PrO1.833, through the formation of the following intermediates: Pr(OH)(CH3COO)2, PrO(CH3COO) and Pr2O2(CO3). PrO1.833 formed at 500, 600, and 700 °C possesses a surface area of 17, 16 and 10 m2/g and crystallites size of 14, 17 and 30 nm, respectively. 相似文献
977.
A phosphorus-containing flame retardant, 4-(5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinan-2-yloxymethyl)-2,6,7-trioxa-1-phospha-bicyclo[2.2.2]octane-1-oxide (MOPO), was synthesized successfully and characterized. The flame retardancy and thermal behavior of a new intumescent flame-retardant (IFR) system for EVA, which was made of MOPO and ammonium polyphosphate (APP), were investigated by limiting oxygen index (LOI) test, vertical burning test (UL-94), cone calorimeter, and thermogravimetric analysis (TGA). An LOI value of 28.4 and UL-94 V-0 rating can be achieved when the total loading of MOPO and APP was 30 wt.%. The results from cone calorimeter indicate that both the heat release rate (HRR) and the total heat release (THR) of IFR-EVA decreased significantly compared with those of neat EVA. TG curves showed that the amount of residues increased significantly when intumescent additives were added; it also could be found that the LOI values increased with the increase in char residues. Meanwhile, morphology of the residues obtained from burning IFR-EVA in LOI test was studied through the SEM observations and rich compact char layers could explain the excellent flame retardance. 相似文献
978.
Alina Sionkowska Justyna Kozlowska Anna Planecka Joanna Skopinska-Wisniewska 《Polymer Degradation and Stability》2008,93(12):2127-2132
The photochemical stability of poly(vinyl pyrrolidone) (PVP) in the presence of 1%, 3% and 5% of collagen has been studied by UV-vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermogravimetry analysis (TG) and derivative thermogravimetry (DTG). Surface properties have been studied by contact angle measurements. PVP samples and samples containing 1%, 3% and 5% of collagen were irradiated with UV light of wavelength λ = 254 nm in air for up to 24 h. The amount of gel created during UV irradiation was estimated.PVP in the presence of 1%, 3% and 5% of collagen is less stable both thermally and photochemically. Collagen enhances photochemical processes leading to crosslinking of PVP. The contact angle measurements and values of surface free energy showed that the wettability of PVP films was changed by the addition of collagen and by UV irradiation. The increase of polarity of samples indicates an efficient photooxidation on the surface upon UV irradiation. 相似文献
979.
We present a simple approach for on-line concentration of SDS-protein complexes by using poly(vinyl alcohol) (PVA) solution in CGE. In comparison to the coated capillary, the presence of EOF in CGE omitted the need to fill the capillaries with polymer solutions prior to the analysis. More importantly, we found that highly reproducible separation of eight proteins by 3.5% PVA was achieved between runs and without the regeneration of high bulk EOF; the RSD of migration times was less than 0.7%. To further improve the concentration sensitivity, neutral PVA was introduced into the capillary with the help of EOF to act as sieving matrix. The occurrence of stacking at the boundary between the PVA and the sample zone is mainly due to the retardation of proteins by PVA. As a result, the LODs at an S/N of 3 for SDS-protein complexes are of the order of sub-nM to several nM. For example, the LOD for BSA is 0.78 nM, which is a 91-fold sensitivity enhancement over the normal injection. In addition, our stacking method has been applied to the analyses of proteins in Escherichia coli cells. The peak for beta-galactosidase (E. coli) was observed after 0.1 microM beta-galactosidase was spiked into the E. coli samples. 相似文献
980.
Toshiaki Yoshioka Tomohito Kameda Shogo Imai Akitsugu Okuwaki 《Polymer Degradation and Stability》2008,93(6):1138-1141
A solution of NaOH dissolved in ethylene glycol (EG) was effective in the dechlorination of poly(vinyl chloride) (PVC) at atmospheric pressure. The degree of dechlorination increased with increasing temperature, reaching a maximum of 97.8% at 190 °C. The dechlorination proceeded under chemical control and exhibited first-order kinetics with an apparent activation energy of 170 kJ mol−1. The apparent rate constant for dechlorination in 1.0 M NaOH/EG was approximately 150 times greater than that in 1.0 M NaOH/H2O. In addition, dechlorination was faster at atmospheric pressure in NaOH/EG than under high pressure in NaOH/H2O. The dechlorination reaction occurs via a combination of E2 and SN2 mechanisms. 相似文献