全文获取类型
收费全文 | 5170篇 |
免费 | 725篇 |
国内免费 | 482篇 |
专业分类
化学 | 5758篇 |
晶体学 | 17篇 |
力学 | 37篇 |
综合类 | 35篇 |
数学 | 175篇 |
物理学 | 355篇 |
出版年
2024年 | 14篇 |
2023年 | 105篇 |
2022年 | 409篇 |
2021年 | 384篇 |
2020年 | 361篇 |
2019年 | 237篇 |
2018年 | 212篇 |
2017年 | 256篇 |
2016年 | 359篇 |
2015年 | 312篇 |
2014年 | 332篇 |
2013年 | 422篇 |
2012年 | 345篇 |
2011年 | 312篇 |
2010年 | 273篇 |
2009年 | 285篇 |
2008年 | 257篇 |
2007年 | 235篇 |
2006年 | 216篇 |
2005年 | 175篇 |
2004年 | 166篇 |
2003年 | 143篇 |
2002年 | 83篇 |
2001年 | 71篇 |
2000年 | 51篇 |
1999年 | 70篇 |
1998年 | 50篇 |
1997年 | 51篇 |
1996年 | 35篇 |
1995年 | 33篇 |
1994年 | 28篇 |
1993年 | 15篇 |
1992年 | 8篇 |
1991年 | 11篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 8篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 7篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有6377条查询结果,搜索用时 15 毫秒
991.
Quantitative Prediction of Rate Constants for Aqueous Racemization To Avoid Pointless Stereoselective Syntheses
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Andrew Ballard Dr. Hiwa O. Ahmad Dr. Stefania Narduolo Lucy Rosa Nikki Chand Dr. David A. Cosgrove Dr. Peter Varkonyi Dr. Nabil Asaad Dr. Simone Tomasi Dr. Niklaas J. Buurma Dr. Andrew G. Leach 《Angewandte Chemie (International ed. in English)》2018,57(4):982-985
Racemization has a large impact upon the biological properties of molecules but the chemical scope of compounds with known rate constants for racemization in aqueous conditions was hitherto limited. To address this remarkable blind spot, we have measured the kinetics for racemization of 28 compounds using circular dichroism and 1H NMR spectroscopy. We show that rate constants for racemization (measured by ourselves and others) correlate well with deprotonation energies from quantum mechanical (QM) and group contribution calculations. Such calculations thus provide predictions of the second‐order rate constants for general‐base‐catalyzed racemization that are usefully accurate. When applied to recent publications describing the stereoselective synthesis of compounds of purported biological value, the calculations reveal that racemization would be sufficiently fast to render these expensive syntheses pointless. 相似文献
992.
Dr. Jens Atzrodt Dr. Volker Derdau Prof. Dr. William J. Kerr Dr. Marc Reid 《Angewandte Chemie (International ed. in English)》2018,57(12):3022-3047
The various applications of hydrogen isotopes (deuterium, D, and tritium, T) in the physical and life sciences demand a range of methods for their installation in an array of molecular architectures. In this Review, we describe recent advances in synthetic C?H functionalisation for hydrogen isotope exchange. 相似文献
993.
《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
994.
《Macromolecular bioscience》2018,18(7)
In two ABA type amphiphilic block copolymers (P1, P2), the hydrophobic B block consists of a bioreducible segmented poly(disulfide) (PDS), while poly‐N‐isopropylacrylamide (PNIPAM) or poly(triethyleneglycol)methylether‐methacrylate (PTEGMA) serve as the hydrophilic A blocks in P1 and P2, respectively, leading to the formation of polymersome and micelle, owing to the difference in the packing parameters. Both exhibit comparable doxorubicin (Dox) encapsulation efficiency, but glutathione (GSH) triggered release appears much faster from the polymersome than micelle owing to the complete degradation of the PDS segment in polymersome morphology unlike in micelle. Dox‐loaded polymers (P1‐Dox and P2‐Dox) exhibit minimum toxicity to normal cells like C2C12. By contrast, P1‐Dox shows excellent killing efficiency to the HeLa cells (cancer cell) (in which the GSH concentration is significantly higher). However, P2‐Dox reveals a rather poor activity even to HeLa cells. Fluorescence microscopy studies show comparable cellular uptake of P1‐Dox and P2‐Dox. But the polymersome entrapped dye escapes fast from the cargo and reach the nucleus, while the drug‐loaded micelle remains trapped in the perinuclear zone explaining the significant difference in the drug delivery performance of polymersome and micelle. 相似文献
995.
《Macromolecular bioscience》2018,18(8)
Reflux precipitation polymerization (RPP) represents an effective approach that enables to prepare various types of polymeric nanogels with precise control over the morphology and structure. Owing to facile loading or modification by a variety of functional moieties, rationally designed nanogels pose the possibility to attain a platform for tailoring functional properties that could be widely used for various biomedical applications, such as multifunctional drug delivery, enrichment of functional peptides, separation of specific proteins, as well as detection of circulating tumor cells. This feature article highlights RPP as a promising polymerization strategy that provides access to facile generation of modular nanostructures or multifunctional properties in a diverse range of biomedical applications, proving that RPP has great potential to become one of the most attractive polymerization techniques in polymer chemistry. 相似文献
996.
从患“白点病”的病鳖体中分离到四株菌,经人工感染试验,仅一株菌对健康稚鳖表现出较强的致病力。对该菌的形态特征、培养特性和生理、生化反应的鉴定认为:该病原菌是嗜水气单胞菌(Aeromonashydrophila)应用药敏纸片法研究了20种化学疗剂对该病原菌的生长抑制作用,结果表明:环丙沙星、氟哌酸、庆大霉素、痢特灵等对病原菌具较强抑制作用,而复方新诺明、头孢拉定、呋喃妥因、麦迪霉素、氨苄青霉素等无抑菌作用.在此基础上进行了药物疗效试验。 相似文献
997.
M. R. Caira E.C. Van Tonder M.M. De Villiers A.P. Lötter 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(1):1-16
Single crystal X-ray structures of solvated forms of theanthelmintic drug Niclosamide reveal distinctly differentmodes of inclusion for different solvents. These modes are,respectively, cavity occupation by water molecules in 1 : 1niclosamide.H2O, channel occupation by tetrahydrofuranmolecules in 1 : 1 niclosamide.THF, and intercalation bytetraethylene glycol molecules in 2 : 1 niclosamide.TEG. Inall three compounds the host drug molecule adopts the same,nearly planar conformation, which is maintained by anintramolecular N-H.O hydrogen bond. Host-guest recognitioninvariably involves hydrogen bonding between the drughydroxyl group and an oxygen acceptor atom of the solventmolecule. The observed modes of solvent inclusion can bereconciled with the behaviour of the crystals on heating. 相似文献
998.
Shome Nath Mitra S. S. Rajan T. R. Govindachari E. Subramanian 《Journal of chemical crystallography》1996,26(3):223-226
The crystal structure of tylophorine (Chemical name 2,3,6,7 tetramethoxy phenanthro [9,10:6, 7] indolizidine. Contribution No. 0871.) methiodide monohydrate has been determined. C25H30NO
4
+
I–·H20, triclinic, P,a=8.831(1)Å, b=10.842(2),c=13.902(2), =105.0(1)o, =104.7(1), =97.3(1),V=1210.22Å3, Z=2,D
x
=1.428 g./cm–3, (CuK)=1.54184Å, (CUK)=107.2 cm–1, F(000)=544,T=295oK,R=0.038,Rw=0.046, for 2331 observed reflections withI2(I). Apart from van der Waals forces, the structure is stabilized by two hydrogen bonds of the type Ow(H) ... O and Ow(H) ... I– involving the water molecule as the donor and atom O4 of the methoxy group and I– as acceptors. 相似文献
999.
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
1000.
Comb-like polymers with biocompatible oxyethylene backbones and amphiphilic side groups were synthesized via polymer-analogous reactions. Using these polymers, indomethacin-loaded polymeric micelles were fabricated with various drug-to-polymer weight ratios using the oil-in-water emulsion technique. In addition, the size, size distribution, CMC, drug-loading content, and entrapment efficiency of the polymeric micelles were analyzed. The volume-weighted diameters of polymeric micelles ranged from 10 to 140 nm and were narrowly distributed for passive targeting drug delivery. The CMCs were lower (approximately 10(-8) M) than for conventional surfactants and block copolymers. 相似文献