全文获取类型
收费全文 | 4402篇 |
免费 | 539篇 |
国内免费 | 180篇 |
专业分类
化学 | 3225篇 |
晶体学 | 31篇 |
力学 | 151篇 |
综合类 | 20篇 |
数学 | 601篇 |
物理学 | 1093篇 |
出版年
2023年 | 69篇 |
2022年 | 77篇 |
2021年 | 123篇 |
2020年 | 192篇 |
2019年 | 189篇 |
2018年 | 157篇 |
2017年 | 131篇 |
2016年 | 215篇 |
2015年 | 190篇 |
2014年 | 226篇 |
2013年 | 308篇 |
2012年 | 328篇 |
2011年 | 350篇 |
2010年 | 237篇 |
2009年 | 207篇 |
2008年 | 271篇 |
2007年 | 217篇 |
2006年 | 204篇 |
2005年 | 181篇 |
2004年 | 167篇 |
2003年 | 155篇 |
2002年 | 104篇 |
2001年 | 59篇 |
2000年 | 55篇 |
1999年 | 63篇 |
1998年 | 39篇 |
1997年 | 44篇 |
1996年 | 50篇 |
1995年 | 50篇 |
1994年 | 46篇 |
1993年 | 27篇 |
1992年 | 28篇 |
1991年 | 28篇 |
1990年 | 22篇 |
1989年 | 21篇 |
1988年 | 18篇 |
1987年 | 19篇 |
1986年 | 15篇 |
1985年 | 30篇 |
1984年 | 23篇 |
1983年 | 13篇 |
1982年 | 17篇 |
1981年 | 20篇 |
1980年 | 15篇 |
1979年 | 13篇 |
1978年 | 13篇 |
1977年 | 18篇 |
1975年 | 12篇 |
1974年 | 14篇 |
1973年 | 13篇 |
排序方式: 共有5121条查询结果,搜索用时 23 毫秒
991.
Total internal reflection microscopy was used to directly measure the interaction potentials between a micron-sized silica sphere and a flat silica surface in the presence of a linear poly(N-isopropylacrylamide) (PNIPAM) aqueous solution. When the PNIPAM concentration was low, no discernible forces were detected. A further increase in PNIPAM concentration resulted in a long-range attraction which was likely due to a combined of the reduced electrostatic interaction between the silica particle and the flat surface after the polymer adsorption and polymer bridges formation. On the other hand, for a fixed PNIPAM concentration, the interaction potential profiles between the particle and flat surface were once again characterized by attraction as temperature was increased. This attractive force can be explained in terms of the conformational changes of PNIPAM chains at the surfaces, which subsequently affected the polymer adsorption and enhanced the segment–segment interaction among the adsorbed polymer chains. 相似文献
992.
Berwyck L. J. Poad Huong T. Pham Michael C. Thomas Jessica R. Nealon J. Larry Campbell Todd W. Mitchell Stephen J. Blanksby 《Journal of the American Society for Mass Spectrometry》2010,21(12):1989-1999
Ozone-induced dissociation (OzID) exploits the gas-phase reaction between mass-selected lipid ions and ozone vapor to determine
the position(s) of unsaturation. In this contribution, we describe the modification of a tandem linear ion-trap mass spectrometer
specifically for OzID analyses wherein ozone vapor is supplied to the collision cell. This instrumental configuration provides
spatial separation between mass-selection, the ozonolysis reaction, and mass-analysis steps in the OzID process and thus delivers
significant enhancements in speed and sensitivity (ca. 30-fold). These improvements allow spectra revealing the double-bond
position(s) within unsaturated lipids to be acquired within 1 s: significantly enhancing the utility of OzID in high-throughput
lipidomic protocols. The stable ozone concentration afforded by this modified instrument also allows direct comparison of
relative reactivity of isomeric lipids and reveals reactivity trends related to (1) double-bond position, (2) substitution
position on the glycerol backbone, and (3) stereochemistry. For cis- and trans-isomers, differences were also observed in the branching ratio of product ions arising from the gas-phase ozonolysis reaction,
suggesting that relative ion abundances could be exploited as markers for double-bond geometry. Additional activation energy
applied to mass-selected lipid ions during injection into the collision cell (with ozone present) was found to yield spectra
containing both OzID and classical-CID fragment ions. This combination CID-OzID acquisition on an ostensibly simple monounsaturated
phosphatidylcholine within a cow brain lipid extract provided evidence for up to four structurally distinct phospholipids
differing in both double-bond position and sn-substitution. 相似文献
993.
Xiao‐Chi Ma Xiulan Xin Bao‐jing Zhang Sha Deng Ji‐hong Yao Chang‐yuan Wang Jian Cui Yan Tian Ke‐xin Liu 《Journal of separation science》2010,33(15):2272-2277
An efficient separation method of using high‐speed counter‐current chromatography was successfully established to directly purify cytotoxic transformed products of cinobufagin by Cordyceps militaris. The two‐phase solvent system composed of n‐hexane–ethyl acetate–methanol–water (4:6:3:4, v/v) was used in high‐speed counter‐current chromatography. A total of 9 mg of 4β,12α‐dihydroxyl‐cinobufagin ( 1 ), 15 mg of 12β‐hydroxyl‐cinobufagin ( 2 ), 8 mg of 5β‐hydroxyl‐cinobufagin ( 3 ), 12 mg of deacetylcinobufagin ( 4 ) and 6 mg of 3‐keto‐cinobufagin ( 5 ) were obtained in a one‐step separation from 400 mg of the crude extract with purity of 98.7, 97.2, 90.6, 99.1 and 99.4%, respectively, as determined by HPLC. Their chemical structures were identified on the basis of 1H‐NMR and 13C‐NMR technology. All products ( 1 – 5 ) showed the potent activities against human carcinoma cervicis (Hela) and malignant melanoma (A375) cells in vitro. 相似文献
994.
Guoxing Zhu Yuanjun Liu Zheng Xu Prof. Dr. Tian Jiang Dr. Chi Zhang Xun Li Gang Qi Dr. 《Chemphyschem》2010,11(11):2432-2437
A facile and robust route for the pre‐synthesized Fe3O4 nanoparticles (NPs) exclusively assembled on both sides of reduced graphene oxide (RGO) sheets with tunable density forming two‐dimensional NPs composite membranes is developed in solution. The assembly is driven by electrostatic attraction, and the nanocomposite sheets display considerable mechanical robustness, such as it can sustain supersonic and solvothermal treatments without NPs falling off, also, can freely float in solution and curl into a tube. The obtained two‐dimensional composite grain membranes exhibit superparamagnetic behavior at room temperature but responds astutely to an external magnetic field. In addition, these magnetic composite membranes show an enhanced absorption capability for microwaves. The grain sheets are attractive for biomedical, sensors, environmental applications and electric‐magnetic devices benefited from large surfaces, high magnetization moment, and superparamagnetic properties. The effective integration of oxide nanocrystals on RGO sheets provides a new way to design semiconductor–carbon nanocomposites for nanodevices or catalytic applications. 相似文献
995.
Li‐Chai Chen I‐Li Chen Chih‐Chiang Huang Chang‐Hui Liao Jhy‐Yih Chen Tai‐Chi Wang 《中国化学会会志》2010,57(6):1331-1340
Some oxime‐containing 3,4‐dihydroquinolin‐2(1H)‐one derivatives were synthesized and evaluated for their antiplatelet and antiproliferative activities. These compounds were synthesized via alkylation of hydroxyl precursors followed by the reaction with NH2OH. The preliminary assays indicated that (Z)‐7‐[2‐(4‐fluorophenyl)‐2‐(hydroxyimino)ethoxy]‐3,4‐dihydroquinolin‐2(1H)‐one (13c) is the most active against U46619 induced platelet aggregation with an IC50 value of 3.51 μM. For the inhibition of AA‐induced aggregation, (E)‐6‐[2‐(hydroxyimino)propoxy]‐3,4‐dihydroquinolin‐2(1H)‐one (15 ) is the most potent with an IC50 value of 1.85 μM. These oxime‐containing 3,4‐dihydroquinolin‐2(1H)‐one derivatives were inactive against thrombin induced platelet aggregation with an IC50 value of greater than 26.78 μM. For the antiproliferative activity, most of these oxime‐containing 3,4‐dihydroquinolin‐2(1H)‐one derivatives were inactive while (Z)‐7‐[2‐(hydroxyimino)‐2‐(naphthalen‐2‐yl)ethoxy]‐3,4‐dihydroquinolin‐2(1H)‐one (13a) exhibited only marginal activities with GI50 value of 7.63, 7.34 and 6.36 μM against the growth of NPC‐TW01, NCI‐H661, and Jurkat respectively. 相似文献
996.
Thao Quyen Cao Nguyen Viet Phong Jang Hoon Kim Dan Gao Hoang Le Tuan Anh Viet-Duc Ngo Le Ba Vinh Young Sang Koh Seo Young Yang 《Molecules (Basel, Switzerland)》2021,26(15)
The bitter melon, Momordica charantia L., was once an important food and medicinal herb. Various studies have focused on the potential treatment of stomach disease with M. charantia and on its anti-diabetic properties. However, very little is known about the specific compounds responsible for its anti-inflammatory activities. In addition, the in vitro inhibitory effect of M. charantia on pro-inflammatory cytokine production by lipopolysaccharide (LPS)-stimulated bone marrow-derived dendritic cells (BMDCs) has not been reported. Phytochemical investigation of M. charantia fruit led to the isolation of 15 compounds (1−15). Their chemical structures were elucidated spectroscopically (one- and two-dimensional nuclear magnetic resonance) and with electrospray ionization mass spectrometry. The anti-inflammatory effects of the isolated compounds were evaluated by measuring the production of the pro-inflammatory cytokines interleukin IL-6, IL-12 p40, and tumor necrosis factor α (TNF-α) in LPS-stimulated BMDCs. The cucurbitanes were potent inhibitors of the cytokines TNF-α, IL-6, and IL-12 p40, indicating promising anti-inflammatory effects. Based on these studies and in silico simulations, we determined that the ligand likely docked in the receptors. These results suggest that cucurbitanes from M. charantia are potential candidates for treating inflammatory diseases. 相似文献
997.
Kuei-Ming Chen Yen-Hsien Yeh Yin-Hao Wu Chen-Hao Chiang Din-Ru Yang Chu-Li Chao Tung-Wei Chi Yen-Hsang Fang Jenq-Dar Tsay Wei-I Lee 《Journal of Crystal Growth》2010,312(24):3574-3578
The bowing curvature of the free-standing GaN substrate significantly decreased almost linearly from 0.67 to 0.056 m−1 (i.e. the bowing radius increased from 1.5 to 17.8 m) with increase in inductively coupled plasma (ICP) etching time at the N-polar face, and eventually changed the bowing direction from convex to concave. Furthermore, the influences of the bowing curvature on the measured full width at half maximum (FWHM) of high-resolution X-ray diffraction (HRXRD) in (0 0 2) reflection were also deduced, which reduced from 176.8 to 88.8 arcsec with increase in ICP etching time. Decrease in the nonhomogeneous distribution of threading dislocations and point defects as well as VGa–ON complex defects on removing the GaN layer from N-polar face, which removed large amount of defects, was one of the reasons that improved the bowing of the free-standing GaN substrate. Another reason was the high aspect ratio of needle-like GaN that appeared at the N-polar face after ICP etching, which released the compressive strain of the free-standing GaN substrate. By doing so, crack-free and extremely flat free-standing GaN substrates with a bowing radius of 17.8 m could be obtained. 相似文献
998.
Ming‐Zhong Wang Cong‐Ying Zhou Man‐Kin Wong Dr. Chi‐Ming Che Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(19):5723-5735
Ruthenium porphyrins (particularly [Ru(2,6‐Cl2tpp)CO]; tpp=tetraphenylporphinato) and RuCl3 can act as oxidation and/or Lewis acid catalysts for direct C‐3 alkylation of indoles, giving the desired products in high yields (up to 82 % based on 60–95 % substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron‐withdrawing or electron‐donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N‐arylindoles to 3‐{[(N‐aryl‐N‐alkyl)amino]methyl}indoles (yield: up to 82 %, conversion: up to 95 %) and the alkylation of N‐alkyl or N‐H indoles to 3‐[p‐(dialkylamino)benzyl]indoles (yield: up to 73 %, conversion: up to 92 %). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp3 C? H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N‐arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three‐component coupling reaction of the in situ generated formaldehyde with an N‐alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium‐labeling experiments are consistent with the alkylation of N‐alkylindoles via pathway B. The relative reaction rates of [Ru(2,6‐Cl2tpp)CO]‐catalyzed oxidative coupling reactions of 4‐X‐substituted N,N‐dimethylanilines with N‐phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants σ (R2=0.989), giving a ρ value of ?1.09. This ρ value and the magnitudes of the intra‐ and intermolecular deuterium isotope effects (kH/kD) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4‐X‐substituted N,N‐dimethylanilines. Ruthenium‐catalyzed three‐component reaction of N‐alkyl/N‐H indoles, paraformaldehyde, and anilines gave 3‐[p‐(dialkylamino)benzyl]indoles in up to 82 % yield (conversion: up to 95 %). 相似文献
999.
Eric Chi‐Ho Kwok Dr. Mei‐Yee Chan Dr. Keith Man‐Chung Wong Dr. Wai Han Lam Prof. Dr. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(40):12244-12254
A series of platinum(II) alkynyl‐based sensitizers has been synthesized and found to show light‐to‐electricity conversion properties. These dyes were developed as sensitizers for the application in nanocrystalline TiO2 dye‐sensitized solar cells (DSSCs). Their photophysical and electrochemical properties were studied. The excited‐state property was probed using nanosecond transient absorption spectroscopy, which showed the formation of a charge‐separated state that arises from the intramolecular photoinduced charge transfer from the platinum(II) alkynylbithienylbenzothiadiazole moiety (donor) to the polypyridyl ligand (acceptor). A lifetime of 3.4 μs was observed for the charge‐separated state. A dye‐sensitized solar cell based on one of the complexes showed a short‐circuit photocurrent of 7.12 mA cm?2, an open circuit voltage of 780 mV, and a fill factor of 0.65, thus giving an overall power conversion efficiency of 3.6 %. 相似文献
1000.
Jyun‐Ting Wu Chi‐Hui Huang Wei‐Chieh Liang Yen‐Lin Wu Jiashing Yu Hsien‐Yeh Chen 《Macromolecular rapid communications》2012,33(10):922-927
Reactive polymer coatings were synthesized via chemical vapor deposition (CVD) polymerization process. These coatings decouple surface design from bulk properties of underlying materials and provide a facile and general route to support thiol‐ene and thiol‐yne reactions on a variety of substrate materials. Through the reported technique, surface functions can be activated through a simple design of thiol‐terminated molecules such as polyethylene glycols (PEGs) or peptides (GRGDYC), and the according biological functions were demonstrated in controlled and low‐fouling protein adsorptions as well as accurately manipulated cell attachments. 相似文献