全文获取类型
收费全文 | 2266篇 |
免费 | 195篇 |
国内免费 | 205篇 |
专业分类
化学 | 2278篇 |
晶体学 | 22篇 |
力学 | 19篇 |
综合类 | 6篇 |
数学 | 15篇 |
物理学 | 326篇 |
出版年
2024年 | 2篇 |
2023年 | 41篇 |
2022年 | 126篇 |
2021年 | 157篇 |
2020年 | 120篇 |
2019年 | 92篇 |
2018年 | 60篇 |
2017年 | 64篇 |
2016年 | 93篇 |
2015年 | 92篇 |
2014年 | 118篇 |
2013年 | 166篇 |
2012年 | 115篇 |
2011年 | 151篇 |
2010年 | 113篇 |
2009年 | 140篇 |
2008年 | 147篇 |
2007年 | 125篇 |
2006年 | 160篇 |
2005年 | 124篇 |
2004年 | 90篇 |
2003年 | 91篇 |
2002年 | 40篇 |
2001年 | 35篇 |
2000年 | 32篇 |
1999年 | 35篇 |
1998年 | 28篇 |
1997年 | 20篇 |
1996年 | 13篇 |
1995年 | 23篇 |
1994年 | 16篇 |
1993年 | 7篇 |
1992年 | 9篇 |
1991年 | 5篇 |
1990年 | 1篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1981年 | 1篇 |
排序方式: 共有2666条查询结果,搜索用时 15 毫秒
61.
Mariusz?T.?Galkowski Pawel?J.?KuleszaEmail author Krzysztof?Miecznikowski Malgorzata?Chojak Henryk?Bala 《Journal of Solid State Electrochemistry》2004,8(6):430-434
We propose a novel composite organic-inorganic coating in the form of a redox polymer film for protection of stainless steel against general corrosion in strong acid medium (2 M H2SO4). We utilize an anion exchange polymer, protonated poly(4-vinylpyridine), into which hexacyanoferrate anions have been introduced. Owing to the presence of Fe(CN)63–/4– at the interface formed by the film and the steel, a sparingly soluble metal hexacyanoferrate (mostly Prussian blue, PB) is formed as an overcoating on the steels surface, presumably on the passive (metal oxide) layer. The redox polymer film on the steel seems to act as a composite three-dimensional bilayer-type coating in which hexacyanoferrate(III,II) anions (that are capable of effective charge storage) exist in the outer portions of the film, whereas the inner PB layer improves the systems overall adherence and stability. By analogy to a conducting polymer (e.g. polyaniline, polypyrrole), introduction of the redox polymer composite film leads to stabilization of the steel substrates potential within the passive range.Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003) 相似文献
62.
A new simple, sensitive, rapid and precise flow injection (FI) procedure based on the formation of copper complexes with some angiotensin converting enzyme (ACE) inhibitors has been developed and evaluated for the analysis of lisinopril (LN), enalapril maleate (EP), ramipril (RP) and perindopril tert-butylamine (PD). In this method, samples were injected into a flowing stream of distilled-deionized water, carried through the packed reactor of CuO for derivatization followed by ultraviolet (UV) detection. The flow rate was 1.5 ml min−1 and column temperature was ambient (25 °C). Lisinopril was injected directly into the flowing stream and the detector response was measured at 262 nm. The hydrolysis products of enalapril maleate, ramipril and perindopril tert-butylamine in 0.2N NaOH were injected after neutralization with 1N HCl and the detector response was measured at 272, 265 and 252 nm, respectively. The developed method was successfully applied to the determination of tested drugs in pharmaceutical preparations at a sampling rate of 60 samples h−1 and a recovery near 100% for all compounds. 相似文献
63.
Bicyclic sulfonamides were synthesized from 4-alkenyl N-alkenylsulfonyl l-prolines using a ring-closure metathesis reaction. Three types of bicyclic sulfonamides varying in the size of the second ring (5,5; 5,6; 5,7) were synthesized. A sulfonamide counterpart of an indolizidinone 2-carboxylic acid was synthesized and evaluated for its activity against the enzyme thrombin. 相似文献
64.
Imines of (1S,9S)-t-butyl-9-amino-octahydro-6,10-dioxo-6H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate undergo thermal (toluene, 110°C) or LiBr-DBU catalysed (MeCN, room temperature) regio- and stereo-specific cycloaddition to a range of chiral dipolarophiles giving enantiopure spiro-cycloadducts in excellent yield. The reactions proceed via intermediate NH azomethine ylides and litho azomethine ylides, respectively and results in the multiplication of chiral centres from 2 (one of which is lost in the process) to 5. 相似文献
65.
A novel, sensitive method for detecting protease inhibitors by using fluorescent protease substrates in gels is described. The protease inhibitors were separated on sodium dodecyl sulfate (SDS)-polyacrylamide gels containing a copolymerized peptide substrate, namely 4-methyl-coumaryl-7-amide (MCA). As the incorporated substrates in the gel, Boc-Phe Ser-Arg-MCA was used for trypsin, Suc-Ala-Ala-Pro-Phe-MCA for alpha-chymotrypsin, and Z-Phe-Arg-MCA for papain. After electrophoresis, washing and incubating the gel with the target protease solutions allowed the substrate to be cleaved by the protease, and the release of the fluorescent 7 amino-4 methyl-coumarin (AMC), which was detected under a UV transilluminator. The uncleaved peptide-MCA substrate remained where the inhibitors were present, and was visualized as dark blue bands on the light-green fluorescent background gel. This new method offers several advantages over other previous methods including: (i) greatly increased sensitivity can be achieved in a shorter period of time, which may be useful for discovering new protease inhibitors in small amounts of crude material; (ii) the procedure is quite simple and quick since the incubation period is very short and no time is needed for staining and destaining steps; (iii) since these probes using substrate specificity/target proteases, they are excellent tools for detection and discrimination of unknown protease inhibitors for various target proteases. 相似文献
66.
The inhibition performance of five azomethine derivatives such as: 1-(4-Methyloxy phenylimino)-1-(phenylhydrazono)-propan-2-one (SB1), 1-(4-Methylphenylimino)-1-(phenylhydrazono) propan-2-one (SB2), 1-(phenylimino)-1(phenylhydrazono)-propan-2-one (SB3), 1-(4-Bromo phenylimino)-1(phenylhydrazono)-propan-2-one (SB4) and 1-(4-Chlorophenylimino)-1(phenylhydrazono) -propan-2-on (SB5) as corrosion inhibitors for mild steel in sulfuric acid 0.5 ?M were investigated using different methods. All experimental results demonstrate that these compounds are eficients inhibitors. The inhibition efficiencies () increase with inhibitors concentration. At 7.5 10?5 ?M, the was 97.27%, 96.31%, 94.23%, 93.19 and 91.64% for SB1, SB2, SB3, SB4 and SB5, respectively. The potentiodynamic polarization results indicated that all the studied inhibitors act as mixed type. The adsorption process on mild steel surface obeyed Langmuir isotherm. The associated activation parameters and thermodynamic have been calculated and discussed. The adsorbed film formed on the metal surface was characterized by SEM and EDX. 相似文献
67.
van de Waterbeemd H Smith DA Jones BC 《Journal of computer-aided molecular design》2001,15(3):273-286
Lipophilicity, often expressed as distribution coefficients (log D) in octanol/water, is an important physicochemical parameter influencing processes such as oral absorption, brain uptake and various pharmacokinetic (PK) properties. Increasing log D values increases oral absorption, plasma protein binding and volume of distribution. However, more lipophilic compounds also become more vulnerable to P450 metabolism, leading to higher clearance. Molecular size and hydrogen bonding capacity are two other properties often considered as important for membrane permeation and pharmacokinetics. Interrelationships among these physicochemical properties are discussed. Increasing size (molecular weight) often gives higher potency, but inevitably also leads to either higher lipophilicity, and hence poorer dissolution/solubility, or to more hydrogen bonding capacity, which limits oral absorption. Differences in optimal properties between gastrointestinal absorption and uptake into the brain are addressed. Special attention is given to the desired lipophilicity of CNS drugs. In examples using -blockers, Ca channel antagonists and peptidic renin inhibitors we will demonstrate how potency and pharmacokinetic properties need to be balanced. 相似文献
68.
用失重法研究了N-甲基-2-巯基咪唑(MMI)在5%盐酸中对铜的酸洗缓蚀性能.探讨了温度和MMI浓度对缓蚀效果的影响,从中得出了MMI在铜表面的吸附等温式,计算了吸附热及MMI的加入对铜在盐酸中腐蚀反应活化能的影响,进而探讨了MMI对铜缓蚀作用的机理.结果表明, 30 ℃下,在5%盐酸中,当MMI的浓度在3 mmol•L-1和8 mmol•L-1之间时,缓蚀率随MMI浓度的增加而迅速增加,当浓度达到8 mmol•L-1时,缓蚀率趋于定值,而当浓度小于3 mmol•L-1时, MMI的加入会加速铜的腐蚀;吸附在铜表面的MMI分子间的作用力整体表现为引力; MMI在铜表面的吸附是吸热反应; MMI的加入降低了铜的腐蚀反应活化能. 相似文献
69.
《中国化学快报》2020,31(5):1281-1287
Extensive structure-activity relationships (SARs) study of JND3229 was conducted to yield a series of new reversible 2-oxo-3,4-dihydropyrimido[4,5-d]pyrimidine privileged scaffold as EGFRC797S inhibitors. One of the most potent compound 6i potently suppressed EGFRL858R/T790M/C797S kinase with an IC50 value of 3.1 nmol/L, and inhibited the proliferation of BaF3 cells harboring EGFRL858R/T790M/C797S and EGFR19D/T790M/C797S mutants with IC50 values of 290 nmol/L and 316 nmol/L, respectively. Further, 6i dose-dependently induced suppression of the phosphorylation of EGFRL858R/T790M/C797S and EGFR19D/T790M/C797S in BaF3 cells. Compound 6i may serve as a promising lead compound for further drug discovery overcoming the acquired resistance of non-small cell lung cancer (NSCLC) patients. 相似文献
70.
Yong Hong Wang Ting Fang Tian Xing Qin Liu Guang Yao Meng 《Journal of membrane science》2006,280(1-2):261-269
The high-quality tubular titania MF membranes are successfully prepared by dip-coating techniques and systematically investigated with regard to their corrosive resistances. The experiments show that dispersants PAA and anatase powder were preferably employed to prepare desired suspensions with solid loading 10–15 wt.% and that suspensions properties significantly affect the final membranes quality. The titania MF membranes with pure water permeability 742.42 l m−2 h−1 bar−1 and 0.1 μm pore diameter have been obtained using the prepared suspensions. The corrosion resistance of titania membranes exhibits that the anatase layers are more stable than the alumina supports in boiling corrosive medium and that the poor quality titania MF membranes become more deteriorated due to its top layer pore blockages and fouling layer formation, which provides a wide range of practical application fields in very hash environments with reliable data supports. 相似文献