全文获取类型
收费全文 | 2283篇 |
免费 | 68篇 |
国内免费 | 3篇 |
专业分类
化学 | 1775篇 |
晶体学 | 33篇 |
力学 | 40篇 |
数学 | 72篇 |
物理学 | 434篇 |
出版年
2023年 | 13篇 |
2022年 | 15篇 |
2021年 | 23篇 |
2020年 | 28篇 |
2019年 | 35篇 |
2018年 | 25篇 |
2017年 | 19篇 |
2016年 | 39篇 |
2015年 | 32篇 |
2014年 | 46篇 |
2013年 | 92篇 |
2012年 | 139篇 |
2011年 | 140篇 |
2010年 | 74篇 |
2009年 | 82篇 |
2008年 | 124篇 |
2007年 | 116篇 |
2006年 | 128篇 |
2005年 | 106篇 |
2004年 | 112篇 |
2003年 | 82篇 |
2002年 | 67篇 |
2001年 | 50篇 |
2000年 | 57篇 |
1999年 | 38篇 |
1998年 | 32篇 |
1997年 | 39篇 |
1996年 | 26篇 |
1995年 | 28篇 |
1994年 | 21篇 |
1993年 | 30篇 |
1992年 | 46篇 |
1991年 | 26篇 |
1990年 | 22篇 |
1989年 | 17篇 |
1988年 | 34篇 |
1987年 | 27篇 |
1986年 | 31篇 |
1985年 | 40篇 |
1984年 | 26篇 |
1983年 | 16篇 |
1982年 | 21篇 |
1981年 | 19篇 |
1980年 | 15篇 |
1979年 | 26篇 |
1978年 | 15篇 |
1977年 | 13篇 |
1975年 | 11篇 |
1974年 | 15篇 |
1973年 | 11篇 |
排序方式: 共有2354条查询结果,搜索用时 250 毫秒
71.
Akiko Tsuhako Jing-Qian He Mariko Mihara Naoko Saino Sentaro Okamoto 《Tetrahedron letters》2007,48(52):9120-9123
Ketones and aldehydes were effectively reduced to the corresponding alcohols (or their silyl ethers) by the reaction with CaH2 and R3SiCl in the presence of a catalytic amount of ZnCl2. In the absence of the carbonyl substrate, the reagent reduced R3SiCl to the corresponding hydrosilane under mild reaction conditions. 相似文献
72.
Isothermal
titration microcalorimetry has been applied to investigate the compatibility
testing of risperidone oral solution with soft-drinks and the interaction
with tea tannin such as (–)-epigallocatechin, (–)-epicatechin,
theaflavin and their gallates. In aqueous solution, risperidone was exothermically
bound to tea tannin with binding affinity (103–104
M–1), small enthalpy and entropy changes
reflecting van der Waal’s interaction to form an insoluble complex at
1:1 molar ratio. The heat effect of risperidone titrated into soft-drinks
containing tannin was exothermic and proportional to the quantity of the complex.
While, no significant heat effect was found for risperidone titrated into
a pet-bottled water and an infusion of parched barley without tea tannin.
These results were agreed with stability testing of risperidone in some soft-drinks
by HPLC method. 相似文献
73.
Organotrichlorogermanes were synthesized by the reaction of elemental germanium, tetrachlorogermane and organic chlorides, methyl, propyl, isopropyl and allyl chlorides. Dichlorogermylene formed by the reaction of elemental germanium with tetrachlorogermane was the reaction intermediate, which was inserted into the carbon-chlorine bond of the organic chloride to give organotrichlorogermane. When isopropyl or allyl chloride was used as an organic chloride, organotrichlorogermane was formed also in the absence of tetrachlorogermane. These chlorides were converted to hydrogen chloride, which subsequently reacted with elemental germanium to give the dichlorogermylene intermediate. The reaction of elemental germanium, tetrachlorogermane and organic chlorides provides a simple and easy method for synthesizing organotrichlorogermanes, and all the raw materials are easily available. 相似文献
74.
The first example of the rearrangement reaction of N-halosulfoximine to α-halo sulfoximine is described. 相似文献
75.
Takayama K Iwata M Hisamichi H Okamoto Y Aoki M Niwa A 《Chemical & pharmaceutical bulletin》2002,50(8):1050-1059
In order to develop novel and orally active phosphodiesterase (PDE) 4 inhibitors, random screening was performed using our chemical library to find YM-10335 possessing the 1,8-naphthyridin-2(1H)-one skeleton which is a completely different structure from rolipram. In this report, the syntheses and structure-activity relationships of the YM-10335 derivatives were described. Some compounds showed selective inhibitory activities for PDE 4 derived from human peripheral blood cells and no effect on the other PDE types (1, 2, 3, 5). The inhibition of the tumor necrosis factor-alpha (TNF-alpha) release in vitro and the carrageenan-induced pleurisy in rats were also described. 相似文献
76.
Cordonier CE Satake K Atarashi M Kawamoto Y Okamoto H Kimura M 《The Journal of organic chemistry》2005,70(9):3425-3436
[reaction: see text] The reaction of 2-methoxy-3H-azepines, in the presence or absence of a nucleophile, with N-bromosuccinimide (NBS) gave a regioselective 1,4-adduct from which the corresponding 2H-azepine derivatives were formed via base-promoted hydrogen bromide elimination, generally in moderate to quantitative yield. Competitive formation of 4-bromo-2-methoxy-3H-azepine by electrophilic substitutuion or 3H-azepin-2-yl 2H-azepin-2-yl ether by transetherification was minimized at lower reaction temperatures. Quantitative substitution of 2-(2',4',6'-trichlorophenoxy)-2H-azepine derivatives, formed in moderate yield from the respective 3H-azepine and NBS in the presence of 2,4,6-trichlorophenol (TCP), by various nucleophiles gave the corresponding 2-substituted 2H-azepine. Among these nucleophiles were alkanethiol and alkylamine that are not tolerated in the reaction of 3H-azepine and NBS. 相似文献
77.
Summary The effect of silanol groups on three types of octadecylmodified column gels using heat-treated silicas by calcination has been studied by high-performance liquid chromatography. After heat-treating at 180°C, 500°C and 950°C, the silicas treated with octadecyldimethylchlorosilane were used for the measurement of physical and chemical analysis. From elemental carbon analysis data, the reactive silanol group concentrations, OH(s), were determined to be 2.0 in the 180°C treated silica, 2.1 in the 500°C treated silica and 1.6 in the 950°C treated silica, respectively (original silica: mean pore diameter 116 Å, specific surface area 298 m2/g, pore volume 1.22 ml/g, particle size 5.0 m). The separation factors, , of pyridine versus phenol were measured to be 0.79 on 180°C treated silica, 0.91 on 500°C treated silica and 1.98 on 950°C treated silica, using acetonitrile-water mixtures as the eluent. And then, on the basis of the physico-chemical and chromatographic data, the three types of octadecyl modified column gels using heat-treated silicas by calcination have been compared. 相似文献
78.
The stereospecific radical polymerization of vinyl esters, methacrylates, and alpha-substituted acrylates was studied. Fluoroalcohols, as a solvent, have remarkable effects on the stereoregularity of the radical polymerizations of vinyl acetate, vinyl pivalate, and vinyl benzoate, affording polymers rich in syndiotacticity, heterotacticity, and isotacticity, respectively. This method was successfully applied to the polymerization of methacrylates to give syndiotactic polymers. The steric repulsion between the entering monomer and the chain-end monomeric unit bound by the solvent through hydrogen bonding is important for the stereochemical control in these systems. Lewis acid catalysts, such as lanthanide trifluoromethanesulfonates and zinc salts, were also effective for the stereocontrol during the radical polymerization of methyl methacrylate, to reduce the syndiotacticity and alpha-(alkoxymethyl)acrylates to synthesize isotactic and syndiotactic polymers. Radical polymerization of the methacrylates bearing a bulky ester group, such as the triphenylmethyl methacrylate derivatives, gave highly isotactic polymers, as in the case of anionic polymerization. In addition, the control of one-handed helical conformation was attained in the radical polymerization of 1-phenyldibenzosuberyl methacrylate using chiral neomenthanethiol or cobalt(II) complexes as an additive. 相似文献
79.
Iida K Todo H Okamoto H Danjo K Leuenberger H 《Chemical & pharmaceutical bulletin》2005,53(4):431-434
An attempt was made to produce carrier particles for dry powder inhalation with lactose carrier particles surface-coated using a Wurster fluidized bed. The lactose carrier particles were coated with lactose aqueous solution containing hydroxypropyl methyl cellulose (HPMC) as a binder using a Wurster coating apparatus. Drug/carrier powder mixtures were prepared consisting of micronized salbutamol sulfate and lactose carriers under various particle surface conditions. These powder mixtures were aerosolized by a Jethaler((R)), and the in vitro deposition properties of salbutamol sulfate were evaluated by a twin impinger. The in vitro inhalation properties of the powder mixture prepared using the coated lactose carrier differed significantly compared with those of the powder mixture prepared using the uncoated lactose carrier, indicating improvements in in vitro inhalation properties of sulbutamol sulfate. In vitro inhalation properties increased with the surface coating time. This surface coating system would thus be valuable for increasing the in vitro inhalation properties of dry powder inhalation with lactose carrier particles. 相似文献
80.
Iida K Hayakawa Y Okamoto H Danjo K Leuenberger H 《Chemical & pharmaceutical bulletin》2001,49(10):1326-1330
The effects of the flow and packing properties of a drug/carrier powder mixture on emission of drug adhering to the carrier from capsules and inhalation devices were investigated. Model powder mixtures were designed consisting of lactose carriers with different particle shapes were prepared by surface treatment and micronized salbutamol sulfate. These powder mixtures were aerosolized by a Spinhaler, and in vitro deposition properties of salbutamol sulfate were evaluated by a twin impinger. The flow properties of the mixed powders were evaluated by the Carr's flowability index (FI) and Hausner's ratio (HR). The packing properties of the mixed powders were determined employing the tapping method. Compared with the powder mixed with the untreated lactose carrier, the FI, HR, and the constant K in Kawakita's equation of the powder mixture prepared using the surface-treated lactose carrier were significantly different, showing that the flow and packing properties of the drug/carrier powder mixture were improved. Using this surface-treated system, the handling of the powder mixture when packing into capsules is improved, which is desirable for handling dry powder inhalants. The fraction (%) of drug emitted from capsules and devices (EM) and the FI of the powder mixture were correlated. As the flow properties improved, the outflow of the powder mixture from capsules and devices became easier, and emission of drug adhering on the carrier from capsules and devices improved. Improvement of the inhalation process, such as the drug particles emitted from the inhalation system, is valuable for increasing inhalation properties of dry powder inhalation. 相似文献