全文获取类型
收费全文 | 9345篇 |
免费 | 1349篇 |
国内免费 | 1038篇 |
专业分类
化学 | 6930篇 |
晶体学 | 111篇 |
力学 | 473篇 |
综合类 | 110篇 |
数学 | 1192篇 |
物理学 | 2916篇 |
出版年
2024年 | 13篇 |
2023年 | 166篇 |
2022年 | 229篇 |
2021年 | 290篇 |
2020年 | 345篇 |
2019年 | 332篇 |
2018年 | 259篇 |
2017年 | 278篇 |
2016年 | 448篇 |
2015年 | 406篇 |
2014年 | 556篇 |
2013年 | 714篇 |
2012年 | 854篇 |
2011年 | 866篇 |
2010年 | 612篇 |
2009年 | 543篇 |
2008年 | 611篇 |
2007年 | 524篇 |
2006年 | 451篇 |
2005年 | 373篇 |
2004年 | 356篇 |
2003年 | 321篇 |
2002年 | 346篇 |
2001年 | 270篇 |
2000年 | 172篇 |
1999年 | 211篇 |
1998年 | 138篇 |
1997年 | 108篇 |
1996年 | 129篇 |
1995年 | 97篇 |
1994年 | 99篇 |
1993年 | 89篇 |
1992年 | 77篇 |
1991年 | 77篇 |
1990年 | 46篇 |
1989年 | 52篇 |
1988年 | 32篇 |
1987年 | 31篇 |
1986年 | 33篇 |
1985年 | 31篇 |
1984年 | 11篇 |
1983年 | 6篇 |
1982年 | 8篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1963年 | 7篇 |
1959年 | 12篇 |
1958年 | 11篇 |
1957年 | 15篇 |
1956年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
Ji XY Zhong ZJ Xue ST Meng S He WY Gao RM Li YH Li ZR 《Chemical & pharmaceutical bulletin》2010,58(11):1436-1441
A series of novel glutarimide compounds were synthesized and their antiviral activities were evaluated. The compounds displaying the strongest antiviral activities included 5, 6f, 7e and 9 against coxsackievirus B3 (Cox B3), 10 and 6f against influenza virus A (influenza A) and 7a against herpes simplex virus 2 (HSV-2). However, most of the synthetic glutarimides showed comparatively much weaker activity against influenza A, Cox B3 and HSV-2 than the natural glutarimide compounds tested. Based on the results, it seemed likely that a conjugated system at the β-substituted moiety provides stronger antiviral activity. 相似文献
982.
Michal Horá?ek Ivana Císa?ová Ji?í Pinkas 《Journal of organometallic chemistry》2010,695(21):2338-1045
The singly tucked-in titanocene [Ti(η5-C5Me5)(η5:η1-C5Me4CH2)] (1) reacts smoothly with ethylene glycol or hydroquinone to give bis(titanoceneoxide) (TiIII) complexes [CH2OTi(η5-C5Me5)2]2 (2) and [(η5-C5Me5)2TiOC6H4OTi(η5-C5Me5)2] (3) containing dimethylene and 1,4-phenylene link, respectively. EPR spectra of 2 in 2-methyltetrahydrofuran glass and 3 in toluene glass revealed that the unpaired d1 electrons are in interaction to form triplet state molecules. The Ti-Ti distance derived from the zero-field splittings D for the two conformations of 2 (7.42 Å and 7.66 Å) are in good agreement with the Ti-Ti distance of 7.2430(7) Å from the X-ray diffraction single-crystal analysis. For 3, however, the Ti-Ti distance derived from D (7.65 Å) is by 1.47 Å shorter than the crystallographic distance of 9.1230(8) Å that indicates an enhancement of the through-space dipole-dipole interaction due to the presence of a conjugated quinonide link. 相似文献
983.
堆焊熔敷层表面纳米晶层摩擦磨损性能研究 总被引:1,自引:1,他引:1
用预压力滚压技术在堆焊修复层表面制备纳米晶层.利用TEM、SEM分析技术研究表面纳米晶层微观结构,利用CETR-3型多功能摩擦磨损试验机考察在干摩擦条件下堆焊层表面纳米晶层的摩擦磨损性能.结果表明堆焊修复层表面经表面纳米化处理后,表面形成厚度约为10μm(晶粒尺寸小于100 nm)的纳米晶层,最表面层平均晶粒尺寸约为10 nm.纳米压痕试验表明纳米晶层的硬度提高,最表面纳米晶层的硬度约为原始堆焊层硬度的3倍.与原始堆焊试样相比,表面纳米化试样的摩擦系数降低了10%,磨损体积降低了25%~30%左右.表面纳米化样品的磨损机制由原始堆焊层的磨粒磨损和黏着磨损转变为磨粒磨损,分析表明晶粒细化导致的高硬度、低塑性是摩擦磨损性能改善和磨损机制改变的主要原因. 相似文献
984.
Ladie Kimberly De La Cruz Xiaoxiao Yang Anna Menshikh Maya Brewer Wen Lu Minjia Wang Siming Wang Xingyue Ji Alyssa Cachuela Haichun Yang David Gallo Chalet Tan Leo Otterbein Mark de Caestecker Binghe Wang 《Chemical science》2021,12(31):10649
Carbon monoxide as an endogenous signaling molecule exhibits pharmacological efficacy in various animal models of organ injury. To address the difficulty in using CO gas as a therapeutic agent for widespread applications, we are interested in developing CO prodrugs through bioreversible caging of CO in an organic compound. Specifically, we have explored the decarboxylation–decarbonylation chemistry of 1,2-dicarbonyl compounds. Examination and optimization of factors favorable for maximal CO release under physiological conditions led to organic CO prodrugs using non-calorific sweeteners as leaving groups attached to the 1,2-dicarbonyl core. Attaching a leaving group with appropriate properties promotes the desired hydrolysis–decarboxylation–decarbonylation sequence of reactions that leads to CO generation. One such CO prodrug was selected to recapitulate the anti-inflammatory effects of CO against LPS-induced TNF-α production in cell culture studies. Oral administration in mice elevated COHb levels to the safe and efficacious levels established in various preclinical and clinical studies. Furthermore, its pharmacological efficacy was demonstrated in mouse models of acute kidney injury. These studies demonstrate the potential of these prodrugs with benign carriers as orally active CO-based therapeutics. This represents the very first example of orally active organic CO prodrugs with a benign carrier that is an FDA-approved sweetener with demonstrated safety profiles in vivo.1,2-Dicarbonyl compounds with FDA-approved sweeteners as leaving groups deliver CO for protection against acute kidney injury in mice. 相似文献
985.
Zhi-gang Yu Zhi Qin Hong-rui Ji Xia Du Yan-hui Chen Ping Pan Heng Wang Yu-yong Liu 《Chromatographia》2010,72(11-12):1073-1081
A method for the simultaneous determination of 11 triazine herbicides residues in river water has been developed. It involves solid-phase extraction (SPE) pretreatment step and rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS-MS). In the SPE pretreatment step, the adsorptive performance of MWCNTs material as SPE adsorbent and the elution capability of five kinds of solvents were investigated; in the LC separation step, a rapid resolution high throughput LC column, was used and the gradient elution mode adopted. The linear correlation coefficients (r 2) of the method for 11 target analytes varied between 0.9930 and 0.9980, the mean recoveries were in the range of 73.0 and 98.0% with relative standard deviations (RSD) 2.6 ~ 4.2%, the method detection limits (MDL) were all below 0.1 ng L?1. An expanded uncertainty of not more than 20% was estimated for each analyte at the spiked concentration of 4.0 μg L?1. The proposed method was applied to the determination of the residue concentrations of 11 pollutants in Songhuajiang River water. 相似文献
986.
Pavel Jandera Jiří Urban Veronika Škeříková Pavel Langmaier Romana Kubíčková Josef Planeta 《Journal of chromatography. A》2010,1217(1):22-33
We prepared hybrid particle-monolithic polymethacrylate columns for micro-HPLC by in situ polymerization in fused silica capillaries pre-packed with 3–5 μm C18 and aminopropyl silica bonded particles, using polymerization mixtures based on laurylmethacrylate–ethylene dimethacrylate (co)polymers for the reversed-phase (RP) mode and [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl) zwitterionic (co)polymers for the hydrophilic interaction (HILIC) mode. The hybrid particle-monolithic columns showed reduced porosity and hold-up volumes, approximately 2–2.5 times lower in comparison to the pure monolithic columns prepared in the whole volume of empty capillaries. The elution volumes of sample compounds are also generally lower in comparison to packed or pure monolithic columns. The efficiency and permeability of the hybrid columns are intermediate in between the properties of the reference pure monolithic and particle-packed columns. The chemistries of the embedded solid particles and of the interparticle monolithic moiety in the hybrid capillary columns contribute to the retention to various degrees, affecting the selectivity of separation. Some hybrid columns provided improved separations of proteins in comparison to the reference particle-packed columns in the reversed-phase mode. Zwitterionic hybrid particle-monolithic columns show dual mode retention HILIC/RP behaviour depending on the composition of the mobile phase and allow separations of polar compounds such as phenolic acids in the HILIC mode at lower concentrations of acetonitrile and, often in shorter analysis time in comparison to particle-packed and full-volume monolithic columns. 相似文献
987.
A novel method using liquid chromatography coupled to electrospray ionization mass spectrometry (LC-ESI-MS) has been optimized and established for the qualitative and quantitative analysis of ten active phenolic compounds originating from the pigeon pea leaves and a medicinal product thereof (Tongluo Shenggu capsules). In the present study, the chromatographic separation was achieved by means of a HiQ Sil C18V reversed-phase column with a mobile phase consisting of methanol and 0.1% formic acid aqueous solution. Low-energy collision-induced dissociation tandem mass spectrometry (CID-MS/MS) using the selected reaction monitoring (SRM) analysis was employed for the detection of ten analytes which included six flavonoids, two isoflavonoids and two stilbenes. All calibration curves showed excellent coefficients of determination (r(2) ≥ 0.9937) within the range of tested concentrations. The intra- and inter-day variations were below 5.36% in terms of relative standard deviation (RSD). The recoveries were 95.08-104.98% with RSDs of 2.06-4.26% for spiked samples of pigeon pea leaves. The method developed was a rapid, efficient and accurate LC-MS/MS method for the detection of phenolic compounds, which can be applied for quality control of pigeon pea leaves and related medicinal products. 相似文献
988.
在覆盖有钨电极的硅衬底上利用多孔阳极氧化铝模板为生长掩膜电沉积合成垂直排列的铜铟硒纳米棒阵列. 多孔阳极氧化铝模板由阳极氧化磁控溅射制备的铝膜制成. 扫描电子显微镜结果表明,该纳米棒阵列结构致密,直径约100 nm长度约1μm,纵横比为10. X射线衍射、微区拉曼光谱和高分辨透射电子显微镜结果表明,真空条件下450 oC退火处理的铜铟硒纳米棒是多晶纯相的黄铜矿结构的铜铟硒,在纳米棒轴向方向上有比较大的晶粒尺寸. 能量色散X射线光谱表明,铜铟硒纳米棒的化学组成接近InSe2的化学计量比,由吸收光谱分析推算铜铟硒纳米棒带隙为0.96 eV. 相似文献
989.
介绍了阿贝-波特空间滤波的实验原理,在Matlab环境下建立了带有图形用户界面(GUI)的计算机仿真平台.不仅可以准确地完成针对不同输入图像、不同滤波要求的滤波过程,还可以通过调整滤波器参数观察滤波效果的差异,形象地展现光学空间滤波过程的物理本质,提高教学效果. 相似文献
990.
Ethynylated phenothiazine based fluorescent boronic acid probes were prepared. Sonogashira coupling reaction was used to introduce
substituted phenylethynylene fragments to the phenothiazine fluorophore to extend the π-conjugation and to enhance the emission
property. The photophysical properties and the binding properties of these probes with hydroxyl acids were investigated. We
found that the probes with significant ICT effect show emissions which are sensitive to solvent polarity. The phenothiazine
moiety is proved to be electron-donating. We found the substitution profile imparts significant effect on the photophysical
properties of the probes. For example, one of the probes shows d-PeT effect, whereas the regioisomer probe with similar π-conjugation
fragment but different substitution profile shows the a-PeT effect. The easy derivatization of phenothiazine fluorophore,
the structure-photophysical property relation and the novel d-PeT fluorescence transduction profile of the phenothiazine based
probes described herein may inspire more investigation into this fascinating research area. 相似文献