全文获取类型
收费全文 | 56197篇 |
免费 | 13514篇 |
国内免费 | 4677篇 |
专业分类
化学 | 55687篇 |
晶体学 | 578篇 |
力学 | 1737篇 |
综合类 | 378篇 |
数学 | 4540篇 |
物理学 | 11468篇 |
出版年
2024年 | 54篇 |
2023年 | 487篇 |
2022年 | 615篇 |
2021年 | 918篇 |
2020年 | 2068篇 |
2019年 | 3388篇 |
2018年 | 1768篇 |
2017年 | 1405篇 |
2016年 | 4385篇 |
2015年 | 4537篇 |
2014年 | 4579篇 |
2013年 | 5584篇 |
2012年 | 4807篇 |
2011年 | 4246篇 |
2010年 | 4211篇 |
2009年 | 4229篇 |
2008年 | 3794篇 |
2007年 | 3021篇 |
2006年 | 2679篇 |
2005年 | 2669篇 |
2004年 | 2270篇 |
2003年 | 2093篇 |
2002年 | 2883篇 |
2001年 | 2080篇 |
2000年 | 1886篇 |
1999年 | 887篇 |
1998年 | 433篇 |
1997年 | 388篇 |
1996年 | 308篇 |
1995年 | 326篇 |
1994年 | 273篇 |
1993年 | 215篇 |
1992年 | 170篇 |
1991年 | 134篇 |
1990年 | 132篇 |
1989年 | 99篇 |
1988年 | 66篇 |
1987年 | 59篇 |
1986年 | 57篇 |
1985年 | 40篇 |
1984年 | 26篇 |
1983年 | 29篇 |
1982年 | 17篇 |
1981年 | 12篇 |
1980年 | 14篇 |
1978年 | 4篇 |
1975年 | 6篇 |
1974年 | 4篇 |
1973年 | 5篇 |
1957年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 140 毫秒
21.
Unexpected benzimidazole ring formation from a quinoneimide species in the presence of ammonium acetate as supporting electrolyte used in the coupling of electrochemistry with mass spectrometry 下载免费PDF全文
22.
The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes 下载免费PDF全文
Prof. Biao Wu Dr. Shaoguang Li Prof. Yibo Lei Prof. Huaiming Hu Dr. Nader de Sousa Amadeu Prof. Dr. Christoph Janiak Dr. Jennifer S. Mathieson Dr. De‐Liang Long Prof. Leroy Cronin Prof. Xiao‐Juan Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2588-2593
By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A2L3 complexes (A represents anion, here orthophosphate PO43?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes. 相似文献
23.
A nanomaterials-based novel molecular beacon has attracted growing attentions in fluorescent assays as many nanomaterials possess excellent quenching efficiency. In this work, a gold-based nanobeacon probe was established to detect organophosphorus pesticides for the first time. The constructed gold-based nanobeacon acted as a signal indicator and could display the decreasing of the intensity in the presence of targets, which competitively bound to single strand DNA. To achieve a high sensitive probe, some parameters including solution pH, temperature and reaction time were investigated and optimized. The gold-based nanobeacon probe assay was proved to be rapid and sensitive to achieve a detection limit of 0.035 μM for isocarbophos, 0.134 μM for profenofos, 0.384 μM for phorate and 2.35 μM for omethoate, respectively. The prepared nanobeacon effectively reduced the background and improved the detection sensitivity and selectivity. The probe is stable, easy to operate and does not need sophisticated instruments. These features makes the probe feasible for screening trace organophosphorus pesticides in real samples. 相似文献
24.
25.
Eco‐friendly ionic liquid assisted capillary electrophoresis and α‐acid glycoprotein‐assisted liquid chromatography for simultaneous determination of anticancer drugs in human fluids 下载免费PDF全文
Deia Abd El‐Hady Hassan M. Albishri Rajesh Rengarajan 《Biomedical chromatography : BMC》2015,29(6):925-934
In the current work, two eco‐friendly analytical methods based on capillary electrophoresis (CE) and reversed phase liquid chromatography (RPLC) were developed for simultaneous determination of the most commonly used anticancer drugs for Hodgkin's disease: methotrexate (MTX), vinblastine, chlorambucil and dacarbazine. A background electrolyte (BGE) of 12.5 mmol/L phosphate buffer at pH 7.4 and 0.1 µmol/L 1‐butyl‐3‐methyl imidazolium bromide (BMImBr) ionic liquid (IL) was used for CE measurements at 250 nm detection wavelength, 20 kV applied voltage and 25 °C. The rinsing protocol was significantly improved to reduce the adsorption of IL on the interior surface of capillary. Moreover, RPLC method was developed on α‐1‐acid glycoprotein (AGP) column. Mobile phase was 10 mmol/L phosphate buffer at pH 6.0 (100% v/v) and flow rate at 0.1 mL/min. As AGP is a chiral column, it was successfully separated l ‐MTX from its enantiomer impurity d ‐MTX. Good linearity of quantitative analysis was achieved with coefficients of determinations (r2) >0.995. The stability of drugs measurements was investigated with adequate recoveries up to 24 h storage time under ambient temperature. The limits of detection were <50 and 90 ng/mL by CE and RPLC, respectively. The using of short‐chain IL as an additive in BGE achieved 600‐fold sensitivity enhancement compared with conventional Capillary Zone Electrophoresis (CZE). Therefore, for the first time, the proposed methods were successfully applied to determine simultaneously the analytes in human plasma and urine samples at clinically relevant concentrations with fast and simple pretreatments. Developed IL‐assisted CE and RPLC methods were also applied to measure MTX levels in patients’ samples over time. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
26.
In the view of substrate availability, atomic efficiency and cost, directly using arenols as coupling partners in cross‐coupling, would be one of the most attractive goals. Up to date, many efforts have been made to activate the C—O bond of phenols with different strategies, for example, through in‐situ formed intermediates, through a catalytic reductive dearomatization‐condensation‐rearomatization sequence or catalytic deoxygenation. In this review, we summarized recent advances in cross‐couplings of arenols as the electrophiles via C—O activation. 相似文献
27.
Polypyrrole Shell@3D‐Ni Metal Core Structured Electrodes for High‐Performance Supercapacitors 下载免费PDF全文
Gao‐Feng Chen Yu‐Zhi Su Pan‐Yong Kuang Zhao‐Qing Liu Dao‐Yi Chen Xu Wu Nan Li Prof. Shi‐Zhang Qiao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4614-4621
Three‐dimensional (3D) nanometal films serving as current collectors have attracted much interest recently owing to their promising application in high‐performance supercapacitors. In the process of the electrochemical reaction, the 3D structure can provide a short diffusion path for fast ion transport, and the highly conductive nanometal may serve as a backbone for facile electron transfer. In this work, a novel polypyrrole (PPy) shell@3D‐Ni‐core composite is developed to enhance the electrochemical performance of conventional PPy. With the introduction of a Ni metal core, the as‐prepared material exhibits a high specific capacitance (726 F g?1 at a charge/discharge rate of 1 A g?1), good rate capability (a decay of 33 % in Csp with charge/discharge rates increasing from 1 to 20 A g?1), and high cycle stability (only a small decrease of 4.2 % in Csp after 1000 cycles at a scan rate of 100 mV s?1). Furthermore, an aqueous symmetric supercapacitor device is fabricated by using the as‐prepared composite as electrodes; the device demonstrates a high energy density (≈21.2 Wh kg?1) and superior long‐term cycle ability (only 4.4 % and 18.6 % loss in Csp after 2000 and 5000 cycles, respectively). 相似文献
28.
Identification of metabolites of rupestonic acid in rat urine by liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry 下载免费PDF全文
Dongyu Gu Yi Yang Qibin Chen Madina Habasi Jiangyu Zhao Haji Akber Aisa 《Biomedical chromatography : BMC》2015,29(4):595-603
Rupestonic acid, a potential anti‐influenza agent, is an important and characteristic compound in Artemisia rupestris L., a well‐known traditional Uighur medicine for the treatment of colds. In the present study, high‐performance liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry was used to detect and identify the metabolites in rat urine after oral administration of rupestonic acid. A total of 10 metabolites were identified or partially characterized. The structure elucidations of the metabolites were performed by comparing the changes in accurate molecular masses and fragment ions with those of the parent compound. The results showed that the main metabolites of rupestonic acid in rat urine were formed by oxidation, hydrogenation and glucuronidation. A metabolism pathway was proposed for the first time based on the characterized structures. This metabolism study can provide essential information for drug discovery, design and clinical application of rupestonic acid. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
29.
Yongjie Zhou Yuqi Mei Tian Luo Wenxue Chen Qiuping Zhong Haiming Chen Weijun Chen 《Molecules (Basel, Switzerland)》2021,26(9)
The contribution of rheological properties and viscoelasticity of the interfacial adsorbed layer to the emulsification mechanism of enzymatic modified sugar beet pectin (SBP) was studied. The component content of each enzymatic modified pectin was lower than that of untreated SBP. Protein and ferulic acid decreased from 5.52% and 1.08% to 0.54% and 0.13%, respectively, resulting in a decrease in thermal stability, apparent viscosity, and molecular weight (Mw). The dynamic interfacial rheological properties showed that the interfacial pressure and modulus (E) decreased significantly with the decrease of functional groups (especially proteins), which also led to the bimodal distribution of particle size. These results indicated that the superior emulsification property of SBP is mainly determined by proteins, followed by ferulic acid, and the existence of other functional groups also promotes the emulsification property of SBP. 相似文献
30.
Sun Yuan Luo Shunlong Lei Xiangyun 《International Journal of Theoretical Physics》2021,60(9):3211-3224
International Journal of Theoretical Physics - Gram matrices arise naturally in the consideration of pair-wise overlap of a family of vectors or quantum pure states, and play an important role in... 相似文献