全文获取类型
收费全文 | 45386篇 |
免费 | 4845篇 |
国内免费 | 3801篇 |
专业分类
化学 | 22363篇 |
晶体学 | 308篇 |
力学 | 2022篇 |
综合类 | 304篇 |
数学 | 3659篇 |
物理学 | 11235篇 |
综合类 | 14141篇 |
出版年
2024年 | 199篇 |
2023年 | 737篇 |
2022年 | 1167篇 |
2021年 | 1289篇 |
2020年 | 1307篇 |
2019年 | 1231篇 |
2018年 | 1034篇 |
2017年 | 985篇 |
2016年 | 1487篇 |
2015年 | 1576篇 |
2014年 | 1989篇 |
2013年 | 2507篇 |
2012年 | 3166篇 |
2011年 | 3213篇 |
2010年 | 2152篇 |
2009年 | 2154篇 |
2008年 | 2397篇 |
2007年 | 2292篇 |
2006年 | 1997篇 |
2005年 | 1818篇 |
2004年 | 1484篇 |
2003年 | 1331篇 |
2002年 | 1451篇 |
2001年 | 1277篇 |
2000年 | 1086篇 |
1999年 | 1498篇 |
1998年 | 1313篇 |
1997年 | 1335篇 |
1996年 | 1349篇 |
1995年 | 1089篇 |
1994年 | 969篇 |
1993年 | 863篇 |
1992年 | 801篇 |
1991年 | 733篇 |
1990年 | 551篇 |
1989年 | 543篇 |
1988年 | 457篇 |
1987年 | 322篇 |
1986年 | 224篇 |
1985年 | 152篇 |
1984年 | 103篇 |
1983年 | 69篇 |
1982年 | 48篇 |
1981年 | 39篇 |
1979年 | 19篇 |
1978年 | 19篇 |
1977年 | 23篇 |
1976年 | 22篇 |
1975年 | 29篇 |
1974年 | 30篇 |
排序方式: 共有10000条查询结果,搜索用时 10 毫秒
991.
Xiaofang Bai Xiuping Zhang Yujiao Sun Mingcheng Huang Prof. Dr. Jiantao Fan Prof. Dr. Shaoyi Xu Prof. Dr. Hui Li 《Angewandte Chemie (International ed. in English)》2023,62(38):e202308704
To date, only a few noble metal oxides exhibit the required efficiency and stability as oxygen evolution reaction (OER) catalysts under the acidic, high-voltage conditions that exist during proton exchange membrane water electrolysis (PEMWE). The high cost and scarcity of these catalysts hinder the large-scale application of PEMWE. Here, we report a novel OER electrocatalyst for OER comprised of uniformly dispersed Ru clusters confined on boron carbon nitride (BCN) support. Compared to RuO2, our BCN-supported catalyst shows enhanced charge transfer. It displays a low overpotential of 164 mV at a current density of 10 mA cm−2, suggesting its excellent OER catalytic activity. This catalyst was able to operate continuously for over 12 h under acidic conditions, whereas RuO2 without any support fails in 1 h. Density functional theory (DFT) calculations confirm that the interaction between the N on BCN support and Ru clusters changes the adsorption capacity and reduces the OER energy barrier, which increases the electrocatalytic activity of Ru. 相似文献
992.
Bingyu Huang Xiannong Tang Yaoshuai Hong Longbin Li Prof. Ting Hu Prof. Kai Yuan Prof. Yiwang Chen 《Angewandte Chemie (International ed. in English)》2023,62(33):e202306667
Catalysts with metal-Nx sites have long been considered as effective electrocatalysts for oxygen reduction reaction (ORR), yet the accurate structure-property correlations of these active sites remain debatable. Report here is a proof-of-concept method to construct 1,4,8,11-tetraaza[14]annulene (TAA)-based polymer nanocomposites with well-managed electronic microenvironment via electron-donors/acceptors interaction of altering electron-withdrawing β-site substituents. DFT calculation proves the optimal −Cl substituted catalyst (CoTAA−Cl@GR) tailored the key OH* intermediate interaction with Co−N4 sites under the d-orbital regulation, hence reaching the top of ORR performance with excellent turnover frequency (0.49 e s−1 site−1). The combination of in situ scanning electrochemical microscopy and variable-frequency square wave voltammetry techniques contribute the great ORR kinetics of CoTAA−Cl@GR to the relatively high accessible site density (7.71×1019 site g−1) and fast electron outbound propagation mechanism. This work provides theoretical guidance for rational design of high-performance catalysts for ORR and beyond. 相似文献
993.
Shuai Zhang Yongjin Wang Prof. Hanchu Huang Prof. Derong Cao 《Angewandte Chemie (International ed. in English)》2023,62(37):e202308524
The ability to extend the polymerizations of thiyl radical propagation to be regulated by existing controlled methods would be highly desirable, yet remained very challenging to achieve because the thiyl radicals still cannot be reversibly controlled by these methods. In this article, we reported a novel strategy that could enable the radical ring-opening polymerization of macrocyclic allylic sulfides, wherein propagating specie is thiyl radical, to be controlled by reversible addition–fragmentation chain transfer (RAFT) agents. The key to the success of this strategy is the propagating thiyl radical can undergo desulfurization with isocyanide and generate a stabilized alkyl radical for reversible control. Systematic optimization of the reaction conditions allowed good control over the polymerization, leading to the formation of polymers with well-defined architectures, exemplified by the radical block copolymerization of macrocyclic allylic sulfides and vinyl monomers and the incorporation of sequence-defined segments into the polymer backbone. This work represents a significant step toward directly enabling the polymerizations of heteroatom-centered radical propagation to be regulated by existing reversible-deactivation radical polymerization techniques. 相似文献
994.
Fei Qi Yayun Pu Daofu Wu Xiaosheng Tang Qiang Huang 《Chemical record (New York, N.Y.)》2023,23(10):e202300078
It is still challenging to design and develop the state-of-the-art photocatalysts toward CO2 photoreduction. Enormous researchers have focused on the halide perovskites in the photocatalytic field for CO2 photoreduction, due to their excellent optical and physical properties. The toxicity of lead-based halide perovskites prevents their large-scale applications in photocatalytic fields. In consequence, lead-free halide perovskites (LFHPs) without the toxicity become the promising alternatives in the photocatalytic application for CO2 photoreduction. In recent years, the rapid advances of LFHPs have offer new chances for the photocatalytic CO2 reduction of LFHPs. In this review, we summarize not only the structures and properties of A2BX6, A2B(I)B(III)X6, and A3B2X9-type LFHPs but also their recent progresses on the photocatalytic CO2 reduction. Furthermore, we also point out the opportunities and perspectives to research LFHPs photocatalysts for CO2 photoreduction in the future. 相似文献
995.
Wenbo Huang Liqiao Shi Manli Liu Zhigang Zhang Fang Liu Tong Long Shaohua Wen Daye Huang Kaimei Wang Ronghua Zhou Wei Fang Hongtao Hu Shaoyong Ke 《Molecules (Basel, Switzerland)》2022,27(5)
Primary arylsulfonamide functional groups feature prominently in diverse pharmaceuticals. However, natural arylsulfonamides are relatively infrequent. In this work, two novel arylsulfonamide natural products were first synthesized, and then a series of novel molecules derived from natural arylsulfonamides were designed and synthesized, and their in vitro cytotoxic activities against A875, HepG2, and MARC145 cell lines were systematically evaluated. The results indicate that some of these arylsulfonamide derivatives exhibit significantly good cytotoxic activity against the tested cell lines compared with the control 5-fluorouracil (5-FU), such as compounds 10l, 10p, 10q, and 10r. In particular, the potential molecule 10q, containing a carbazole moiety, exhibited the highest inhibitory activity against all tested cell lines, with IC50 values of 4.19 ± 0.78, 3.55 ± 0.63, and 2.95 ± 0.78 μg/mL, respectively. This will offer the potential to discover novel drug-like compounds from the sparsely populated area of natural products that can lead to effective anticancer agents. 相似文献
996.
Yumei Li Xinxin Zhang Chunwen Lu Peng Lu Chongxu Yin Zhengmao Ye Zhaosong Huang 《Molecules (Basel, Switzerland)》2022,27(8)
A xylanase-producing strain, identified as Streptomyces sp. T7, was isolated from soil by our lab. The endo-β-1,4-xylanase (xynST7) gene was found in the genome sequence of strain T7, which was cloned and expressed in Escherichia coli. XynST7 belonged to the glycoside hydrolase family 10, with a molecular mass of approximately 47 kDa. The optimum pH and temperature of XynST7 were pH 6.0 and 60 °C, respectively, and it showed wide pH and temperature adaptability and stability, retaining more than half of its enzyme activity between pH 5.0 and 11.0 below 80 °C. XynST7 showed only endo-β-1,4-xylanase activity without cellulase- or β-xylosidase activity, and it showed maximal hydrolysis for corncob xylan in all the test substrates. Then, XynST7 was used for the production of xylo-oligosaccharides (XOSs) by hydrolyzing xylan extracted from raw corncobs. The maximum yield of the XOS was 8.61 ± 0.13 mg/mL using 15 U/mL of XynST7 and 1.5% corncob xylan after 10 h of incubation at 60 °C. The resulting hydrolysate products mainly consisted of xylobiose and xylotriose. These data indicated that XynST7 might by a promising tool for various industrial applications. 相似文献
997.
Meng-Xing Huang Yan-Quan Chen Run-Duo Liu Yue Huang Chen Zhang 《Molecules (Basel, Switzerland)》2022,27(11)
Dipyridamole, apart from its well-known antiplatelet and phosphodiesterase inhibitory activities, is a promising old drug for the treatment of pulmonary fibrosis. However, dipyridamole shows poor pharmacokinetic properties with a half-life (T1/2) of 7 min in rat liver microsomes (RLM). To improve the metabolic stability of dipyridamole, a series of pyrimidopyrimidine derivatives have been designed with the assistance of molecular docking. Among all the twenty-four synthesized compounds, compound (S)-4h showed outstanding metabolic stability (T1/2 = 67 min) in RLM, with an IC50 of 332 nM against PDE5. Furthermore, some interesting structure–activity relationships (SAR) were explained with the assistance of molecular docking. 相似文献
998.
Yi-Lin He Pei-Zhi Huang Hong-Ying Yang Wei-Jiao Feng Zhao-Cai Li Kun Gao 《Molecules (Basel, Switzerland)》2022,27(11)
Two new neolignans jatrolignans, C (1) and D (2), a pair of epimers, were isolated from the whole plants of Jatropha curcas L. (Euphorbiaceae). Their structures were determined with HRESIMS, IR, and NMR data analysis, and electronic circular dichroism (ECD) experiments via a comparison of the experimental and the calculated ECD spectra. Their antichlamydial activity was evaluated in Chlamydia abortus. They both showed dose-dependent antichlamydial effects. Significant growth inhibitory effects were observed at a minimum concentration of 40 μM. 相似文献
999.
Developing low-cost and high-activity transition metal oxide electrocatalysts for an efficient oxygen evolution reaction (OER) at a large current density is highly demanded for industrial application and remains a big challenge. Herein, we report vertically aligned cobalt doped Ni–Fe based oxide (Co–NiO/Fe2O3) arrays as a robust OER electrocatalyst via a simple method combining hydrothermal reaction with heat treatment. Density functional theory calculation and XRD Rietveld refinement reveal that Co preferentially occupies the Ni sites compared to Fe in the Ni–Fe based oxides. The electronic structures of the Co–NiO/Fe2O3 could be further optimized, leading to the improvement of the intrinsic electronic conductivity and d-band center energy level and the decrease in the reaction energy barrier of the rate-determining step for the OER, thus accelerating its OER electrocatalytic activity. The Co–NiO/Fe2O3 nanosheet arrays display state-of-the-art OER activities at a large current density for industrial demands among Fe–Co–Ni based oxide electrocatalysts, which only require an ultra-low overpotential of 230 mV at a high current density of 500 mA cm−2, and exhibit superb durability at 500 mA cm−2 for at least 300 h without obvious degradation. The Co–NiO/Fe2O3 nanosheet arrays also have a small Tafel slope of 33.9 mV dec−1, demonstrating fast reaction kinetics. This work affords a simple and effective method to design and construct transition metal oxide based electrocatalysts for efficient water oxidation.Co–NiO/Fe2O3 nanosheets featuring Co substitution on Ni sites can effectively regulate electronic structures and exhibit high OER activities with low overpotential (η500 = 230 mV), small Tafel slope (33.9 mV dec−1) and superb durability for 300 h. 相似文献
1000.
Yixuan Tang Shihui Huang Xingxing Chen Junzhang Huang Qianwen Lin Lei Huang Shuping Wang Qihua Zhu Yungen Xu Yi Zou 《Molecules (Basel, Switzerland)》2022,27(19)
Protein arginine methyltransferases 5 (PRMT5) is a clinically promising epigenetic target that is upregulated in a variety of tumors. Currently, there are several PRMT5 inhibitors under preclinical or clinical development, however the established clinical inhibitors show favorable toxicity. Thus, it remains an unmet need to discover novel and structurally diverse PRMT5 inhibitors with characterized therapeutic utility. Herein, a series of tetrahydroisoquinoline (THIQ) derivatives were designed and synthesized as PRMT5 inhibitors using GSK-3326595 as the lead compound. Among them, compound 20 (IC50: 4.2 nM) exhibits more potent PRMT5 inhibitory activity than GSK-3326595 (IC50: 9.2 nM). In addition, compound 20 shows high anti-proliferative effects on MV-4-11 and MDA-MB-468 tumor cells and low cytotoxicity on AML-12 hepatocytes. Furthermore, compound 20 possesses acceptable pharmacokinetic profiles and displays considerable in vivo antitumor efficacy in a MV-4-11 xenograft model. Taken together, compound 20 is an antitumor compound worthy of further study. 相似文献