全文获取类型
收费全文 | 49287篇 |
免费 | 6352篇 |
国内免费 | 4747篇 |
专业分类
化学 | 25773篇 |
晶体学 | 361篇 |
力学 | 2227篇 |
综合类 | 241篇 |
数学 | 4280篇 |
物理学 | 13548篇 |
无线电 | 13956篇 |
出版年
2024年 | 169篇 |
2023年 | 1145篇 |
2022年 | 1362篇 |
2021年 | 1865篇 |
2020年 | 1786篇 |
2019年 | 1599篇 |
2018年 | 1380篇 |
2017年 | 1325篇 |
2016年 | 1880篇 |
2015年 | 2035篇 |
2014年 | 2476篇 |
2013年 | 3184篇 |
2012年 | 3936篇 |
2011年 | 3859篇 |
2010年 | 2785篇 |
2009年 | 2754篇 |
2008年 | 2973篇 |
2007年 | 2643篇 |
2006年 | 2560篇 |
2005年 | 2252篇 |
2004年 | 1747篇 |
2003年 | 1390篇 |
2002年 | 1245篇 |
2001年 | 1071篇 |
2000年 | 1039篇 |
1999年 | 1175篇 |
1998年 | 1032篇 |
1997年 | 934篇 |
1996年 | 990篇 |
1995年 | 856篇 |
1994年 | 779篇 |
1993年 | 678篇 |
1992年 | 620篇 |
1991年 | 486篇 |
1990年 | 415篇 |
1989年 | 298篇 |
1988年 | 266篇 |
1987年 | 235篇 |
1986年 | 166篇 |
1985年 | 182篇 |
1984年 | 152篇 |
1983年 | 131篇 |
1982年 | 98篇 |
1981年 | 66篇 |
1980年 | 58篇 |
1979年 | 38篇 |
1978年 | 30篇 |
1976年 | 31篇 |
1975年 | 36篇 |
1974年 | 26篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Shin-Hun Juang Min-Tsang Hsieh Pei-Ling Hsu Ju-Ling Chen Hui-Kang Liu Fong-Pin Liang Sheng-Chu Kuo Chen-Yuan Chiu Shing-Hwa Liu Chen-Hsi Chou Tian-Shung Wu Hsin-Yi Hung 《Molecules (Basel, Switzerland)》2021,26(1)
Constitutive androstane receptor (CAR) activation has found to ameliorate diabetes in animal models. However, no CAR agonists are available clinically. Therefore, a safe and effective CAR activator would be an alternative option. In this study, sixty courmarin derivatives either synthesized or purified from Artemisia capillaris were screened for CAR activation activity. Chemical modifications were on position 5,6,7,8 with mono-, di-, tri-, or tetra-substitutions. Among all the compounds subjected for in vitro CAR activation screening, 6,7-diprenoxycoumarin was the most effective and was selected for further preclinical studies. Chemical modification on the 6 position and unsaturated chains were generally beneficial. Electron-withdrawn groups as well as long unsaturated chains were hazardous to the activity. Mechanism of action studies showed that CAR activation of 6,7-diprenoxycoumarin might be through the inhibition of EGFR signaling and upregulating PP2Ac methylation. To sum up, modification mimicking natural occurring coumarins shed light on CAR studies and the established screening system provides a rapid method for the discovery and development of CAR activators. In addition, one CAR activator, scoparone, did showed anti-diabetes effect in db/db mice without elevation of insulin levels. 相似文献
992.
Nasopharyngeal carcinoma (NPC) frequently occurs in Southern China. The main treatments of NPC are chemotherapy and radiotherapy. However, chemo-resistance arises as a big obstacle in treating NPC. Therefore, there is a great need to develop new compounds that could reverse tumor drug resistance. In this study, eight matrine derivatives containing thiophene group were designed and synthesized. Structures of these 8 compounds were characterized by 1H-NMR, 13C-NMR, and high-resolution mass spectrometer (HRMS). The cytotoxicity and preliminary synergistic effects of these 8 compounds were detected against nasopharyngeal carcinoma (NPC) cells and cisplatin-resistant NPC cells (CNE2/CDDP), respectively. Furthermore, the in vivo and in vitro tumor resistance reversal effects of compound 3f were evaluated. Moreover, docking studies were performed in Bclw (2Y6W). The results displayed that compound 3f showed synergistic inhibitory effects with cisplatin against CNE2/CDDP cells proliferation via apoptosis induction. Docking results revealed that compound 3f may exert its effects via inhibiting anti-apoptosis protein Bcl-w. 相似文献
993.
Desulfurized gypsum (DG) as a soil modifier imparts it with bulk solid sulfite. The Fe(III)–sulfite process in the liquid phase has shown great potential for the rapid removal of As(III), but the performance and mechanism of this process using DG as a sulfite source in aqueous solution remains unclear. In this work, employing solid CaSO3 as a source of SO32−, we have studied the effects of different conditions (e.g., pH, Fe dosage, sulfite dosage) on As(III) oxidation in the Fe(III)–CaSO3 system. The results show that 72.1% of As(III) was removed from solution by centrifugal treatment for 60 min at near-neutral pH. Quenching experiments have indicated that oxidation efficiencies of As(III) are due at 67.5% to HO•, 17.5% to SO5•− and 15% to SO4•−. This finding may have promising implications in developing a new cost-effective technology for the treatment of arsenic-containing water using DG. 相似文献
994.
Xingge Wu Zhigang Zhang Zhiyong He Zhaojun Wang Fang Qin Maomao Zeng Jie Chen 《Molecules (Basel, Switzerland)》2021,26(5)
The aim of this research was to investigate the effect of the number of freeze–thaw cycles (0, 1, 3, 5, and 7) on porcine longissimus protein and lipid oxidation, as well as changes in heterocyclic aromatic amines (HAAs) and advanced glycation end products (AGEs) and their precursors. We analyzed the relationship among HAAs, AGEs, oxidation, and precursors and found the following results after seven freeze–thaw cycles. The HAAs, Norharman and Harman, were 20.33% and 16.67% higher, respectively. The AGEs, Nε-carboxyethyllysine (CEL) and Nε-carboxymethyllysine (CML), were 11.81% and 14.02% higher, respectively. Glucose, creatine, and creatinine were reduced by 33.92%, 5.93%, and 1.12%, respectively after seven freeze–thaw cycles. Norharman was significantly correlated with thiobarbituric acid reactive substances (TBARS; r2 = 0.910) and glucose (r2 = −0.914). Harman was significantly correlated to TBARS (r2 = 0.951), carbonyl (r2 = 0.990), and glucose (r2 = −0.920). CEL was correlated to TBARS (r2 = 0.992) and carbonyl (r2 = 0.933). These changes suggest that oxidation and the Maillard reaction during freeze–thaw cycles promote HAA and AGE production in raw pork. 相似文献
995.
Yiqun Dai Xiaolong Sun Bohan Li Hui Ma Pingping Wu Yingping Zhang Meilin Zhu Hong-Mei Li Minjian Qin Cheng-Zhu Wu 《Molecules (Basel, Switzerland)》2021,26(6)
Nasopharyngeal carcinoma (NPC) is a common malignant head and neck tumor. Drug resistance and distant metastasis are the predominant cause of treatment failure in NPC patients. Hispidulin is a flavonoid extracted from the bioassay-guided separation of the EtOH extract of Salvia plebeia with strong anti-proliferative activity in nasopharyngeal carcinoma cells (CNE-2Z). In this study, the effects of hispidulin on proliferation, invasion, migration, and apoptosis were investigated in CNE-2Z cells. The [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] (MTT) assay and the colony formation assay revealed that hispidulin could inhibit CNE-2Z cell proliferation. Hispidulin (25, 50, 100 μM) also induced apoptosis in a dose-dependent manner in CNE-2Z cells. The expression of Akt was reduced, and the expression of the ratio of Bax/Bcl-2 was increased. In addition, scratch wound and transwell assays proved that hispidulin (6.25, 12.5, 25 μM) could inhibited the migration and invasion in CNE-2Z cells. The expressions of HIF-1α, MMP-9, and MMP-2 were decreased, while the MMPs inhibitor TIMP1 was enhanced by hispidulin. Moreover, hispidulin exhibited potent suppression tumor growth and low toxicity in CNE-2Z cancer-bearing mice at a dosage of 20 mg/kg/day. Thus, hispidulin appears to be a potentially effective agent for NPC treatment. 相似文献
996.
Construction of Hybrid Bimetallic Uranyl Compounds Based on a Preassembled Terpyridine Metalloligand
Xianghe Kong Dr. Kongqiu Hu Dr. Lei Mei Dr. Qunyan Wu Zhiwei Huang Kang Liu Prof. Zhifang Chai Prof. Changming Nie Prof. Weiqun Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):2124-2130
Six hybrid uranyl–transition metal compounds [UO2Ni(cptpy)2(HCOO)2(DMF)(H2O)] ( 1 ), [UO2Ni(cptpy)2(BTPA)2] ( 2 ), [UO2Fe(cptpy)2(HCOO)2(DMF)(H2O)] ( 3 ), [UO2Fe(cptpy)2(BTPA)2] ( 4 ), [UO2Co(cptpy)2(HCOO)2(DMF)(H2O)] ( 5 ), and [UO2Co(cptpy)2(BTPA)2] ( 6 ), based on bifunctional ligand 4′-(4-carboxyphenyl)-2,2′:6′,2′′-terpyridine (Hcptpy) are reported (H2BTPA = 4,4′-biphenyldicarboxylic acid). Single-crystal XRD revealed that all six compounds feature similar metalloligands, which consist of two cptpy− anions and one transition metal cation. The metalloligand M(cptpy)2 can be considered to be an extended linear dicarboxylic ligand with length of 22.12 Å. Compounds 1 , 3 , and 5 are isomers, and all of them feature 1D chain structures. The adjacent 1D chains are connected together by hydrogen bonds and π–π interactions to form a 3D porous structure, which is filled with solvent molecules and can be exchanged with I2. Compounds 2 , 4 , and 6 are also isomers, and all of them feature 2D honeycomb (6,3) networks with hexagonal units of dimensions 41.91×26.89 Å, which are the largest among uranyl compounds with honeycomb networks. The large aperture allows two sets of equivalent networks to be entangled together to result in a 2D+2D→3D polycatenated framework. Remarkably, these uranyl compounds exhibit high catalytic activity for cycloaddition of carbon dioxide. Moreover, the geometric and electronic structures of compounds 1 and 2 are systematically discussed on the basis of DFT calculations. 相似文献
997.
Anzhou Yang Jingchun Wang Keying Su Wu Lei Xiaoyu Qiu Yawen Tang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(15):4869-4875
The surface hydroxyl groups of NixCu1−x(OH)2 play a crucial role in governing their conversion efficiency into NixCu1−xOx(OH)2−x during the electro-chemical pre-activation process, thus affecting the integral ammonia oxidation reaction (AOR) reactivity. Herein, the rational design of hierarchical porous NiCu double hydroxide nanotyres (NiCu DHTs) was reported for the first time by considering hydroxyl-rich interfaces to promote pre-activation efficiency and intrinsic structural superiority (i.e., annulus, porosity) to accelerate AOR kinetics. A systematic investigation of the structure–function relationship was conducted by manipulating a series of NiCu DHs with tunable intercalations and morphologies. Remarkably, the NiCu DHTs exhibit superior AOR activity (onset potential of 1.31 V with 7.52 mA cm−2 at 1.5 V) and high ammonia sensitivity (detection limit of 9 μm ), manifesting one of the best non-noble metal AOR electrocatalysts and electro-analytical electrodetectors. This work deepens the understanding of the crucial role of surface hydroxyl groups on determining the catalytic performance in alkaline medium. 相似文献
998.
Zirconium-based metal-organic framework materials (Zr−MOFs) have more practical usage over most conventional benchmark porous materials and even many other MOFs due to the excellent structural stability, rich coordination forms, and various active sites. However, their mass-production and application are restricted by the high-cost raw materials, complex synthesis procedures, harsh reaction conditions, and unexpected environmental impact. Based on the principles of “Green Chemistry”, considerable efforts have been done for breaking through the limitations, and significant progress has been made in the sustainable synthesis of Zr−MOFs over the past decade. In this review, the advancements of green raw materials and green synthesis methods in the synthesis of Zr−MOFs are reviewed, along with the corresponding drawbacks. The challenges and prospects are discussed and outlooked, expecting to provide guidance for the acceleration of the industrialization and commercialization of Zr−MOFs. 相似文献
999.
Dr. Yong Wu Dr. Shanshan Cao Dr. Iskander Douair Prof. Laurent Maron Prof. Xihe Bi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(19):5999-6006
The [2+1] cycloaddition reaction of a metal carbene with an alkene can produce important cyclopropane products for synthetic intermediates, materials, and pharmaceutical applications. However, this reaction is often accompanied by side reactions, such as coupling and self-coupling, so that the yield of the cyclopropanation product of non-silver transition-metal carbenes and hindered alkenes is generally lower than 50 %. To solve this problem, the addition of a low concentration of diazo compound (decomposition of sulfonyl hydrazones) to alkenes catalyzed by either CuOAc or PdCl2 was studied, but side reactions could still not be avoided. Interestingly, however, the yield of cyclopropanation products for such hindered alkenes were as high as 99 % with AgOTf as a catalyst. To explain this unexpected phenomenon, reaction pathways have been computed for four different catalysts by using DFT. By combining the results of these calculations with those obtained experimentally, it can be concluded that the efficiency of the silver catalyst is due to the barrierless concerted cycloaddition step and the kinetic inhibition of side reactions by a high concentration of alkene. 相似文献
1000.
Zhaorui Li Dr. Kristin Werner Lu Chen Aiping Jia Dr. Kun Qian Dr. Jian-Qiang Zhong Dr. Rui You Dr. Lihui Wu Liyuan Zhang Dr. Haibin Pan Prof. Dr. Xin-Ping Wu Prof. Dr. Xue-Qing Gong Dr. Shamil Shaikhutdinov Prof. Weixin Huang Prof. Dr. Hans-Joachim Freund 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(16):5268-5276
The study reports the first attempt to address the interplay between surface and bulk in hydride formation in ceria (CeO2) by combining experiment, using surface sensitive and bulk sensitive spectroscopic techniques on the two sample systems, i.e., CeO2(111) thin films and CeO2 powders, and theoretical calculations of CeO2(111) surfaces with oxygen vacancies (Ov) at the surface and in the bulk. We show that, on a stoichiometric CeO2(111) surface, H2 dissociates and forms surface hydroxyls (OH). On the pre-reduced CeO2−x samples, both films and powders, hydroxyls and hydrides (Ce−H) are formed on the surface as well as in the bulk, accompanied by the Ce3+ ↔ Ce4+ redox reaction. As the Ov concentration increases, hydroxyl is destabilized and hydride becomes more stable. Surface hydroxyl is more stable than bulk hydroxyl, whereas bulk hydride is more stable than surface hydride. The surface hydride formation is the kinetically favorable process at relatively low temperatures, and the resulting surface hydride may diffuse into the bulk region and be stabilized therein. At higher temperatures, surface hydroxyls can react to produce water and create additional oxygen vacancies, increasing its concentration, which controls the H2/CeO2 interaction. The results demonstrate a large diversity of reaction pathways, which have to be taken into account for better understanding of reactivity of ceria-based catalysts in a hydrogen-rich atmosphere. 相似文献