全文获取类型
收费全文 | 19757篇 |
免费 | 3449篇 |
国内免费 | 2260篇 |
专业分类
化学 | 14205篇 |
晶体学 | 244篇 |
力学 | 1234篇 |
综合类 | 193篇 |
数学 | 2072篇 |
物理学 | 7518篇 |
出版年
2024年 | 20篇 |
2023年 | 447篇 |
2022年 | 416篇 |
2021年 | 620篇 |
2020年 | 803篇 |
2019年 | 777篇 |
2018年 | 632篇 |
2017年 | 609篇 |
2016年 | 939篇 |
2015年 | 916篇 |
2014年 | 1063篇 |
2013年 | 1382篇 |
2012年 | 1814篇 |
2011年 | 1902篇 |
2010年 | 1256篇 |
2009年 | 1117篇 |
2008年 | 1306篇 |
2007年 | 1292篇 |
2006年 | 1141篇 |
2005年 | 1020篇 |
2004年 | 727篇 |
2003年 | 613篇 |
2002年 | 514篇 |
2001年 | 411篇 |
2000年 | 395篇 |
1999年 | 459篇 |
1998年 | 340篇 |
1997年 | 351篇 |
1996年 | 276篇 |
1995年 | 288篇 |
1994年 | 296篇 |
1993年 | 242篇 |
1992年 | 194篇 |
1991年 | 197篇 |
1990年 | 176篇 |
1989年 | 109篇 |
1988年 | 85篇 |
1987年 | 90篇 |
1986年 | 59篇 |
1985年 | 44篇 |
1984年 | 41篇 |
1983年 | 24篇 |
1982年 | 25篇 |
1981年 | 18篇 |
1980年 | 13篇 |
1975年 | 2篇 |
1957年 | 4篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
Li Song Jiaxiang Lin Yang He Jingqing Li Jing Sheng Shichun Jiang Dinghai Huang 《Journal of Polymer Science.Polymer Physics》2019,57(3):142-151
Time‐dependent demixing enthalpy recovery behavior of aqueous poly(vinyl methyl ether) (PVME) solutions exhibits distinct recovery characteristics in three concentration regions. The absence of recovery behavior below a water concentration of 38.3 wt % indicates that the PVME coil is in a globular state. The typically sigmoidal recovery behavior of demixing enthalpy above 38.3 wt % is ascribed to the reswelling of the collapsed polymer coils induced by the entropic effect. The increase in difference between the upper and lower limits indicates the continued swelling of the PVME coils. Above 65 wt %, a dominant diluting effect can be observed, and a much longer phase separation time is needed to reach the expected lower limit. In contrast, the recovery of demixing enthalpy in a wide range of water concentration (from 38.3 to 90 wt %) exhibits the same feature. The infrared spectroscopy results are in agreement with the above macroscopic differential scanning calorimetry results. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 142–151 相似文献
102.
Qimin Jiang Yongzhuang Du Wenyan Huang Jianhai Chen Hongjun Yang Xiaoqiang Xue Li Jiang Bibiao Jiang 《Journal of polymer science. Part A, Polymer chemistry》2019,57(7):833-840
In this article, we report the radical polymerization in the presence of peroxide and commercially available or designed reducing agent monomer (RAM) for the preparation of branched poly(methyl methacrylate)s (PMMAs). The reaction behavior of the RAM was studied by NMR. Triple‐detection SEC (TD‐SEC) analysis was used to confirm the branching structure of the prepared PMMAs and to investigate the influence of peroxide concentration and RAM concentration on molecular weight and branched structure. The obtained branched PMMAs exhibited high molecular weights and relatively narrow polydispersities at high conversion of MMA. Interestingly, a significant increase in molecular weight and degree of branching of the obtained polymers are observed in higher BPO concentration, these results are quite different from that reported in the literature. The unique radical polymerization mechanism in the RAM/BPO redox‐initiated radical polymerization system resulted in branched PMMAs with high molecular weights at relatively high RAM and BPO concentrations. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 833–840 相似文献
103.
104.
Tianming Dai Weifan Jiang Zizheng Guo Zhenyu Wang Mingping Huang Guorui Zhong Chuxin Liang Xuzhe Pei Renke Dai 《Biomedical chromatography : BMC》2019,33(9)
Withaferin A (WA) is one of the major bioactive steroidal lactones with extensive pharmacological activities present in the plant Withania somnifera. The absolute oral bioavailability of WA remains unknown and human‐related in vitro data are not available. Therefore, in the present study, the absolute oral bioavailability of WA in male rats and the in vitro screening of absorption factors by Q‐trap and LC–MS/MS analysis were conducted to explore possible clinical properties of WA. The developed and validated analytical methods were successfully applied to the pharmacokinetic studies and in vitro measurement of WA. The oral bioavailability was determined to be 32.4 ± 4.8% based on intravenous (5 mg/kg) and oral (10 mg/kg) administrations of WA in male rats. The in vitro results showed that WA could be easily transported across Caco‐2 cells and WA did not show as a substrate for P‐glycoprotein. Moreover, the stability of WA was similar between male rat and human in simulated gastric fluid (stable), in intestinal microflora solution (slow decrease) and in liver microsomes (rapid depletion, with a half‐life of 5.6 min). As such, the first‐pass metabolism of WA was further verified by rat intestine‐liver in situ perfusion, revealing that WA rapidly decreased and 27.1% remained within 1 h, while the content of three major metabolites (M1, M4, M5) identified by Q‐trap increased. This perfusion result is consistent with the oral bioavailability results in vivo. The first‐pass metabolism of WA might be the main barrier in achieving good oral bioavailability in male rats and it is predicted to be similar in humans. This study may hold clinical significance. 相似文献
105.
Xue Liu Wenting Mao Dr. Jingang Jiang Dr. Xinqing Lu Mingming Peng Dr. Hao Xu Prof. Lu Han Prof. Shun-ai Che Prof. Peng Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(17):4520-4529
The conversion of the alkali-treated intergrowth germanosilicate CIT-13 into the single-crystalline high-silica ECNU-21 (named after East China Normal University) zeolite, with a novel topology and a highly crystalline zeolite framework, has been realized through a creative top-down strategy involving a mild alkaline-induced multistep process consisting of structural degradation and reconstruction. Instead of acid treatment, hydrolysis in aqueous ammonia solution not only readily cleaved the chemically weak Ge(Si)−O−Ge bonds located within the interlayer double four ring (D4R) units of CIT-13, but also cleaved the metastable Si−O−Si bonds therein. This led to extensive removal of the D4R units, and also generated silanol groups on adjacent silica-rich layers, which then condensed to form a novel daughter structure upon calcination. Individual oxygen bridges in the reassembled ECNU-21 replaced the germanium-rich D4R units in CIT-13, thereby eliminating the original intergrowth phenomenon along the b axis. With an ordered crystalline structure of 10-ring (R) channels as well as suitable germanium-related Lewis acid sites, ECNU-21 serves as a stable solid Lewis acid catalyst for the shape-selective hydration of ethylene oxide (EO) to ethylene glycol (EG) at greatly reduced H2O/EO ratios and reaction temperature in comparison with the noncatalytic industrial process. 相似文献
106.
Dr. Longhai Zhang Prof. Tong Wei Dr. Zimu Jiang Prof. Zhuangjun Fan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(19):5022-5027
To optimize the cycle life and rate performance of lithium-ion batteries (LIBs), ultra-fine Fe2O3 nanowires with a diameter of approximately 2 nm uniformly anchored on a cross-linked graphene ribbon network are fabricated. The unique three-dimensional structure can effectively improve the electrical conductivity and facilitate ion diffusion, especially cross-plane diffusion. Moreover, Fe2O3 nanowires on graphene ribbons (Fe2O3/GR) are easily accessible for lithium ions compared with the traditional graphene sheets (Fe2O3/GS). In addition, the well-developed elastic network can not only undergo the drastic volume expansion during repetitive cycling, but also protect the bulk electrode from further pulverization. As a result, the Fe2O3/GR hybrid exhibits high rate and long cycle life Li storage performance (632 mAh g−1 at 5 A g−1, and 471 mAh g−1 capacity maintained even after 3000 cycles). Especially at high mass loading (≈4 mg cm−2), the Fe2O3/GR can still deliver higher reversible capacity (223 mAh g−1 even at 2 A g−1) compared with the Fe2O3/GS (37 mAh g−1) for LIBs. 相似文献
107.
Jing Zhou Shihua Song Feng Jiang Chunling Fu Prof. Shengming Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(42):9948-9958
Herein, we report the total synthesis of traumatic lactone and rhizobialide by utilizing allenoic acid to construct the lactone ring. The key starting materials, allenoic acids, could be prepared by the ATA (allenation of terminal alkynes) of a terminal alkyne with an aldehyde that contained a protected hydroxyl group followed by hydrolysis. Importantly, the asymmetric synthesis could be realized just by replacing racemic diphenylprinol with (R)- or (S)-diphenylprinol to deliver the optically active allenoate. 相似文献
108.
Na-Na Jiang Shu-Zong Du Yan-Song Ye Hui Yan Xing-Wei Yang Jian Yang Yin Nian Gang Xu 《Tetrahedron letters》2019,60(45):151220
Hyphenone A (1), a new type of bicyclic polyprenylated acylphloroglucinols (BPAPs) featured with an unprecedented 3,3-diisoprenylated 1,3,5-trione core, were characterized from the roots of Hypericum henryi together with two new congeners (hyphenones B–C, 2–3) and five known biosynthetic related PPAPs. Biogenetically, 1 should be derived from a novel 3,3,5,5-tetraisoprenylated MPAPs precursor. Their structures were elucidated by comprehensive spectroscopic data and X-ray diffraction. Moreover, 1–3 were identified as the first PPAPs type Cav3.1 T-type calcium channel (TTCC) inhibitors, with IC50 values of 7.07, 6.19, and 5.47 μM, respectively. 相似文献
109.
Jiaguo Huang Yan Lyu Jingchao Li Penghui Cheng Yuyan Jiang Kanyi Pu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(49):17960-17968
Despite its high morbidity and mortality, contrast‐induced acute kidney injury (CIAKI) remains a diagnostic dilemma because it relies on in vitro detection of insensitive late‐stage blood and urinary biomarkers. We report the synthesis of an activatable duplex reporter (ADR) for real‐time in vivo imaging of CIAKI. ADR is equipped with chemiluminescence and near‐infrared fluorescence (NIRF) signaling channels that can be activated by oxidative stress (superoxide anion, O2.?) and lysosomal damage (N‐acetyl‐β‐d ‐glucosaminidase, NAG), respectively. By virtue of its high renal clearance efficiency (80 % injected doses after 24 h injection), ADR detects sequential upregulation of O2.? and NAG in the kidneys of living mice prior to a significant decrease in glomerular filtration rate (GFR) and tissue damage in the course of CIAKI. ADR outperforms the typical clinical assays and detects CIAKI at least 8 h (NIRF) and up to 16 h (chemiluminescence) earlier. 相似文献
110.
Long‐Zhang Dong Lei Zhang Jiang Liu Qing Huang Meng Lu Wen‐Xin Ji Ya‐Qian Lan 《Angewandte Chemie (International ed. in English)》2020,59(7):2659-2663
A series of stable heterometallic Fe2M cluster‐based MOFs ( NNU‐31‐M , M=Co, Ni, Zn) photocatalysts are presented. They can achieve the overall conversion of CO2 and H2O into HCOOH and O2 without the assistance of additional sacrificial agent and photosensitizer. The heterometallic cluster units and photosensitive ligands excited by visible light generate separated electrons and holes. Then, low‐valent metal M accepts electrons to reduce CO2, and high‐valent Fe uses holes to oxidize H2O. This is the first MOF photocatalyst system to finish artificial photosynthetic full reaction. It is noted that NNU‐31‐Zn exhibits the highest HCOOH yield of 26.3 μmol g?1 h?1 (selectivity of ca. 100 %). Furthermore, the DFT calculations based on crystal structures demonstrate the photocatalytic reaction mechanism. This work proposes a new strategy for how to design crystalline photocatalyst to realize artificial photosynthetic overall reaction. 相似文献