全文获取类型
收费全文 | 527篇 |
免费 | 66篇 |
国内免费 | 101篇 |
专业分类
化学 | 522篇 |
晶体学 | 7篇 |
力学 | 18篇 |
综合类 | 7篇 |
数学 | 65篇 |
物理学 | 75篇 |
出版年
2024年 | 2篇 |
2023年 | 23篇 |
2022年 | 31篇 |
2021年 | 47篇 |
2020年 | 62篇 |
2019年 | 44篇 |
2018年 | 43篇 |
2017年 | 20篇 |
2016年 | 48篇 |
2015年 | 42篇 |
2014年 | 44篇 |
2013年 | 41篇 |
2012年 | 43篇 |
2011年 | 56篇 |
2010年 | 22篇 |
2009年 | 30篇 |
2008年 | 18篇 |
2007年 | 15篇 |
2006年 | 14篇 |
2005年 | 12篇 |
2004年 | 6篇 |
2003年 | 5篇 |
2002年 | 3篇 |
2001年 | 1篇 |
2000年 | 3篇 |
1999年 | 1篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 6篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 2篇 |
排序方式: 共有694条查询结果,搜索用时 15 毫秒
31.
Yingying Wang Zhuangdong Yuan Yunjie Guo Xuxiao Ma Zitong Meng Jingquan Sha Haifeng Zhang 《无机化学与普通化学杂志》2020,646(20):1696-1701
Two dinuclear LnIII-based clusters, namely [Dy2L2(NO3)2(DME)4] ( 1 ) and [Gd2L2(NO3)2(DME)4] ( 2 ) [H2L = (E)-2-((2-hydroxybenzylidene)amino)phenol] were obtained under hydrothermal condition. Two LnIII ions are bridged by two phenolic hydroxyl oxygen atoms, and the distances of them are 3.829 Å (Dy1–Dy1A) and 3.860 Å (Gd1–Gd1A). Two Dy1–O–Dy1A and Gd1–O–Gd1A angles are 109.4° and 109.8°, respectively. Magnetic studies reveal a weak antiferromagnetic interaction between Gd ions in complex 2 , and single-molecule magnet behavior for 1 with Ueff = 49.9 K and τ0 = 1.54 × 10–6 s. 相似文献
32.
随着现场分析对于快速、便携和经济型检测的需求,分析仪器的便携化和微型化备受关注。3D打印技术的不断发展,将会极大推动小型化、便携式实验设备的开发和研制。分析仪器的微型化有助于促进资源不足地区在医疗现场、食品安全和环境污染等方面的现场监测。目前,用于蛋白质分离的凝胶电泳装置多为实验室用小型化分析仪器,可用于现场快速分离蛋白质的小型化仪器尚未见报道。该研究设计加工了一款便携式凝胶电泳装置,用于蛋白质的快速分离检测。首先,通过3D打印加工的凝胶电泳装置可在实验室内方便、快捷、低成本的复制。其次,通过对预染蛋白质相对分子质量标准的分离测试,对该系统结构进行优化。优化后该凝胶电泳装置电泳槽的尺寸仅为15 mm×20 mm×17 mm,采用3D打印技术可在5 h内加工完成,耗费打印材料10 mL。正负极所用电泳缓冲液共需4 mL,所使用的25 V锂电池可实现100 h左右的工作时间。装置优化后可实现蛋白质的快速高效分离。随后,在5种常用蛋白质相对分子质量标准的分离中,该装置与商业化平板凝胶电泳分离效果相当,同时具备更快的分离速度。该研究在便携式凝胶电泳装置的开发及其在蛋白质快速分离方面取得了初步成果,但在分离完成后立即对蛋白质进行定量分析以及更多实际样品的应用方面还需要进一步研究。 相似文献
33.
Yunqin Zhang Zixi Chen Yingying Huang Shaojun He Xingkuan Yang Zhibing Wu Xiufang Wang Guozhi Xiao 《Angewandte Chemie (International ed. in English)》2020,59(19):7576-7584
The synthesis of long, branched, and complex carbohydrate sequences remains a challenging task in chemical synthesis. Reported here is an efficient and modular one‐pot synthesis of a nona‐decasaccharide and shorter sequences from Psidium guajava polysaccharides, which have the potent α‐glucosidase inhibitory activity. The synthetic strategy features: 1) several one‐pot glycosylation reactions on the basis of N‐phenyltrifluoroacetimidate (PTFAI) and Yu glycosylation to streamline the chemical synthesis of oligosaccharides, 2) the successful and efficient assembly sequences (first O3′, second O5′, final O2′) toward the challenging 2,3,5‐branched Araf motif, 3) the stereoselective 1,2‐cis‐glucosylation by reagent control, and 4) the convergent [6+6+7] one‐pot coupling reaction for the final assembly of the target nona‐decasaccharide. This orthogonal one‐pot glycosylation strategy can streamline the chemical synthesis of long, branched, and complicated carbohydrate chains. 相似文献
34.
Siyuan Li Weidong Zhang Qiang Wu Lei Fan Xinyang Wang Xiao Wang Zeyu Shen Yi He Yingying Lu 《Angewandte Chemie (International ed. in English)》2020,59(35):14935-14941
A rechargeable Li metal anode coupled with a high‐voltage cathode is a promising approach to high‐energy‐density batteries exceeding 300 Wh kg?1. Reported here is an advanced dual‐additive electrolyte containing a unique solvation structure and it comprises a tris(pentafluorophenyl)borane additive and LiNO3 in a carbonate‐based electrolyte. This system generates a robust outer Li2O solid electrolyte interface and F‐ and B‐containing conformal cathode electrolyte interphase. The resulting stable ion transport kinetics enables excellent cycling of Li/LiNi0.8Mn0.1Co0.1O2 for 140 cycles with 80 % capacity retention under highly challenging conditions (≈295.1 Wh kg?1 at cell‐level). The electrolyte also exhibits high cycling stability for a 4.6 V LiCoO2 (160 cycles with 89.8 % capacity retention) cathode and 4.95 V LiNi0.5Mn1.5O4 cathode. 相似文献
35.
Zexi Liu Jing Ai Prashant Kumar Enming You Xiong Zhou Xi Liu Zhongqun Tian Petr Bou Yingying Duan Lu Han Nicholas A. Kotov Songyuan Ding Shunai Che 《Angewandte Chemie (International ed. in English)》2020,59(35):15226-15231
A surface‐enhanced Raman scattering‐chiral anisotropy (SERS‐ChA) effect is reported that combines chiral discrimination and surface Raman scattering enhancement on chiral nanostructured Au films (CNAFs) equipped in the normal Raman scattering Spectrometer. The CNAFs provided remarkably higher enhancement factors of Raman scattering (EFs) for particular enantiomers, and the SERS intensity was proportional to the enantiomeric excesses (ee) values. Except for molecules with mesomeric species, all of the tested enantiomers exhibited high SERS‐ChA asymmetry factors (g), ranging between 1.34 and 1.99 regardless of polarities, sizes, chromophores, concentrations and ee. The effect might be attributed to selective resonance coupling between the induced electric and magnetic dipoles associated with enantiomers and chiral plasmonic modes of CNAFs. 相似文献
36.
The extraordinarily rapid growth of malignant tumors depends heavily on the glucose metabolism by the pathways of glycolysis and mitochondrial oxidative phosphorylation to generate adenosine 5′-triphosphate (ATP) for maintaining cell proliferation and tumor growth. This study reports a tumor chemical suffocation therapeutic strategy by concurrently suppressing both glycolysis and mitochondrial oxidative phosphorylation (OXPHOS) via the co-deliveries of EDTA and rotenone into a glutathione (GSH)-overexpressed tumor microenvironment. EDTA is to block the glycolytic pathway through inhibiting the activity of glycolytic enzymes via the chelation of magnesium ion, a co-worker of glycolytic enzymes, despite the presence of Ca2+. Meanwhile rotenone is to inhibit the mitochondrial OXPHOS. This work provides a novel tumor suffocation strategy by the co-deliveries of glucose metabolism inhibitors, especially by de-functioning glycolytic enzymes via eliminating their co-worker magnesium.The EDTA- and Rotenone-loaded MPER nanoparticles have been synthesized to suffocate tumor cells to death through inhibiting glycolytic process and mitochondrial oxidative phosphorylation simultaneously in vitro and in vivo. 相似文献
37.
Xianping Qiu Huipeng Zhou Xiaofei Zhang Tinghua Xu Xingliang Liu Yingying Zhao 《Tetrahedron letters》2008,49(52):7446-7449
Two porphyrins with oligo-phenothiazine arms have been synthesized by a combination of Heck and Adler reaction, and their photophysical properties have been investigated by absorption and steady-state fluorescence spectroscopy. It is found that the excitation energy transfer occurs from the phenothiazine units to the porphyrin core, and that the porphyrins can emit intense red light with high fluorescent quantum yields. 相似文献
38.
39.
Double Michael addition of nitromethane to divinyl ketones: A remarkably positive effect of additive
Yongqi Yao Yingying Liu Ling Ye Feng Chen Xinying Li Zhigang Zhao Xuefeng Li 《Tetrahedron》2017,73(16):2311-2315
An efficient double Michael addition of nitromethane to divinyl ketones was established in good to high yields (75–99%). A wide range of cyclohexanones were obtained with excellent diastereocontrol (up to >20:1 dr) and enantioinduction (91–99% ee) in a one-pot fashion. The involvement of basic additive significantly enhanced the reactivity of this cascade sequence. 相似文献
40.
在MPW1PW91/6-311G(d,p)水平上优化了标题反应各驻点物种的几何构型,并在相同水平上通过频率计算和内禀反应坐标(IRC)分析对过渡态结构及连接性进行了验证.采用QCISD(T)/6-311G(d,p)方法对所有驻点及反应路径的部分选择点进行单点能校正,分别构建了CH3SO+HO2反应体系的单、三重态反应势能剖面.研究结果表明,CH3SO+HO2反应体系存在6条反应通道7条路径,优势通道(1)R→3IM→P1(CH3SOH+3O2)发生在三重态势能面上,此通道包含两条路径,其表观活化能分别为12.01和-30.04kJ?mol-1,主路径(2)R→3IM→3TS2→P1(CH3SOH+3O2)是一个无势垒氢迁移过程.利用经典过渡态理论(TST)与变分过渡态理论(CVT)并结合小曲率隧道效应模型(SCT),分别计算了主路径(2)在200~2500K温度范围内的速率常数kTST,kCVT和kCVT/SCT,在此温度区间内的表观反应速率常数三参数表达式为kCVT/SCT=4.08×10-24T3.13exp(8012.2/T)cm3imolecule-1is-1,具有负温度系数效应.速率常数计算结果显示,变分效应在计算温度段内影响较小,而量子力学隧道效应在低温段有显著影响. 相似文献