全文获取类型
收费全文 | 26960篇 |
免费 | 4291篇 |
国内免费 | 4046篇 |
专业分类
化学 | 20648篇 |
晶体学 | 426篇 |
力学 | 1315篇 |
综合类 | 296篇 |
数学 | 2952篇 |
物理学 | 9660篇 |
出版年
2024年 | 94篇 |
2023年 | 490篇 |
2022年 | 932篇 |
2021年 | 1020篇 |
2020年 | 1065篇 |
2019年 | 1128篇 |
2018年 | 947篇 |
2017年 | 989篇 |
2016年 | 1294篇 |
2015年 | 1336篇 |
2014年 | 1671篇 |
2013年 | 2075篇 |
2012年 | 2488篇 |
2011年 | 2555篇 |
2010年 | 1953篇 |
2009年 | 1837篇 |
2008年 | 1950篇 |
2007年 | 1804篇 |
2006年 | 1686篇 |
2005年 | 1346篇 |
2004年 | 987篇 |
2003年 | 786篇 |
2002年 | 740篇 |
2001年 | 652篇 |
2000年 | 574篇 |
1999年 | 481篇 |
1998年 | 355篇 |
1997年 | 312篇 |
1996年 | 266篇 |
1995年 | 254篇 |
1994年 | 233篇 |
1993年 | 168篇 |
1992年 | 146篇 |
1991年 | 135篇 |
1990年 | 121篇 |
1989年 | 89篇 |
1988年 | 73篇 |
1987年 | 53篇 |
1986年 | 61篇 |
1985年 | 49篇 |
1984年 | 19篇 |
1983年 | 18篇 |
1982年 | 19篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 3篇 |
1971年 | 4篇 |
1957年 | 4篇 |
1936年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
961.
Qingqing Shao Shujiang Tu Chunmei Li Longji Cao Dianxiang Zhou Bo Jiang Yan Zhang Wenjuan Hao Qian Wang 《Journal of heterocyclic chemistry》2008,45(2):411-416
Triaza‐benzo[b]fluoren‐6‐one derivatives were synthesized via the three‐component reaction of aldehyde, cyclohexane‐1,3‐dione compound and 2‐aminobenzimidazole in water under microwave irradiation. The new protocol has the advantages of excellent yield, low cost, reduced environment impact, wide scope and convenient procedure. 相似文献
962.
Yan Song Xiao-Qing Yu Su Chen 《Journal of polymer science. Part A, Polymer chemistry》2024,62(3):447-462
Fiber-spinning chemistry (FSC) has emerged as a promising micro-reaction platform due to its high-specific surface area, efficient heat and mass transfer, and enhanced reaction rate. The FSC strategy employs spinning fibers as microreactors, lessening the emissions of volatile organic compounds (VOCs), and realizing the design of micro/nanoscale fibers and the synthesis of nanomaterials. In this review, we highlight the latest advancements in FSC in respect of preparation mechanisms and technical advantages. Various FSC strategies, including microfluidic spinning, electro-microfluidic spinning (EMS), and microfluidic blow spinning (MBS) are emphasized. In particular, the regulation of microfluidic chips in the FSC process is introduced. Additionally, the application of the FSC strategy is summarized in the synthesis of fluorescent nanomaterials, nonweaving for multidimensional fibers, and all-weather smart textiles. Finally, the advanced progress and future perspectives are discussed. Overall, this review will provide theoretical guidance for the design of well-defined micro/nanoscale fibers based on the FSC platforms. 相似文献
963.
超大硅胺基取代的低价锗化合物可以构建新颖的化学结构,提供有学术价值的新发现。二配位的超大硅胺基氯锗宾Ge(N(SiiPr3)2)Cl (1)具有空的4p轨道和孤电子对。针对这2个特点,研究了化合物1的热构型转换和菲醌氧化加成反应。1的温热分解生成了立方四锗卡宾 Ge4(NSiiPr3)4 (2),与菲醌(L)定量氧化加成生成了胺基一氯菲二酚合锗(Ⅳ):[Ge(N(SiiPr3)2)(L)Cl] (3)。表征了2个产物的单晶结构与组成。四锗卡宾2本质上是锗异腈的四聚体,分子呈现出畸变的立方体构型,4个Ge原子和4个N原子构成了中心立方体的 8个顶点。其中 Ge—N键长为 0.203 6(3) nm,N—Ge—N与 Ge—N—Ge的键角分别为 85.51(18)°和94.32(16)°,立方体的侧面接近平行四边形。理论计算首次揭示了四锗卡宾2的成键面貌。自然键轨道(NBO)给出Ge4N4骨架上的20个分子轨道。轨道定域化的计算结果完好地呈现出4对Ge孤对电子、12个Ge—N键和4个Si—N键的定域轨道,能量分别为-12.22、-15.12 和-20.12 eV。Ge 孤对电子主要保留了 4s 电子的特性,而 Ge—N 键主要由 N 的 2s 轨道(18.4%)和 2p 轨道(71.3%)、Ge的4s轨道(0.75%)和4p轨道(9.43%)综合贡献形成。在化合物3的分子中,GeⅣ采取sp3杂化,由于空间位阻与非对称配位,与另外4个配位原子形成非对称四面体构型。 相似文献
964.
Yan Jin Qiu-Chen Peng Jing-Wen Xie Prof. Dr. Kai Li Prof. Dr. Shuang-Quan Zang 《Angewandte Chemie (International ed. in English)》2023,62(19):e202301000
In this study, a pair of chiral copper(I) cluster-assembled materials (R/S- 2 ) was prepared, exhibiting unique photo-response characteristics with a concentration-wavelength correlation property in DMSO solution. By the combination of R/S- 2 with a polymethyl methacrylate (PMMA) matrix, the first photo-activated circularly polarized luminescence (CPL) film was developed, the CPL signal (glum=9×10−3) of which could be induced by UV light irradiation. Moreover, the film exhibited a reversible photo-response and extremely good fatigue resistance. Mechanism study revealed that the photo-response properties of the R/S- 2 solution and film are attributed to the aggregation-induced emission (AIE) characteristics of R/S- 2 and a photo-induced deoxygenation process. This study enriches the types of luminescent cluster-assembled molecules and provides a new strategy for the construction of metal cluster-based stimuli-responsive composite materials. 相似文献
965.
Dr. Yunxiang Li Dr. Yan Guo Dr. Deyan Luan Prof. Xiaojun Gu Prof. Xiong Wen Lou 《Angewandte Chemie (International ed. in English)》2023,62(44):e202310847
Developing highly efficient catalytic sites for O2 reduction to H2O2, while ensuring the fast injection of energetic electrons into these sites, is crucial for artificial H2O2 photosynthesis but remains challenging. Herein, we report a strongly coupled hybrid photocatalyst comprising polymeric carbon nitride (CN) and a two-dimensional conductive Zn-containing metal–organic framework (Zn-MOF) (denoted as CN/Zn-MOF(lc)/400; lc, low crystallinity; 400, annealing temperature in °C), in which the catalytic capability of Zn-MOF(lc) for H2O2 production is unlocked by the annealing-induced effects. As revealed by experimental and theoretical calculation results, the Zn sites coordinated to four O (Zn-O4) in Zn-MOF(lc) are thermally activated to a relatively electron-rich state due to the annealing-induced local structure shrinkage, which favors the formation of a key *OOH intermediate of 2e− O2 reduction on these sites. Moreover, the annealing treatment facilitates the photoelectron migration from the CN photocatalyst to the Zn-MOF(lc) catalytic unit. As a result, the optimized catalyst exhibits dramatically enhanced H2O2 production activity and excellent stability under visible light irradiation. 相似文献
966.
As a liquid‐liquid partition chromatography, counter‐current chromatography has advantages in large sample loading capacity without irreversible adsorption, which has been widely applied in separation and purification fields. The main factors, including partition coefficient, two‐phase solvent systems, apparatus, and operating parameters greatly affect the separation process of counter‐current chromatography. To promote the applications of counter‐current chromatography, it is essential to develop theoretical research to master the principles of counter‐current chromatographic separations so as to achieve predictions before laborious trials. In this article, recent progress about separation prediction methods are reviewed from a point of the steady and unsteady state of the mass transfer process of counter‐current chromatography and its mass transfer characteristics, and then it is divided into three aspects: prediction of partition coefficient, modeling the thermodynamic process of counter‐current chromatography, and modeling the dynamic process of counter‐current chromatography. 相似文献
967.
Dr. Pengyang Xin Linqi Xu Wenpei Dong Linlin Mao Prof. Jingjing Guo Dr. Jingjing Bi Dr. Shouwei Zhang Yan Pei Prof. Chang-Po Chen 《Angewandte Chemie (International ed. in English)》2023,62(8):e202217859
Different types of natural K+ channels share similar core modules and cation permeability characteristics. In this study, we have developed novel artificial K+ channels by rebuilding the core modules of natural K+ channels in artificial systems. All the channels displayed high selectivity for K+ over Na+ and exhibited a selectivity sequence of K+≈Rb+ during the transport process, which is highly consistent with the cation permeability characteristics of natural K+ channels. More importantly, these artificial channels could be efficiently inserted into cell membranes and mediate the transmembrane transport of K+, disrupting the cellular K+ homeostasis and eventually triggering the apoptosis of cells. These findings demonstrate that, by rebuilding the core modules of natural K+ channels in artificial systems, the structures, transport behaviors, and physiological functions of natural K+ channels can be mimicked in synthetic channels. 相似文献
968.
Chun-Hua Yan 《中国科学:化学(英文版)》2021,(2):169-170
During the past decade,the power conversion efficiencies(PCEs)of organic-inorganic hybrid perovskite solar cells(PSCs)have exceeded 25%[1],which is expected to be one of the candidates for the next generation of thin-film photovoltaic technology.Fundamentally speaking,the performance of PSCs mainly depends on the light absorption capacity,defect passivation and photo-induced exciton separation and extraction of perovskite films.Under the light illumination,photo-induced excitons were separated and extracted by the built-in electric field of PSCs. 相似文献
969.
Liangcong Hu Xudong Xie Hang Xue Tiantian Wang Adriana C. Panayi Ze Lin Yuan Xiong Faqi Cao Chengcheng Yan Lang Chen Peng Cheng Kangkang Zha Yun Sun Guodong Liu Chenyan Yu Yiqiang Hu Ranyang Tao Wu Zhou Bobin Mi Guohui Liu 《Experimental & molecular medicine》2022,54(7):961
MicroRNAs (miRNAs) broadly regulate normal biological functions of bone and the progression of fracture healing and osteoporosis. Recently, it has been reported that miR-1224-5p in fracture plasma is a potential therapy for osteogenesis. To investigate the roles of miR-1224-5p and the Rap1 signaling pathway in fracture healing and osteoporosis development and progression, we used BMMs, BMSCs, and skull osteoblast precursor cells for in vitro osteogenesis and osteoclastogenesis studies. Osteoblastogenesis and osteoclastogenesis were detected by ALP, ARS, and TRAP staining and bone slice resorption pit assays. The miR-1224-5p target gene was assessed by siRNA-mediated target gene knockdown and luciferase reporter assays. To explore the Rap1 pathway, we performed high-throughput sequencing, western blotting, RT-PCR, chromatin immunoprecipitation assays and immunohistochemical staining. In vivo, bone healing was judged by the cortical femoral defect, cranial bone defect and femoral fracture models. Progression of osteoporosis was evaluated by an ovariectomy model and an aged osteoporosis model. We discovered that the expression of miR-1224-5p was positively correlated with fracture healing progression. Moreover, in vitro, overexpression of miR-1224-5p slowed Rankl-induced osteoclast differentiation and promoted osteoblast differentiation via the Rap1-signaling pathway by targeting ADCY2. In addition, in vivo overexpression of miR-1224-5p significantly promoted fracture healing and ameliorated the progression of osteoporosis caused by estrogen deficiency or aging. Furthermore, knockdown of miRNA-1224-5p inhibited bone regeneration in mice and accelerated the progression of osteoporosis in elderly mice. Taken together, these results identify miR-1224-5p as a key bone osteogenic regulator, which may be a potential therapeutic target for osteoporosis and fracture nonunion.Subject terms: Translational research, Cell signalling 相似文献
970.
Xinhua Zhou Xu Chen Liping Fan Huirong Dong Yan Ren Xiangming Chen 《Molecules (Basel, Switzerland)》2022,27(23)
Diterpenoids are considered the major bioactive components in Scutellaria barbata to treat cancer and inflammation, but few comprehensive profiling studies of diterpenoids have been reported. Herein, a stepwise diagnostic product ions (DPIs) filtering strategy for efficient and targeted profiling of diterpenoids in Scutellaria barbata was developed using UHPLC-Q-Exactive-Orbitrap-MS. After UHPLC-HRMS/MS analysis of six diterpenoid reference standards, fragmentation behaviors of these references were studied to provide DPIs. Then, stepwise DPIs filtering aimed to reduce the potential interferences of matrix ions and achieve more chromatographic peaks was conducted to rapidly screen the diterpenoids. The results demonstrated that stepwise DPIs were capable of simplifying the workload in data post-processing and the effective acquisition of low abundance compounds. Subsequently, DPIs and MS/MS fragment patterns were adopted to identify the targeted diterpenoids. As a result, 381 diterpenoids were unambiguously or tentatively identified, while 141 of them with completely new molecular weights were potential new diterpenoids for Scutellaria barbata. These results demonstrate that the developed stepwise DPIs filtering method could be employed as an efficient, reliable, and valuable strategy to screen and identify the diterpenoid profile in Scutellaria barbata. This might accelerate and simplify target constituent profiling from traditional Chinese medicine (TCM) extracts. 相似文献