全文获取类型
收费全文 | 8876篇 |
免费 | 1659篇 |
国内免费 | 2423篇 |
专业分类
化学 | 4161篇 |
晶体学 | 35篇 |
力学 | 1404篇 |
综合类 | 143篇 |
数学 | 2446篇 |
物理学 | 4769篇 |
出版年
2023年 | 95篇 |
2022年 | 157篇 |
2021年 | 128篇 |
2020年 | 136篇 |
2019年 | 127篇 |
2018年 | 195篇 |
2017年 | 87篇 |
2016年 | 195篇 |
2015年 | 221篇 |
2014年 | 378篇 |
2013年 | 338篇 |
2012年 | 447篇 |
2011年 | 426篇 |
2010年 | 411篇 |
2009年 | 319篇 |
2008年 | 241篇 |
2007年 | 481篇 |
2006年 | 460篇 |
2005年 | 554篇 |
2004年 | 523篇 |
2003年 | 360篇 |
2002年 | 440篇 |
2001年 | 529篇 |
2000年 | 426篇 |
1999年 | 520篇 |
1998年 | 229篇 |
1997年 | 150篇 |
1996年 | 196篇 |
1995年 | 263篇 |
1994年 | 212篇 |
1993年 | 223篇 |
1992年 | 211篇 |
1991年 | 157篇 |
1990年 | 197篇 |
1989年 | 188篇 |
1988年 | 226篇 |
1987年 | 236篇 |
1986年 | 192篇 |
1985年 | 266篇 |
1984年 | 173篇 |
1983年 | 115篇 |
1982年 | 110篇 |
1981年 | 89篇 |
1975年 | 114篇 |
1959年 | 83篇 |
1958年 | 125篇 |
1957年 | 126篇 |
1956年 | 110篇 |
1955年 | 119篇 |
1954年 | 92篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
41.
Raman spectroscopy provides information on bone chemical composition and structure via widely used metrics including mineral to matrix ratio, mineral crystallinity and carbonate content, collagen crosslinking ratio and depolarization ratios. These metrics are correlated with bone material properties, such as hardness, plasticity and Young''s modulus. We review application of Raman spectroscopy to two important irradiated animalmodels: the mouse tibia, amodel for damage to cortical bone sites including the rib (breast cancer) and to healthy tissue adjacent to extremity sarcomas, and the rat mandible, a model for radiation damage in head and neck cancer radiotherapy. Longitudinal studies of irradiated mouse tibia demonstrate that radiation-induced matrix abnormalities can persist even 26 weeks postradiation. Polarized Raman spectroscopy shows formation of more ordered orientation of both mineral and collagen. At 8 weeks post-radiation, irradiated rat hemimandible exhibits transient hypermineralization, increased collagen cross-linking and decreased depolarization ratios of mineral and collagen. A standard radioprotectant, amifostine, mitigates rat mandible radiation damage, with none remaining detectable 18 weeks post-radiation. Already a powerful tool to monitor radiation damage, Raman spectroscopy may be important in development of new radiotherapy protocols and radioprotective agents. Further in vivo studies of radiation effects on the rodent models are underway, as are development of methodologies for eventual use in human subjects. 相似文献
42.
Amruthalakshmi Vijayakumar Ranjusha Rajagopalan Anoop S.Sushamakumariamma Jickson Joseph Amrutha Ajay Shantikumar V Nair Deepak Krishna M.S Avinash Balakrishnan 《天然气化学杂志》2015,(3):337-345
The present study provides detailed experimental results on the synthesis and characterization of carbonized lithium titanate spinel(LTO) composites as electrode materials for lithium ion capacitor.The LTO particles were grafted with a porous carbon layer obtained from the pyrolysis of camphor.The graphitic nature of the carbon was confirmed through Raman spectroscopy.The relative contributions from the capacitive and diffusion controlled processes underlying these electrodes were mathematically modeled.Electron transport mechanism underlying these electrodes was determined by measuring the work functions(φ) of LTO and carbon grafted LTO using ultraviolet photoelectron spectroscopy.These carbon grafted LTO composites exhibited an energy density of 330 m Wh L-1and a peak power density of 2.8 k W L-1,when employed as electrodes in coin cells with excellent cycling stability at the end of 4000 cycles. 相似文献
43.
本文用不同浓度的氢氧化钠溶液修饰天然沙粒并通过扫描电镜、静态氮吸附和红外光谱法考察了修饰天然沙粒的表面结构、比表面积和功能基团,优化了修饰条件;以修饰天然沙粒为填料制备分离富集微柱,采用FAAS着重研究了修饰沙粒对Pb2+的动态吸附及其在痕量Pb2+分离富集和测定中的应用;结果表明:天然沙粒被修饰后其表面形貌、比表面积、表面孔体积和粒径分布发生变化,表面变得更粗糙,孔体积和比表面积增大,硅羟基红外吸收峰强度也明显增强;其比表面积为12.55m2/g,平均孔(坑)径为25.29nm,平均孔体积48.04mm3/g(D<8.3 nm);在室温下,溶液pH为5.5,上样流速为1.50mL·min-1时,修饰天然沙粒对Pb2+的动态吸附量可达到32.6 mg/g,吸附率为93.6%,选用0.5mol·L-1的盐酸溶液以3.0mL·min-1流速进行洗脱,洗脱率为97%;适用于痕量Pb2+的分离富集和测定,结果令人满意。 相似文献
44.
A series of novel imidazo[1,2-b]isoxazoles 3 and their Mannich bases 4–6 were synthesized via convenient reactions. The reaction of 3-aminoisoxazole 1 with substituted phenacyl bromides 2 in dry ethanol afforded the corresponding 6-methyl-3-aryl imidazo[1,2-b]isoxazoles 3 in good yields.Compounds 3 on treatment with 37% formaline and secondary amines furnished the corresponding novel Mannich bases viz., 6-methyl-3-aryl-2-(morpholine/pyrrolidin-1-yl/piperidin-1-yl)-methyl-imidazo[1,2-b]isoxazoles 4–6. 相似文献
45.
Ying Zhang Yong-Guang Gao You-Di Shi Lian-Qian Tan Jessica S. Yue Zhong-Lin Lu 《中国化学快报》2015,26(7):894-898
A novel [12]aneN3-based BODIPY sensor 1 can be applied in the sequential recognition of Cu2 and ADP in aqueous solution and living cells with high selectivity and sensitivity 相似文献
46.
Hua-Hua Wang Yi-Yu Jiang Mian HR Mahmood Hai-Yang Liu Herman H.Y. Sung Ian D. Williams Chi K. Chang 《中国化学快报》2015,26(5):529-533
Tetrakis(alloxycarbonyl)porphyrin and its β-octafluoro-substituted derivatives were synthesized via Lindsey method and transformed to their zinc complexes.Single crystal X-ray structures of corresponding Zn(Ⅱ) porphyrins revealed that β-octafluorination will give more compactness of porphyrin moieties in the crystal structure owing to the hydrogen bonding interactions involving β-fluorine atoms.An unusual six-coordinated Zn(Ⅱ) was found via intramolecular coordination of oxygen atom of meso-substituents with central Zn(Ⅱ). 相似文献
47.
K.Vignarooban J.Lin A.Arvay S.Kolli I.Kruusenberg K.Tammeveski L.Munukutla A.M.Kannan 《催化学报》2015,(4):458-472
Low temperature fuel cells are an attractive technology for transportation and residential applica‐tions due to their quick start up and shut down capabilities. This review analyzed the current status of nanocatalysts for proton exchange membrane fuel cells and alkaline membrane fuel cells. The preparation process influences the performance of the nanocatalyst. Several synthesis methods are covered for noble and non‐noble metal catalysts on various catalyst supports including carbon nanotubes, carbon nanofibers, nanowires, and graphenes. Ex situ and in situ characterization methods like scanning electron microscopy, transmission electron microscopy, X‐ray photoelectron spectroscopy and fuel cell testing of the nanocatalysts on various supports for both proton exchange and alkaline membrane fuel cells are discussed. The accelerated durability estimate of the nanocat‐alysts, predicted by measuring changes in the electrochemically active surface area using a voltage cycling method, is considered one of the most reliable and valuable method for establishing durabil‐ity. 相似文献
48.
We report the fabrication and characterization of a magnetically recyclable Fe3O4@Nico@Ag catalyst for reduction reactions in the liquid phase. Fe3O4 is a magnetic core and nicotinic acid was used as the linker for Ag. The characterization was done with X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, vibrating sample magnetometry (VSM), and ultraviolet-visible spectroscopy. VSM measurements proved the super-paramagnetic property of the catalyst. 相似文献
49.
The high activity and selectivity of H‐Beta and H‐ZSM‐12 zeolites in the dimerization of norbornene was established.The norbornene conversion reached 100% in chlorinated paraffin and argon gas medium,with a selectivity of dimer formation of 88%–98%.Four stereo‐isomers of the bis‐2,2'‐norbornylidene structure were identified in the dimer fraction,with the(Z)‐anti‐bis‐2,2'‐norbornylidene prevailing over the others. 相似文献
50.
光催化反应发生在半导体材料的表面,材料表面的原子/电子结构直接影响光催化剂的活性或选择性。因此,发展具有特定晶面的半导体光催化剂受到各国学者的普遍关注,被认为是调控光催化材料性能的有效途径之一。自2008年yang等首次合成高表面能{001}晶面占优的锐钛矿TiO2单晶以来,控制合成暴露不同晶面TiO2晶体的研究得到了迅猛的发展,已发展了多种方法合成了具有不同晶面的TiO2晶体。研究表明,选择性地暴露特定的活性晶面能够显著地提高光催化剂的活性或者改变光催化反应的选择性。但是,含有完整晶面构型的TiO2单晶样品的颗粒尺寸一般都较大,通常为几微米,因而显著增加了光生载流子传输与分离的难度,并且导致材料较小的比表面积,限制了对光催化活性的进一步提高。能否在合成含特定晶面单晶的同时增加多孔结构成为有效解决这一问题的关键。最近, Crossland等采用晶种模板法成功合成了介孔的锐钛矿TiO2单晶,并且通过光电器件研究证实了采用该思路可进一步提高材料的光电性能。金红石TiO2在光催化全分解水方面具有独特的优势,然而关于多孔单晶金红石TiO2的研究相对较少,尤其是合成热力学不稳定的高表面能{111}晶面完全暴露的多孔金红石单晶面临较大的技术挑战因而一直未见文献报道。本文利用晶种模板法,以TiCl4溶液为含Ti前驱体、NaF为形貌控制剂、采用水热处理制备出不同比例{111}晶面的介孔金红石单晶。我们前期工作表明, NaF可作为形貌控制剂合成低表面能{110)晶面占优的介孔金红石单晶。本文发现,通过改变NaF的添加量,可有效调变{111}/{110}晶面比例,最终合成完全暴露{111}高表面能的介孔金红石TiO2单晶。扫描电镜结果显示,当添加20 mg NaF时,合成{110}占优的具有高长径比的介孔晶体;当NaF用量增加到40 mg时{110}晶面进一步缩短;至80 mg时则制备出{111})高能面完全暴露的金红石TiO2晶体。值得注意的是,对比研究表明,不采用模板合成了与多孔晶体完全相对应的不同{111}/(110}晶面比例的实心金红石晶体。透射电镜及选区电子衍射以及结合X射线衍射进一步证实,多孔的金红石TiO2晶体与实心金红石单晶均都为单晶结构,孔结构贯穿于样品内部且具有较高的晶面结晶性。氮气吸附实验发现,虽然三个不同晶面比例介孔金红石单晶样品间的形貌具有显著的差异,但比表面积非常相近(分别为24,25,28 m2/g),孔径也都为50 nm左右,该值与所用SiO2模板球的直径以及TEM观察结果相一致。光催化产氢性能结果表明,选择性的暴露活性晶面显著提高了光催化活性,仅含高能面{111}的介孔金红石单晶样品具有最高的产氢速率(约800μmol h–1 g–1),比常规{110}晶面占优的介孔单晶样品速率提高了约一倍。尤其比实心单晶样品的产氢速率提高了至少一个数量级,这应归结于介孔结构特性所导致的表面反应活性位增加、电子传输距离缩短以及光吸收增强协同作用的结果。 相似文献