全文获取类型
收费全文 | 20713篇 |
免费 | 3415篇 |
国内免费 | 2296篇 |
专业分类
化学 | 14740篇 |
晶体学 | 260篇 |
力学 | 1257篇 |
综合类 | 187篇 |
数学 | 2069篇 |
物理学 | 7911篇 |
出版年
2024年 | 76篇 |
2023年 | 468篇 |
2022年 | 671篇 |
2021年 | 757篇 |
2020年 | 818篇 |
2019年 | 792篇 |
2018年 | 666篇 |
2017年 | 624篇 |
2016年 | 975篇 |
2015年 | 981篇 |
2014年 | 1112篇 |
2013年 | 1446篇 |
2012年 | 1861篇 |
2011年 | 1895篇 |
2010年 | 1251篇 |
2009年 | 1107篇 |
2008年 | 1301篇 |
2007年 | 1282篇 |
2006年 | 1129篇 |
2005年 | 1007篇 |
2004年 | 720篇 |
2003年 | 628篇 |
2002年 | 568篇 |
2001年 | 430篇 |
2000年 | 413篇 |
1999年 | 471篇 |
1998年 | 355篇 |
1997年 | 370篇 |
1996年 | 312篇 |
1995年 | 296篇 |
1994年 | 302篇 |
1993年 | 246篇 |
1992年 | 196篇 |
1991年 | 198篇 |
1990年 | 177篇 |
1989年 | 112篇 |
1988年 | 87篇 |
1987年 | 89篇 |
1986年 | 60篇 |
1985年 | 44篇 |
1984年 | 43篇 |
1983年 | 24篇 |
1982年 | 25篇 |
1981年 | 18篇 |
1980年 | 14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
181.
Michael A. Brook Jianxiong Jiang Philippa Heritage Brian Underdown Mark R. McDermott 《Colloids and surfaces. B, Biointerfaces》1997,9(6):391-295
Silicone-coated starch/protein (human serum albumin, HSA) microparticles were prepared by precipitation of a starch/HSA/DMSO/water (water-in-oil) emulsion into acetone containing a silicone: the silicone polymer was either unfunctionalized (SiMe3 terminated, PDMS) or functionalized at its termini with Si(OEt)3 groups (TES-PDMS). The microparticles of approximate diameter 2–7 μm were highly hydrophobic with advancing contact angles 115°. Over several minutes, however, the contact angle decreased to ca. 40–70°. Soxhlet extraction with water led to degradation of the microparticles, irrespective of the nature of their silicone coating, as evidenced by release of the protein from them. Intraperitoneal (IP) or gastric administration of the two different particles to mice, however, showed a clear difference between the two silicones. The microparticles coated with either PDMS or TES-PDMS led to very different immune responses. Oral administration of the microparticles prepared with functionalized silicone elicited a significant production of antibodies, whereas the particles prepared with the unfunctionalized silicone (PDMS) were only weakly active. By contrast, the IP results demonstrated that particles coated with PDMS elicited an immune response that was established much more rapidly than with the particles modified with TES-PDMS. It is proposed that the TES-PDMS forms a physically adhering film or covalent bond to the protein molecules, which serves to protect the microparticle from biological degradation in the gut and/or facilitates the microparticle/protein interaction with the immune system. 相似文献
182.
Two new pyrrolizidines named lankongensisine A (1), B (2) were isolated from the roots of Ligularia lankongensis collected in Lijiang, Yunnan, and their structures were established by spectroscopic analysis. 相似文献
183.
Two new layered transition metal oxalatophosphates, (H(3)TREN)[M(2)(HPO(4))(C(2)O(4))(2.5)].3H(2)O (M = Mn(II) and Fe(II)), have been synthesized by hydrothermal methods in the presence of a structure-directing organic amine, tris(2-aminoethyl)amine, and characterized by single-crystal X-ray diffraction and magnetic susceptibility. They are the first metal oxalatophosphates which adopt a two-dimensional honeycomb structure with the organic cations and water molecules intercalated in between. Within a layer, there are 12-membered pores made from 6 Mn, 1 phosphate, and 5 oxalate units. Measurements of field dependence of magnetization and variable-temperature susceptibilities under different fields were performed on a polycrystalline sample of the manganese compound. The results indicate a phase transition from a paramagnetic to an antiferromagnetic coupled state at about 12 K. Crystal data for the manganese compound follow: triclinic, space group Ponemacr; (No. 2), a = 8.8385(6) A, b = 9.0586(6) A, c = 16.020(1) A, alpha = 77.616(1) degrees, beta = 83.359(1) degrees, gamma = 68.251(1) degrees, and Z = 2. Crystal data for the iron compound are the same as those for the manganese compound except a = 8.7776(9) A, b = 8.9257(9) A, c = 15.884(2) A, alpha = 78.630(2) degrees, beta = 84.018(2) degrees, and gamma = 67.372(2) degrees. 相似文献
184.
用两种方法分别将四足配体铽配合物[TbL(NO3)]^2+和[TbL]^3+插层组装到了蒙脱土(MT)层板间,制备出超分子复合发光材料[TbL(NO3)^2+-MT和[TbL]^3+-MT。方法一:通过离子交换反应让配离子[TbL(NO3)]^2+取代钠+基蒙脱土(Na-MT)中的Na^+离子,插层组装到蒙脱土层板间。方法二:用配体L与铽基蒙脱土(Tb-MT)反应,使配体插入蒙脱土层板间与Tb^3+离子配位。用元素分析、XRD,FT-IR,UV-vis和热分析对材料进行了表征,并对其荧光性质进行了研究。结果表明,复合材料保持了蒙脱土良好的层柱结构特征,其层间距d001值与插层配离予的直径吻合较好,配离子以单层形式分布于蒙脱土层板间,复合材料中配合物的热稳定性有明显提高。在紫外光激发下,复合材料发出较强的Tb^3+特征荧光,其发射光谱与相应配合物的发射光谱很相似;复合材料中配合物的相对荧光强度较相应纯配合物有明显提高。荧光寿命较长;配合物的激发波长向可见光区发生位移,说明插层组装实现了对配合物激发波长的调制作用。 相似文献
185.
本文研究了在表面活性剂存在性,铝与溴代二甲氨基苯基荧光酮的显色反应。在弱酸性介质中,Al^3+BDMAF-CTMAB三元配合物在水浴加热至70℃-80℃时形成,其最大吸收波长为577nm,Al^3+:BDMAF=1:2,表观摩尔吸光系数为1.34×10^5L.mol^-1.cm^-1,表观稳定常数为7.4×10^5。在PH9.5-10.5的氨性缓冲介质中,Al^3+-F^--BDMAF-非离子表面 相似文献
186.
187.
188.
Guang-Ming Yang Peng Cheng Dai-Zheng Liao Zong-Hui Jiang Shi-Ping Yan Geng-Lin Wang Xin-Kan Yao Hong-Gen Wang 《Journal of Cluster Science》1998,9(4):465-471
The preparation, magnetic properties, and crystal structure of [(salen)Cu]4[(salen)Fe(H2O)2]2(ClO4)2 via hydrogen bonding are described [salen=N,N-ethylenebis (salicylideneiminate)]. Crystals are triclinic, of space group
, with cell constants a=12.853(3), b=13.921(3), c=14.251(3) Å, =68.68(3)°, =87.86(3)°, =86.82(3)°, and Z=1. The structure was solved and refined to R=0.064 and R=0.068. The structure comprises the hexanuclear units which result from the linking of four mononuclear fragments [(salen)Cu] and two mononuclear fragment [(salen)Fe(H2O)]+, through Cu -O H -O -Fe -O -H O -Cu hydrogen bonds of coordinating H2O. In this complex, FeIII ions are in almost square-planar surroundings. The temperature dependences of the magnetic susceptibilities of the complex have been studied in the 4.2–300 K range, indicating the presence of an antiferromagnetic interactions between metal ions. 相似文献
189.
两种结构钼磷酸的催化氧化行为 总被引:11,自引:0,他引:11
考察了Dawson与Keggin结构钼磷酸的催化氧化行为,并与结构特性进行了关联,结果发现,Dawson结构的杂多酸对氧化脱氢及插入氧反应均有更高的活性。 相似文献
190.
Development of high-performance liquid chromatographic fingerprints for distinguishing Chinese Angelica from related umbelliferae herbs 总被引:6,自引:0,他引:6
Lu GH Chan K Liang YZ Leung K Chan CL Jiang ZH Zhao ZZ 《Journal of chromatography. A》2005,1073(1-2):383-392
A high-performance liquid chromatographic (HPLC) fingerprint of Chinese Angelica (CA) was developed basing on the consistent chromatograms of 40 CA samples (Angelica sinensis (Oliv.) Diels). The unique properties of this HPLC fingerprints were validated by analyzing 13 related herbs including 4 Japanese Angelicae Root samples (JA, A. acutiloba Kitagawa and A. acutiloba Kitagawa var. sugiyame Hikino), 6 Szechwan Lovage Rhizome samples (SL, Ligusticum chuanxiong Hort.) and 3 Cnidium Rhizome samples (CR, Cnidium officinale Makino). Both correlation coefficients of similarity in chromatograms and relative peak areas of characteristic compounds were calculated for quantitative expression of the HPLC fingerprints. The amount of senkyunolide A in CA was less than 30-fold of that in SL and CR samples, which was used as a chemical marker to distinguish them. JA was easily distinguished from CA, SL and CR based on either chromatographic patterns or the amount of coniferyl ferulate. No obvious difference between SL and CR chromatograms except the relative amount of some compounds, suggesting that SL and CR might have very close relationship in terms of chemotaxonomy. Ferulic acid and Z-ligustilide were unequivocally determined whilst senkyunolide I, senkyunolide H, coniferyl ferulate, senkyunolide A, butylphthalide, E-ligustilide, E-butylidenephthalide, Z-butylidenephthalide and levistolide A were tentatively identified in chromatograms based on their atmospheric pressure chemical ionization (APCI) MS data and the comparison of their UV spectra with those published in literatures. 相似文献