全文获取类型
收费全文 | 3003篇 |
免费 | 425篇 |
国内免费 | 244篇 |
专业分类
化学 | 3137篇 |
力学 | 34篇 |
综合类 | 9篇 |
数学 | 188篇 |
物理学 | 304篇 |
出版年
2024年 | 13篇 |
2023年 | 103篇 |
2022年 | 186篇 |
2021年 | 243篇 |
2020年 | 234篇 |
2019年 | 177篇 |
2018年 | 133篇 |
2017年 | 133篇 |
2016年 | 228篇 |
2015年 | 201篇 |
2014年 | 241篇 |
2013年 | 284篇 |
2012年 | 196篇 |
2011年 | 215篇 |
2010年 | 139篇 |
2009年 | 172篇 |
2008年 | 165篇 |
2007年 | 159篇 |
2006年 | 88篇 |
2005年 | 93篇 |
2004年 | 61篇 |
2003年 | 53篇 |
2002年 | 32篇 |
2001年 | 20篇 |
2000年 | 18篇 |
1999年 | 26篇 |
1998年 | 11篇 |
1997年 | 5篇 |
1996年 | 7篇 |
1995年 | 7篇 |
1994年 | 7篇 |
1993年 | 1篇 |
1992年 | 6篇 |
1991年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有3672条查询结果,搜索用时 15 毫秒
1.
Dmitry S. Zimnitsky Tatiana L. Yurkshtovich Pavel M. Bychkovsky 《Journal of polymer science. Part A, Polymer chemistry》2004,42(19):4785-4791
Samples of oxidized cellulose (OC) with various carboxyl contents and degrees of crystallinity were obtained by the oxidation of native and mercerized cellulose with a solution of nitrogen(IV) oxide in CCl4. A detailed characterization of these OC samples was performed. The effect of oxidation conditions (concentration of N2O4 in the solution and oxidation time) and starting cellulose material on OC characteristics (carboxyl, carbonyl and nitrogen content, degree of crystallinity and polymerization, surface area and swelling, and acidic properties) was investigated. Reactivity in the oxidation process was higher in mercerized cellulose than in native cellulose. The action of dilute solutions (10–15%) of N2O4 did not affect the degree of crystallinity of cellulose samples. Under these conditions, the oxidation took place mainly in amorphous regions and on the surface of crystallites. Oxidation in a concentrated (40%) N2O4 solution led to the destruction of crystallites, which increased the surface area and swelling of cellulose in water. The surface area and the swelling of OC samples increased with a decrease in the index of crystallinity. The acidic properties of OC were shown to increase with an increase of swelling in water. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4785–4791, 2004 相似文献
2.
A nanoscale
multivalent platinum drug based on a poly(amidoamine) [PAMAM] dendrimer (generation
4.5, carboxylate surface) has been synthesized and fully characterized using
a variety of spectroscopic, chromatographic and thermal methods. Treatment
of the dendrimer with an aqueous solution containing an excess diaquo(cis-1,2-diaminocyclohexane)platinum(II) produces
a conjugate containing approximately forty (diaminocyclohexane)platinum(II)
moieties at the surface of the dendrimer. This material undergoes smooth two-stage
thermal decomposition to provide residual platinum oxide reflecting the platinum
loading in the drug. 相似文献
3.
Xiao Huang Bishwa Ranjan Nayak Tao Lu Lowe 《Journal of polymer science. Part A, Polymer chemistry》2004,42(20):5054-5066
A series of novel multifunctional hydrogels that combined the merits of both thermoresponsive and biodegradable polymeric materials were designed, synthesized, and characterized. The hydrogels were copolymeric networks composed of N‐isopropylacrylamide (NIPAAM) as a thermoresponsive component, poly(L‐lactic acid) (PLLA) as a hydrolytically degradable and hydrophobic component, and dextran as an enzymatically degradable and hydrophilic component. The chemical structures of the hydrogels were characterized by an attenuated total reflection–Fourier transform infrared spectroscopy (ATR–FTIR) technique. The hydrogels were thermoresponsive, showing a lower critical solution temperature (LCST) at approximately 32 °C, and their swelling properties strongly depended on temperature changes, the balance of the hydrophilic/hydrophobic components, and the degradation of the PLLA component. The degradation of the hydrogels caused by hydrolytic cleavage of ester bonds in the PLLA component was faster at 25 °C below the LCST than at 37 °C above the LCST, determined by the ATR–FTIR technique. Due to their multifunctional properties, the designed hydrogels show great potential for biomedical applications, including drug delivery and tissue engineering. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5054–5066, 2004 相似文献
4.
Previous work carried out in our laboratories has focused on the formation and investigation of a dextran and concanavalin A (con A) based gel, which has the ability to alter its conformational structure in the presence and absence of free and terminal glucoses such that a gel–sol phase transition occurs. Here we report the diffusion and rheological investigations in to the effects of the addition of insulin and varyingconcentrations of magnesium chloride hexahydrate (Mg2Cl26H2O) at 20 and 37 °C. Rheological examination of glucose-sensitive (dextran-con A) gels were conducted using a cone and plate viscometer used in continual rotation and oscillatory modes. The results are interpreted in terms of the structure of the gel network and suggest rheological assessment provides an effective method of assessing the properties of gel systems. The subsequent testing of such formulations in in-vitro diffusion experiments revealed a reduction in the rate of diffusivity in the insulin marker, poly R-478 dye. The performance of this self-regulating drug delivery system has been examined and the addition of insulin and magnesium chloride may alter the way in which the gel operates as a drug delivery device and in the delivery of insulin. This may have implications for other ligands. 相似文献
5.
温度及pH敏感的树枝状高分子衍生物合成及药物控制释放研究 总被引:3,自引:0,他引:3
对合成的系列聚酰胺-胺型(PAMAM)树枝状高分子进行端基的羟基化和氯乙酰化两步修饰,使PAMAM最外层接上烷基氯.以修饰产物为引发剂,通过原子转移自由基引发甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)聚合得到树枝状PAMAM高分子衍生物,并对其结构用FTIR、1H-NMR和粒径分析进行了表征.紫外可见分光光度仪测定证实此高分子具有温度及pH敏感性.通过对小分子药物控制释放研究表明,此树枝状高分子衍生物通过环境pH值可有效地控制小分子药物的释放. 相似文献
6.
无机层状复合氢氧化物中顺铂-DNA模型分子的选择性插入 总被引:5,自引:0,他引:5
药物分子的选择性包裹和控制释放是药物研究领域中具有挑战性的研究方向。本文研究表明:顺铂-DNA模型分子cis-[Pt(NH3)2(5′-GMP)2](5′-GMP 5′-单磷酸鸟苷)可插入无机层状复合氢氧化物[Zn0.68Al0.32(OH)2](NO3)0.32·mH2O。但另一种层状复合氢氧化物[LiAl2(OH)6]Cl·H2O由于其阳离子层中正电荷密度较高、阳离子层与层间阴离子之间静电作用较强,因而顺铂-DNA模型分子不能通过离子交换方式插入其层间。光谱数据证实插入层间的顺铂-DNA模型分子结构不变。这可能为铂-DNA分子的传递提供新的方法。 相似文献
7.
Gary H. Van Domeselaar Glen S. Kwon Lena C. Andrew David S. Wishart 《Colloids and surfaces. B, Biointerfaces》2003,30(4):323-334
This work describes a simple, versatile solid-phase peptide-synthesis (SPPS) method for preparing micelle-forming poly(ethylene oxide)-block-peptide block copolymers for drug delivery. To demonstrate its utility, this SPPS method was used to construct two series of micelle-forming block copolymers (one of constant core-composition and variable length; the other of constant core length and variable composition). The block copolymers were then used to study in detail the effect of size and composition on micellization. The various block copolymers were prepared by a combination of SPPS for the peptide block, followed by solution–phase conjugation of the peptide block with a proprionic acid derivative of poly(ethylene oxide) (PEO) to form the PEO-b-peptide block copolymer. The composition of each block component was characterized by mass spectrometry (MALDI and ES-MS). Block copolymer compositions were characterized by 1H NMR. All the block copolymers were found to form micelles as judged by transmission electron microscopy (TEM) and light scattering analysis. To demonstrate their potential as drug delivery systems, micelles prepared from one member of the PEO-b-peptide block copolymer series were physically loaded with the anticancer drug doxorubicin (DOX). Micelle static and dynamic stability were found to correlate strongly with micelle core length. In contrast, these same micellization properties appear to be a complex function of core composition, and no clear trends could be identified from among the set of compositionally varying, fixed length block copolymer micelles. We conclude that SPPS can be used to construct biocompatible block copolymers with well-defined core lengths and compositions, which in turn can be used to study and to tailor the behavior of block copolymer micelles. 相似文献
8.
This paper describes the synthesis of three neutral water soluble poly(amidoamine) (PAMAM) dendrimer derivatives. The ability of the two larger dendrimers to bind small acidic hydrophobic molecules is reported. Spectroscopic data and pH behaviour suggested that the acidic hydrophobes were forming stable ion pairs with the dendrimer's internal, basic tertiary nitrogens. With respect to forming 1:1 and 2:1 substrate/dendrimer complexes, both of the larger dendrimers were equally efficient at binding. All dendrimer/substrate complexes were completely miscible with water in all proportions (i.e. infinitely water soluble). When the bound substrates are drug moieties, then the resulting complexes could be considered as potential drug delivery systems. Flow calorimetry demonstrated that the dendrimers were able to release their hydrophobic guests when in contact with a biological cell. 相似文献
9.
The drug-loaded alginate/poly-L-arginine/chitosan ternary complex microcapsules were prepared by mixing method, absorption method and the combined method of mixing and absorption, respectively. The effect of drug-loading methods on drug load, the encapsulation efficiency and the release properties of the complex microcapsules were investigated. The results showed that the absorption process is a dominating factor to greatly increase the drug load of Hb into microcapsules. Upon loading Hb into microcapsules by combined method of mixing and absorption, the drug load (19.9%) is up to the maximum value, and the encapsulation efficiency is 93.8%. Moreover, the drug release is a zero-order kinetics process for the ternary complex microcapsules made by mixing. For the complex microcapsules made by absorption, the drug release is a first-order kinetics. However, for the complex microcapsules made by combining the mixing and the absorption, the drug release obeys a first-order kinetics during the first eighteen hours, changing afterwards to a zero-order kinetics process. Effect of drug-loading methods on drug load and encapsulation efficiency of alginate/poly-L-arginine/chitosan ternary complex microcapsules. 相似文献
10.