首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   695篇
  免费   42篇
  国内免费   22篇
化学   729篇
晶体学   1篇
力学   5篇
综合类   2篇
数学   1篇
物理学   21篇
  2023年   4篇
  2022年   8篇
  2021年   11篇
  2020年   14篇
  2019年   28篇
  2018年   17篇
  2017年   20篇
  2016年   31篇
  2015年   26篇
  2014年   32篇
  2013年   56篇
  2012年   40篇
  2011年   35篇
  2010年   42篇
  2009年   47篇
  2008年   55篇
  2007年   47篇
  2006年   43篇
  2005年   48篇
  2004年   44篇
  2003年   36篇
  2002年   32篇
  2001年   15篇
  2000年   4篇
  1999年   4篇
  1998年   4篇
  1997年   2篇
  1996年   1篇
  1995年   2篇
  1994年   5篇
  1993年   4篇
  1992年   1篇
  1984年   1篇
排序方式: 共有759条查询结果,搜索用时 31 毫秒
1.
In order to reduce the pollutants of environment and electromagnetic waves, environment friendly polymer foams with outstanding electromagnetic interference shielding are imminently required. In this paper, a kind of electromagnetic shielding, biodegradable nanocomposite foam was fabricated by blending poly (butylene succinate) (PBS) with carbon nanotubes (CNTs) followed by foaming with supercritical CO2. The crystallization temperature and melting temperature of PBS/CNTs nanocomposites with 4 wt % of CNTs increased remarkably by 6 °C and 3.1 °C compared with that of pure PBS and a double crystal melting peak of various PBS samples appeared in DSC curves. Increasing the CNT content from 0 to 4 wt % leads to an increase of approximately 3 orders of magnitude in storage modulus and nearly 9 orders of magnitude in enhancement of electrical properties. Furthermore, CNTs endowed PBS nanocomposite foam with adjustable electromagnetic interference (EMI) shielding property, giving a specific EMI shielding effectiveness of 28.5 dB cm3/g. This study provides a promising methodology for preparing biodegradable, lightweight PBS/CNTs foam with outstanding electromagnetic shielding properties.  相似文献   
2.
The use of biopolymers has gained priority in tissue engineering and biotechnology, both as dressing material and for enhancing treatment efficiency. There is a demand for new biopolymers designed with protease inhibitors and antimicrobials. LL‐37 is an important antimicrobial peptide in human skin and exhibits a broad spectrum of antimicrobial activity against bacteria, fungi, and viral pathogens. Using lignin which is an abundant carbohydrate polymer in nature and a polyacrylic acid, we prepared a lignin/caprolactone biodegradable film by plastifying caprolactone and polyacyrlic acid. Lignin/caprolactone biodegradable film was activated with CDI and then immobilized LL‐37 peptide. The structure was elucidated in terms of its functional groups by attenuated total reflectance‐fourier transform infrared spectroscopy (ATR‐FTIR), and the morphology of the lignin/caprolactone biodegradable film was characterized by scanning electron microscopy (SEM) before and after the immobilization process. The amount of LL‐37 immobilized was determined by ELISA method. It was found that 97% of LL‐37 peptide was successfully immobilized onto the lignin/caprolactone biodegradable film. Antimicrobial activity was determined in the lignin/caprolactone biodegradable film samples by quantitative antimicrobial activity method. According to the results, LL‐37 immobilized lignin/caprolactone biodegradable film samples were effective on test organisms; Gram‐positive Staphylococcus aureus and Gram‐negative Escherichia coli. In bio‐compatibility assays, the ability to support tissue cell integration was detected by using 3 T3 mouse fibroblasts. Samples were examined under transverse microscope, non‐immobilized sample showed a huge cellular death, whereas LL‐37 immobilized lignin/caprolactone biodegradable film had identical cellular growth with the control group. This dual functional lignin/caprolactone biodegradable film with enhanced antibacterial properties and increased tissue cell compatibility may be used to design new materials for various types of biological applications.  相似文献   
3.
The development of biodegradable materials for tailored applications, particularly in the field of polymeric films and sheets, is a challenging technological goal as well as a contribution to help protect the environment. Poly(lactic) acid (PLA) is a promising substitute for several oil-based polymers; however, to overcome its thermal and mechanical drawbacks, researchers have developed solutions such as blending PLA with polybutylene adipate terephthalate (PBAT), which is capable of increasing the ductility of the final material. In this study, PLA/PBAT binary blends, with minimum possible content of nonrenewable materials, were examined from processing, thermal, morphological, and rheological perspective. An optimized PLA/PBAT ratio was chosen as the polymeric basis to obtain a biodegradable formulation by adding a biobased plasticizer and appropriate fillers to produce a micrometer film with tailored flexibility and tear resistance. The processing technology involved flat-die extrusion, followed by calendering. The tearing resistance of the produced film was investigated, and the results were compared with literature data. A study on the essential work of fracture was implemented to explore the mode III out-of-plane fracture resistance starting from a trouser tear test.  相似文献   
4.
The kinetic of D,L-lactide polymerization in presence of biocompatible zirconium acetylacetonate initiator was studied by differential scanning calorimetry in isothermal mode at various temperatures and initiator concentrations. The enthalpy of D,L-lactide polymerization measured directly in DSC cell was found to be ΔH=−17.8±1.4 kJ mol−1. Kinetic curves of D,L-lactide polymerization and propagation rate constants were determined for polymerization with zirconium acetylacetonate at concentrations of 250–1000 ppm and temperature of 160–220 °C. Using model or reversible polymerization the following kinetic and thermodynamic parameters were calculated: activation energy Ea=44.51±5.35 kJ mol−1, preexponential constant lnA=15.47±1.38, entropy of polymerization ΔS=−25.14 J mol−1 K−1. The effect of reaction conditions on the molecular weight of poly(D,L-lactide) was shown.  相似文献   
5.
Polypeptides have received noticeable attention in the biomedical field due to their structural versatility and biomimetic properties. Particularly, polypeptides that are responsive to biological stimuli, such as mildly acidic extracellular and intracellular conditions, have great potential as delivery carriers for therapeutics. However, synthesis of high-molecular-weight acid-labile peptides is often daunting due to highly restrictive polymerization conditions and limitations in preserving acid-degradable functional groups. For instance, the popular N-carboxyanhydride (NCA) ring-opening polymerization (ROP) is efficient, but acid-labile NCA monomers are difficult to synthesize and store. In this study, acid-labile polypeptides with high molecular weights were synthesized under mild, permissive conditions using carboxylated urethane derivative monomers which are stable for ease of handling. The polymerization was successful in various organic solvents at room temperature, and did not require additional energy or initiation to drive the formation of NCA intermediates. The polymerization was also rapid enough to be independent of inert atmosphere. The strategy explored here to synthesize high-molecular-weight acid-labile polypeptides offers significant advantages including facile synthesis of acid-labile urethane derivative monomers that are stable, even in contact with moisture, and fast polymerization under easily achievable conditions. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 280–286  相似文献   
6.
7.
Well‐defined 1,4‐diketo‐3,6‐di(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole (DTDPP) labeled polycaprolactones (PCL) with different chain lengths were synthesized and characterized. The effect of polymer chain lengths on the optical properties of DTDPP in solid states was studied by UV‐Vis absorption spectroscopy as well as steady‐state and dynamic fluorescence spectroscopies. Our results indicate that when the PCL side chain is extended to a certain length, the intermolecular aggregation of DTDPP units can be reduced significantly due to segregation effect of PCL. This approach offers a new facile strategy to address the common problem of aggregation‐caused quenching existing in organic fluorophores. These highly fluorescent biodegradable PCL polymers may find broad biomedical applications such as fluorescence‐based bioimaging and tissue engineering. © 2015 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym. Chem. 2015 , 53, 1032–1042  相似文献   
8.
Polymersomes have gained much interest within the biomedical field as drug delivery systems due to their ability to transport and protect cargo from the harsh environment inside the body. For an improved drug efficacy, control over cargo release is however also an important factor to take into account. An often employed method is to incorporate pH sensitive groups in the vesicle membrane, which induce disassembly and content release when the particles have reached a target site in the body with the appropriate pH, such as the acidic microenvironment of tumor tissue or the endosome. In this paper, biodegradable poly(ethylene glycol)-poly(caprolactone-gradient-trimethylene carbonate)-based polymeric vesicles have been developed with disassembly features at mild acidic conditions. Modifying the polymer backbone with imidazole moieties results in vesicle disassembly upon protonation due to the lowered pH. Furthermore, upon increasing the pH efficient re-assembly into vesicles is observed due to the switchable amphiphilic nature of the polymer. When this re-assembly process is conducted in presence of cargo, enhanced encapsulation is achieved. Furthermore, the potency of the polymeric system for future biomedical applications such as adjuvant delivery is demonstrated.  相似文献   
9.
Poly([R]‐3‐hydroxybutyrate) (PHB), a natural biodegradable polyester, has attracted much attention as a new biomaterial because of its sustainability and good biocompatibility. In this study, it is discovered that PHB can be conveniently functionalized to obtain a number of platform chain architectures that may provide a wide range of functional copolymers. In a transesterification reaction, linear (di‐hydroxylated) and star shaped (tri‐ and tetra‐hydroxylated) PHB oligomers are synthesized, followed by copolymerization with 2‐(dimethylamino)ethyl methacrylate and quaternization with benzyl bromide to afford antimicrobial properties. The antimicrobial activities of the quaternary salts against clinically relevant pathogens on the interactions with outer and cytoplasmic membranes, lethal mechanisms, multipassage resistance, and synergy effect with antibiotics are investigated. Cationic PHB copolymers show effectiveness as antimicrobial agents, with minimum inhibitory concentration values 0.24–0.65 µm (or µmol dm?3) (or 32–128 µg mL?1) against Gram‐positive and Gram‐negative bacteria. Modifying the copolymer architectures into star shapes results in enhanced effectiveness to disrupt the membrane integrity. Synergistic effects are attained for all the quaternized PHB derivatives when they are used together with tobramycin. Multipassage resistance does not occur in both the linear and star derivatives against Gram‐negative bacteria after 20 passages.  相似文献   
10.
The allyl phosphoester group is shown to be a protecting group for the synthesis of anionic polyphosphodiesters. Our strategy relies on the synthesis of a cyclic phosphate monomer bearing a pendant allyl phosphoester group, its easy purification by fractional distillation, its organocatalyzed ring‐opening polymerization by 1,8‐diazobicyclo[5.4.0]undec‐7‐ene (DBU) and 1‐[3,5‐bis(trifluoromethyl)phenyl]‐3‐cyclohexyl‐thiourea (TU). Finally, the deprotection of the allyl phosphoester group is carried out by reaction with sodium benzenethiolate in the absence of any detectable degradation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2642–2648  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号