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   1854篇
  免费   107篇
  国内免费   10篇
化学   1410篇
晶体学   27篇
力学   52篇
数学   94篇
物理学   388篇
  2024年   4篇
  2023年   16篇
  2022年   41篇
  2021年   48篇
  2020年   46篇
  2019年   51篇
  2018年   31篇
  2017年   35篇
  2016年   75篇
  2015年   60篇
  2014年   90篇
  2013年   146篇
  2012年   155篇
  2011年   173篇
  2010年   104篇
  2009年   83篇
  2008年   124篇
  2007年   103篇
  2006年   97篇
  2005年   76篇
  2004年   91篇
  2003年   62篇
  2002年   53篇
  2001年   39篇
  2000年   35篇
  1999年   15篇
  1998年   10篇
  1997年   6篇
  1996年   16篇
  1995年   9篇
  1994年   11篇
  1993年   10篇
  1992年   12篇
  1991年   5篇
  1990年   8篇
  1989年   4篇
  1988年   3篇
  1987年   2篇
  1986年   6篇
  1985年   3篇
  1983年   1篇
  1982年   2篇
  1981年   2篇
  1980年   1篇
  1979年   3篇
  1978年   1篇
  1977年   2篇
  1976年   1篇
排序方式: 共有1971条查询结果,搜索用时 15 毫秒
111.
A novel sensing material, MnFe2O4/polyaniline (PANI), was fabricated by doping PANI to MnFe2O4 on a modified glassy carbon electrode (GCE). This sensing material was characterized using X‐ray diffraction (XRD), scanning electron microscopy (SEM), and high‐resolution transmission electron microscopy (HR‐TEM). Using a cyclic voltammetry electrochemical‐sensing method, we tested MnFe2O4/PANI, and an acetaminophen concentration of 0.0625–5 mM was recorded. Furthermore, the sensor responses were 2.05–22.44. The detection limit was 2.23 × 10?7 M. Strong selectivity was observed for MnFe2O4/PANI, which is a possible sensing mechanism.  相似文献   
112.
We reported on two polymer semiconducting copolymers based on porphyrin compounds, poly[9,9-dioctylfluorene-co-5,15-bis(hexoxybenzyl)-10,20-bis(benzo-4-yl)porphyrin] (PFPor) and poly[9-(heptadecan-9-yl)carbazole-co-5,15-bis(hexoxybenzyl)-10,20-bis(benzo-4-yl)porphyrin] (PCPor), for use as organic photovoltaic materials. The thermal, optical, electrochemical, and photovoltaic properties of the two polymers were investigated. In addition, PC61BM and PC71BM were introduced as acceptor materials to confirm the acceptor effect in bulk heterojunction photovoltaic devices. Moreover, in order to establish acceptor effects, morphologies of polymer/PCBM blend films were analyzed through atomic force microscopy (AFM). PFPor and PCPor exhibited the best device performance with power conversion efficiencies (PCE) of 0.62% and 0.76%, respectively, upon the introduction of PC71BM as the acceptor in the device where 86 wt.% of the PC71BM was contained in the active layer (pol:PC71BM = 1:6, w/w).  相似文献   
113.
Chemosensors are developed to image zinc ions. Fluorescence enhancement due to Zn2+ binding is an excellent way to detect its presence. A chemosensor for Zn2+ based on dipicolylamine (DPA) groups connected by a pyridyl amide backbone has been synthesized. Addition of 2-chloroacetyl chloride to 2,6-diaminopyridine affords 2,6-bis(chloroethylamido)pyridine, which is converted to the sensor BADPA-P by 2,2′-dipicolylamine displacement of chlorine. This compound along with two others, the mono-DPA, ADPA-P and the benzyl in place of pyridyl, BADPA-B, present three potential Zn2+ sensors. It was found that BADPA-P in the presence of Zn2+ shows a large increase in fluorescence, whether in polar organic or aqueous environments. Its fluorescence in the presence of Cd2+, unlike with Zn2+, is not enhanced when excited at longer wavelengths. Proton NMR measurements, indicate two Zn2+ ions bind to BADPA-P. Also, Zn2+ enhances fluorescence even when other metal ions are present.  相似文献   
114.
A new kind of organic-inorganic hybrid polymer, poly(tetraphenyl)silole siloxane, was invented and synthesized for realization of its unique charge trap properties. The organic portions consisting of (tetraphenyl)silole rings were responsible for negative charge trapping, while the Si-O-Si inorganic linkages provided the intrachain energy barrier for controlling electron transport. The polysilole siloxane dielectric thin films were fabricated by spin-coating and curing of the polymers, followed by characterization with spectroscopic ellipsometry (SE), near edge X-ray absorption fine structure spectroscopy (NEXAFS), and photoemission spectroscopy (PES). The abrupt increase in density and decrease in thickness of the thin film at a curing temperature of 100 °C was attributed to a thermodynamically preferred state in the nanoscopic arrangement of the polymer chains; this was due to cofacial π-π interactions in a skewed manner between peripheral phenyl groups of the (tetraphenyl)silole rings of the adjacent polymer chains. Using the NEXAFS spectrum to assess high electron affinity, the LUMO energy level of the dielectric thin film cured at 150 °C was positioned 1 eV above the Fermi energy level (E(F)). The electron trapping of the dielectric thin films was confirmed from the positive flat band shift (ΔV(FB)) in the capacitance-voltage (C-V) measurements performed within the metal-insulator-semiconductor (MIS) device structure, which strongly verified the polymer design concept. From the simple kinetics model of the electron transport, it was proposed that the flat band shift (ΔV(FB)) or trap density of the negative charges (|ρ|) was logarithmically proportional to the decay constant (β) for the electron-tunneling process. When a phenyl group of a silole ring in a polymer chain was inserted into the two available phenyl groups of another silole ring in another polymer chain, the electron transfer between the groups was enhanced, decreasing the trap density of the negative charges (|ρ|). For the thermodynamically preferred state generating the high refractive index, the distance between the two phenyl groups of the adjacent polymer chains was estimated to be in the range of 0.27-0.36 nm.  相似文献   
115.
The incorporation of permeation enhancers in topical preparations has been recognized as a simple and valuable approach to improve the penetration of antifungal agents into toenails. In this study, to improve the toenail delivery of efinaconazole (EFN), a triazole derivative for onychomycosis treatment, topical solutions containing different penetration enhancers were designed, and the permeation profiles were evaluated using bovine hoof models. In an in vitro permeation study in a Franz diffusion cell, hydroalcoholic solutions (HSs) containing lipophilic enhancers, particularly prepared with propylene glycol dicaprylocaprate (Labrafac PG), had 41% higher penetration than the HS base. Moreover, the combination of hydroxypropyl-β-cyclodextrin with Labrafac PG further facilitated the penetration of EFN across the hoof membrane. In addition, this novel topical solution prepared with both lipophilic and hydrophilic enhancers was physicochemically stable, with no drug degradation under ambient conditions (25 °C, for 10 months). Therefore, this HS system can be a promising tool for enhancing the toenail permeability and therapeutic efficacy of EFN.  相似文献   
116.
Gout is a type of inflammatory arthritis caused by the deposition of monosodium uric acid (MSU) crystals in tissues. The etiology of gout is directly linked to the NLRP3 inflammasome, since MSU crystals are NLRP3 inflammasome activators. Therefore, we decided to search for a small-molecule inhibitor of the NLRP3 inflammasome for the prevention of gout inflammation. We found that loganin suppressed MSU crystals-induced caspase-1 (p20) and interleukin (IL)-1β production and apoptosis-associated speck-like protein containing a caspase recruitment domain (ASC) specks formation in mouse primary macrophages, showing its ability to inhibit the NLRP3 inflammasome. In an air pouch inflammation model, oral administration of loganin to mice prevented MSU crystals-induced production of mature IL-1β and IL-18 in air pouch exudates, resulting in decreased neutrophil recruitment. Furthermore, oral administration of loganin suppressed MSU crystals-induced gout inflammation in a mouse foot gout model, which was accompanied by the inhibition of the NLRP3 inflammasome. Loganin blocked de novo synthesis of mitochondrial DNA in air pouches and foot tissues injected with MSU crystals. Consistently, loganin prevented MSU crystals-induced mitochondrial damage in macrophages, as it increased mitochondrial membrane potential and decreased the amount of mitochondrial reactive oxygen species. These data demonstrate that loganin suppresses NLRP3 inflammasome activation by inhibiting mitochondrial stress. These results suggest a novel pharmacological strategy to prevent gout inflammation by blocking NLRP3 inflammasome activation and mitochondrial dysfunction.  相似文献   
117.
Imide-siloxane block copolymer/silica hybrid membranes with covalent bonds were prepared via sol–gel reaction. The structural informations of these hybrid membranes were obtained by using Fourier transform-infrared spectrometry (FT-IR), 29Si nuclear magnetic resonance (29Si NMR), XPS and thermogravimetric analysis (TGA). The gas separation properties of the hybrid membranes were also investigated in terms of organosiloxane (PDMS) or silica content at various temperatures. In the hybrids, the addition of PDMS phase increased the permeabilities of gases such as He, CO2, O2, and N2, indicating that the gas transport occurred mainly through rubbery organic matrix. Meanwhile, the PDMS phase contributed the decreased gas selectivities to nitrogen but the reduction in selectivities was very small in comparison with other siloxane containing polymeric membranes. This might be due to the restriction of chain mobility by the existence of inorganic component such as silica network in the hybrids. Additionally, the increase of silica content in these hybrid membranes considerably retarded the falling-off of gas selectivity at elevated temperature. The increase of silica content in hybrid membranes resulted in well-formed silica networks and hence these inorganic components restricted the plasticization of organic matrix by the thermal segmental motion of organic components, leading to preventing the large decrease of the gas selectivity.  相似文献   
118.
New discotic nematic liquid crystals have been prepared through intermolecular hydrogen bonding between the core of 1,3,5-trihydroxybenzene (phloroglucinol, PG) or 1,3,5-tris(4-hydroxyphenyl)benzene (THPB) and the peripheral molecules of stilbazole derivatives. The various nematic phases formed by new hydrogen bonding building blocks were investigated by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. The first discotic complexes of PG and trans-4-alkoxy-4′-stilbazoles exhibited nematic columnar (NC) and hexagonal columnar phases depending on the length of alkyl chains, which were considered as the basic discotic structure. Several structural variations on the building blocks were attempted to examine their effects on the liquid crystalline properties of discotic complexes. The nematic lateral phase (NL) with enhanced intercolumnar order was observed for the complexes of PG and trans-4-cyanoalkoxy-4′ stilbazoles due probably to the strong dipole interactions between cyano groups at the end of alkoxy chains. By introducing the nonlinear structure in three arms of supramolecular discotic mesogen, a discotic nematic phase (ND) was observed for the complex of THPB and trans-4-octyloxy-4 -stilbazole. The single hydrogen bonding between phenol and pyridine moieties in this study provides a simple and effective method for preparing the rarely found discotic nematic liquid crystals.  相似文献   
119.
Cancer cell metabolism is characterized by an enhanced uptake and utilization of glucose, a phenomenon known as the Warburg effect. The persistent activation of aerobic glycolysis in cancer cells can be linked to activation of oncogenes or loss of tumor suppressors, thereby fundamentally advancing cancer progression. In this respect, inhibition of glycolytic capacity may contribute to an anticancer effect on malignant cells. Understanding the mechanisms of aerobic glycolysis may present a new basis for cancer treatment. Accordingly, interrupting lactate fermentation and/or other cancer-promoting metabolic sites may provide a promising strategy to halt tumor development. In this review, we will discuss dysregulated and reprogrammed cancer metabolism followed by clinical relevance of the metabolic enzymes, such as hexokinase, phosphofructokinase, pyruvate kinase M2, lactate dehydrogenase, pyruvate dehydrogenase kinase and glutaminase. The proper intervention of these metabolic sites may provide a therapeutic advantage that can help overcome resistance to chemotherapy or radiotherapy.  相似文献   
120.
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