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   538710篇
  免费   5807篇
  国内免费   1526篇
化学   289403篇
晶体学   7741篇
力学   23614篇
综合类   18篇
数学   62588篇
物理学   162679篇
  2021年   4411篇
  2020年   4916篇
  2019年   5281篇
  2018年   6802篇
  2017年   6656篇
  2016年   10361篇
  2015年   6549篇
  2014年   10050篇
  2013年   24420篇
  2012年   18744篇
  2011年   23135篇
  2010年   16161篇
  2009年   16037篇
  2008年   21199篇
  2007年   21160篇
  2006年   19702篇
  2005年   17755篇
  2004年   16330篇
  2003年   14340篇
  2002年   14251篇
  2001年   15999篇
  2000年   12162篇
  1999年   9505篇
  1998年   8033篇
  1997年   7706篇
  1996年   7429篇
  1995年   6699篇
  1994年   6655篇
  1993年   6378篇
  1992年   7179篇
  1991年   7275篇
  1990年   6904篇
  1989年   6741篇
  1988年   6767篇
  1987年   6603篇
  1986年   6245篇
  1985年   8086篇
  1984年   8309篇
  1983年   6694篇
  1982年   6893篇
  1981年   6768篇
  1980年   6322篇
  1979年   6856篇
  1978年   7081篇
  1977年   6876篇
  1976年   6872篇
  1975年   6423篇
  1974年   6468篇
  1973年   6409篇
  1972年   4499篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
61.
Copolymers of monomers 2,4‐dichlorophenyl methacrylate (2,4‐DMA) and methyl methacrylate (MMA) were synthesized with different monomer feed ratios using toluene as a solvent and 2,2′‐azobisisobutyronitrile (AIBN) as an initiator at 70 °C. The copolymers were characterized by IR‐spectroscopy, and copolymer composition was determined with UV‐spectroscopy. The linearization method of Fineman–Ross was employed to obtain the monomer reactivity ratios. The molecular weights and polydispersity indexes were determined by gel permeation chromatography (GPC). Thermogravimetric analyses of polymers were carried out in nitrogen atmosphere. The homo‐ and copolymers were tested for their antimicrobial properties against selected microorganisms. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5227–5234, 2004  相似文献   
62.
3,3′,5,5′‐Tetrakis(2‐chloro‐2‐propyl)biphenyl (biphenyl tetracumyl chloride, BPTCC) and 1,3‐bis[3,5‐bis(2‐chloro‐2‐propyl)phenoxy]propane (diphenoxypropane tetracumyl chloride, DPPTCC) were synthesized as initiators for quasiliving cationic polymerization of isobutylene (IB). In the synthesis of BPTCC, tetrafunctionality was achieved via the coupling of dimethyl 5‐bromoisophthalate (DMBI) using nickel dibromide bis(triphenylphosphine) and zinc in the presence of a base; in the synthesis of DPPTCC, two equivalents of dimethyl 5‐hydroxyisophthalate were linked via reaction with 1,3‐dibromopropane in the presence of potassium carbonate. Both initiators were used to initiate the polymerization of IB under quasiliving cationic polymerization conditions. PIB initiated from BPTCC revealed a chain end/molecule value (as determined by 1H‐NMR) of 3.85, verifying the nearly exclusive production of 4‐arm polyisobutylene (PIB). GPC analysis revealed a narrow peak representing the target four‐arm PIB, with a slight shoulder at high elution volumes (low molecular weights). GPC analysis of the PIB initiated by DPPTCC revealed multimodal distributions, suggesting the formation of two‐, three‐, and four‐arm star polymers during the polymerization. This behavior was attributed to Friedel–Crafts alkylation of the initiator core after the addition of one IB unit, which was activated by the electron‐donating oxytrimethyleneoxy linking moiety. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5942–5953, 2004  相似文献   
63.
During the past three decades there has been an intense debate on the quality of health care. Errors in medicine, practice variations, competence of physicians, scarcity and lack of resources have all been reasons for discussing the quality of care. A clear definition of quality should explain the nature of the debate, improve uniformity of speech and facilitate meaningful actions such as quality assurance or quality improvement. However, in due course many different definitions have been proposed and principles of quality assurance in health care have been frequently questioned, because of their industrial nature. It raises questions on our understanding of quality in health care. In this paper, we (i) explore the nature of the quality concept, (ii) explain its meaning by Wittgenstein's theory on rule-following, and (iii) argue for understanding medical care as a reflexive practice, in order to integrate the meaning of quality in medical care.  相似文献   
64.
The production of high‐solid‐content, low‐viscosity latexes is an active field in both industry and academia. The viscosity of polymer dispersions has a clear dependence on the particle size distribution (PSD). An example is the rule of thumb that a bimodal PSD enables the reduction of the viscosity with respect to monomodal systems. Despite important progress in theoretical work, not much has been done to quantitatively predict the low shear viscosity of aqueous polymer dispersions as a function of the complex PSD. In this work, the capability of a low‐shear‐viscosity equation to quantitatively account for the influence of both the PSD and the physicochemical characteristics of the dispersions is experimentally assessed. An analysis, consistent with theoretical concepts, of the data with semiempirical correlations is proposed. Next, with values of the parameters of the viscosity equation obtained experimentally, the effect of a latex with a 70% solid content on the low shear viscosity is examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3936–3946, 2004  相似文献   
65.
Films of amorphous polystyrene (PS) with a weight-average molecular weight (Mw) of 225 × 103 g/mol were bonded in a T-peel test geometry, and the fracture energy (G) of a PS/PS interface was measured at the ambient temperature as a function of the healing time (th) and healing temperature (Th). G was found to develop with (th)1/2 at Th = Tg-bulk − 33 °C (where Tg-bulk is the glass-transition temperature of the bulk sample), and log G was found to develop with 1/Th at Tg-bulk − 43 °C ≤ ThTg-bulk − 23 °C. The smallest measured value of G = 1.4 J/m2 was at least one order of magnitude larger than the work of adhesion required to reversibly separate the PS surfaces. These three observations indicated that the development of G at the PS/PS interface in the temperature range investigated (<Tg-bulk) was controlled by the diffusion of chain segments feasible above the glass-transition temperature of the interfacial layer, in agreement with our previous findings for fracture stress development at several polymer/polymer interfaces well below Tg-bulk. Close values of G = 8–9 J/m2 were measured for the symmetric interfaces of polydisperse PS [Mw = 225 × 103, weight-average molecular weight/number-average molecular weight (Mw/Mn) = 3] and monodisperse PS (Mw = 200 × 103, Mw/Mn = 1.04) after healing at Th = Tg-bulk − 33 °C for 24 h. This implies that the self-bonding of high-molecular-weight PS at such relatively low temperatures is not governed by polydispersity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1861–1867, 2004  相似文献   
66.
A new method for the synthesis of exfoliated graphite and polyaniline (PANI)/graphite nanocomposites was developed. Exfoliated graphite nanosheets were prepared through the microwave irradiation and sonication of synthesized expandable graphite. The nanocomposites were fabricated via the in situ polymerization of the monomer at the presence of graphite nanosheets. The as-synthesized graphite nanosheets and PANI/graphite nanocomposite materials were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The conductivity of the PANI/graphite nanocomposites was dramatically increased over that of pure PANI. TGA indicated that the incorporation of graphite greatly improved the thermal stability of PANI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1972–1978, 2004  相似文献   
67.
The microstructure and fracture behavior of epoxy mixtures containing two monomers of different molecular weights were studied. The variation of the fracture toughness by the addition of other modifiers was also investigated. Several amounts of high‐molecular‐weight diglycidyl ether of bisphenol A (DGEBA) oligomer were added to a nearly pure DGEBA monomer. The mixtures were cured with an aromatic amine, showing phase separation after curing. The curing behavior of the epoxy mixtures was investigated with thermal measurements. A significant enhancement of the fracture toughness was accompanied by slight increases in both the rigidity and strength of the mixtures that corresponded to the content of the high‐molecular‐weight epoxy resin. Dynamic mechanical and atomic force microscopy measurements indicated that the generated two‐phase morphology was a function of the content of the epoxy resin added. The influence of the addition of an oligomer or a thermoplastic on the morphologies and mechanical properties of both epoxy‐containing mixtures was also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3920–3933, 2004  相似文献   
68.
A crystalline δ form of a syndiotactic polystyrene (sPS) membrane was prepared from a solution of sPS (1 wt %) and p‐chlorotoluene (p‐CT) by a solution‐casting method. The mesophase (δ empty form) of sPS was obtained by the extraction of the guest solvent from the δ form of sPS by a stepwise solvent‐extraction method. The sPS/p‐CT mesophase membrane [p‐CT (A‐M)] was used for the sorption of 1 mol % p‐CT for different times and for the sorption of different concentrations of p‐CT, chlorobenzene (CB), p‐xylene (p‐X), toluene, and chloroform for 48 h. The presence of solvents in the sPS membrane was confirmed by IR analysis. A thermal study revealed that the sorption amount of 1 mol % p‐CT increased with increasing immersion time, and the sorption amounts of different solvents increased with increasing solvent concentration. Differential scanning calorimetry results showed that the desorption peak temperature increased as the amount of the solvent increased in the clathrated sPS membrane. Wide‐angle X‐ray diffraction results showed that 2θ at 8.25° was slightly shifted toward 8°, and there was no change in the peak position at 10° for p‐CT (A‐M), which was immersed in different solvents (1 mol %); however, the intensity of 2θ at 10° was not similar for all the samples. Among the solvents used for the sorption studies at 1 mol %, p‐CT (A‐M) could sorb more p‐CT and CB than p‐X, toluene, and chloroform. The solvent sorption isotherm was the Langmuir sorption mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3439–3446, 2004  相似文献   
69.
Large melting point depressions for organic nanocrystals, in comparison with those of the bulk, were observed in an associative polymer: telechelic, pyrene‐labeled poly(dimethylsiloxane) (Py‐PDMS‐Py). Nanocrystals formed within nanoaggregates of pyrenyl units that were immiscible in poly(dimethylsiloxane). For 5 and 7 kg/mol Py‐PDMS‐Py, physical gels resulted, with melting points exceeding 40 °C and with small‐angle X‐ray scattering peaks indicating that the crystals were nanoconfined, were 2–3 nm long, and contained roughly 18–30 pyrenyl dye end units. In contrast, 30 kg/mol Py‐PDMS‐PY was not a gel and exhibited no scattering peak at room temperature; however, after 12 h of annealing at ?5 °C, multiple melting peaks were present at 5–30 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3470–3475, 2004  相似文献   
70.
We developed a new mammalian cell-based luciferase reporter gene assay for androgenic and antiandrogenic activities of chemicals and environmental samples. Environmental samples usually have a complex matrix that may contain the constituents acting as androgen receptor (AR) agonists, AR antagonists or aryl hydrocarbon receptor (AhR) agonists. AhR agonists are known to elicit the antiandrogenic effect through cross-talk between AR and AhR signal transduction pathways. In this study, PC3/AR human prostate carcinoma cells were transiently transfected with a prostate-specific antigen (PSA) promoter-driven luciferase expression plasmid. The cells were treated with a test compound or an environmental sample for 24 h at 37 degrees C and then measured for luciferase activity. The luciferase activity was induced by dihydrotestosterone (DHT) in a concentration-dependent manner in a concentration range from 10 fM to 1 nM. R1881, a synthetic androgen receptor agonist, induced luciferase activity and its inductive effects was additive to that of DHT. The luciferase activity was not induced by cortisol, a glucocorticoid, progesterone, a progestin, and 17beta-estradiol, an estrogen in a concentration range of up to 1 microM. DHT-induced luciferase activity was reduced by bicalutamide and cyproterone acetate, AR antagonists, and also by benzo[a]pyrene, an aryl hydrocarbon receptor agonist, through AhR-mediated pathways. All of these findings indicate that the present assay system correctly responds to AR agonists, AR antagonists and AhR agonist and, therefore, it is a powerful tool for the sensitive and selective screening of chemicals and environmental samples for their androgenic and antiandrogenic activities. We developed the first assay system, in which the expression of luciferase was driven by the promoter of a prostate-specific antigen gene, a typical human androgen-regulated gene.  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