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   350篇
  免费   7篇
  国内免费   4篇
化学   228篇
晶体学   3篇
力学   16篇
数学   54篇
物理学   60篇
  2024年   3篇
  2023年   4篇
  2022年   21篇
  2021年   11篇
  2020年   20篇
  2019年   15篇
  2018年   10篇
  2017年   12篇
  2016年   24篇
  2015年   14篇
  2014年   10篇
  2013年   33篇
  2012年   27篇
  2011年   24篇
  2010年   14篇
  2009年   8篇
  2008年   18篇
  2007年   14篇
  2006年   14篇
  2005年   9篇
  2004年   7篇
  2003年   8篇
  2002年   6篇
  2000年   5篇
  1999年   1篇
  1998年   1篇
  1997年   2篇
  1996年   4篇
  1995年   1篇
  1994年   5篇
  1993年   2篇
  1992年   3篇
  1990年   1篇
  1989年   1篇
  1987年   1篇
  1985年   3篇
  1984年   2篇
  1983年   2篇
  1980年   1篇
排序方式: 共有361条查询结果,搜索用时 15 毫秒
81.
Plate heat exchangers (PHE) are used for a wide range of applications, thus utilizing new and unique heat sources is of crucial importance. R744 has a low critical temperature, which makes its thermophysical properties variation smoother than other supercritical fluids. As a result, it can be used as a reliable hot stream for PHE, particularly at high temperatures. The local design approach was constructed via MATLAB integrated with the NIST database for real gases. Recently produced HFOs (R1234yf, R1234ze(E), R1234ze(Z), and R1233zd(E)) were utilized as cold fluids flowing through three phases: Liquid-phase, two-phase, and gas-phase. A two-step study was performed to examine the following parameters: Heat transfer coefficients, pressure drop, and effectiveness. In the first step, these parameters were analyzed with a variable number of plates to determine a suitable number for the next step. Then, the effects of hot stream pressure and cold stream superheating difference were investigated with variable cold channel mass fluxes. For the first step, the results showed insignificant differences in the investigated parameters for the number of plates higher than 40. Meanwhile, the second step showed that increasing the hot stream pressure from 10 to 12 MPa enhanced the two-phase convection coefficients by 17%, 23%, 75%, and 50% for R1234yf, R1234ze(E), R1234ze(Z), and R1233zd(E), respectively. In contrast, increasing the cold stream superheating temperature difference from 5 K to 20 reduced the two-phase convection coefficients by 14%, 16%, 53%, and 26% for R1234yf, R1234ze(E), R1234ze(Z), and R1233zd(E), respectively. Therefore, the R744 is suitable for PHE as a driving heat source, particularly at higher R744 inlet pressure and low cold stream superheating difference.  相似文献   
82.
Silver nanoparticles (AgNPs) have recently gained interest in the medical field because of their biological features. The present study aimed at screening Rhizophora apiculata secondary metabolites, quantifying their flavonoids and total phenolics content, green synthesis and characterization of R. apiculata silver nanoparticles. In addition, an assessment of in vitro cytotoxic, antioxidant, anti-inflammatory and wound healing activity of R. apiculata and its synthesized AgNPs was carried out. The powdered plant material (leaves) was subjected to Soxhlet extraction to obtain R. apiculata aqueous extract. The R. apiculata extract was used as a reducing agent in synthesizing AgNPs from silver nitrate. The synthesized AgNPs were characterized by UV-Vis, SEM-EDX, XRD, FTIR, particle size analyzer and zeta potential. Further aqueous leaf extract of R. apiculata and AgNPs was subjected for in vitro antioxidant, anti-inflammatory, wound healing and cytotoxic activity against A375 (Skin cancer), A549 (Lung cancer), and KB-3-1 (Oral cancer) cell lines. All experiments were repeated three times (n = 3), and the results were given as the mean ± SEM. The flavonoids and total phenolics content in R. apiculata extract were 44.18 ± 0.086 mg/g of quercetin and 53.24 ± 0.028 mg/g of gallic acid, respectively. SEM analysis revealed R. apiculata AgNPs with diameters ranging from 35 to 100 nm. XRD confirmed that the synthesized silver nanoparticles were crystalline in nature. The cytotoxicity cell viability assay revealed that the AgNPs were less toxic (IC50 105.5 µg/mL) compared to the R. apiculata extract (IC50 47.47 µg/mL) against the non-cancerous fibroblast L929 cell line. Antioxidant, anti-inflammatory, and cytotoxicity tests revealed that AgNPs had significantly more activity than the plant extract. The AgNPs inhibited protein denaturation by a mean percentage of 71.65%, which was equivalent to the standard anti-inflammatory medication diclofenac (94.24%). The AgNPs showed considerable cytotoxic effect, and the percentage of cell viability against skin cancer, lung cancer, and oral cancer cell lines was 31.84%, 56.09% and 22.59%, respectively. R. apiculata AgNPs demonstrated stronger cell migration and percentage of wound closure (82.79%) compared to the plant extract (75.23%). The overall results revealed that R. apiculata AgNPs exhibited potential antioxidant, anti-inflammatory, wound healing, and cytotoxic properties. In future, R. apiculata should be further explored to unmask its therapeutic potential and the mechanistic pathways of AgNPs should be studied in detail in in vivo animal models.  相似文献   
83.
84.
Plant proteome databases were mined for a flavin monooxygenase (YUCCA), tryptophan decarboxylase (TDC), nitrilase (NIT), and aldehyde oxidase (AO) enzymes that could be involved in the tryptophan-dependent pathway of auxin biosynthesis. Phylogenetic trees for enzyme sequences obtained were constructed. The YUCCA and TDC trees showed that these enzymes were conserved across the plant kingdom and therefore could be involved in auxin synthesis. YUCCAs branched into two clades. Most experimentally studied YUCCAs were found in the first clade. The second clade which has representatives from only seed plants contained Arabidopsis sequences linked to embryonic development. Therefore, sequences in this clade were suggested to be evolved with seed development. Examination of TDC activity and expression had previously linked this enzyme to secondary products synthesis. However, the phylogenetic finding of a conserved TDC clade across land plants suggested its essential role in plant growth. Phylogenetic analysis of AOs showed that plants inherited one AO. Recent gene duplication was suggested as AO sequences from each species were similar to each other rather than to AO from other species. Taken together and based on the experimental support of the involvement of AO in abscisic synthesis, AO was excluded as an intermediate in IAA production. Phylogenetic tree for NIT showed that the first clade contained sequences from species across the plant kingdom whereas the second branch contained sequences from only Brassicaceae. Even though NIT4 orthologues were conserved in the second clade, their major role seems to be detoxification of hydrogen cyanide rather than producing IAA.  相似文献   
85.
Unprotected nucleosides (ROH) were reacted with two polymers bound to N,N-diisopropylamino-1,3,2-oxathiaphospholane in the presence of 1H-terazole. Oxidation with tert-butyl hydroperoxide or sulfurization with Beaucage's reagent, followed by the 1,3,2-oxathiaphospholane ring opening with unprotected nucleosides or carbohydrates (R'OH) in the presence of DBU, afforded nucleoside-(5'-5')-nucleoside or nucleoside-carbohydrate phosphodiester and thiophosphodiester derivatives through the elimination of polymer-bound ethylene episulfide. This strategy offers the advantages of facile isolation of final products and monosubstitution of unprotected nucleosides and carbohydrates.  相似文献   
86.
Seven tetrazole-thione complexes, [Pd2(κ2-ptt)4]( 1 ), trans-[Pd(k1-S-ptt)2(PPh3)2] ( 2 ), trans-[Pd(k1-S-ptt)2(SPPh3)2] ( 3 ), trans-[Pd(k1-S-ptt)2(OPPh3)2] ( 4 ), [Pd(k1-N-ptt)2(k2-dppe)] ( 5a ), [Pd(k1-S-ptt)2(k2-dppe)] ( 5b ), [Pd(k1-S-ptt)2(k2-dppeS2)] ( 6 ), and [Pd(k1-S-ptt)2(k2-dppeO2)] ( 7 ), were prepared from 1-phenyl-1H-tetrazole-5-thiol (Hptt), with substituted phosphines. These complexes were investigated by CHNS analysis; infrared (IR), nuclear magnetic resonance (NMR) (1H and 31P), and ultraviolet–visible (UV–Vis) spectroscopy; and single-crystal X-ray data for 5b . In Complex 1 , the ptt ligand adopted μ2- k-N, k-S bridging mode to afford a dimeric complex, whereas in Complexes 2–4 , 6 , and 7 , the ptt was covalently coordinated via sulfur atom of the thiol group as a solo product. In contrast, in Complex 5 , the ptt ligand was bonded in a monodentate fashion through a deprotonated tetrazole ring nitrogen atom in isomer 5a or via a thiolato sulfur atom in isomer 5b . These linkage isomers were clearly shown in the 31P-{1H} NMR. To explain the adoption of the ligand binding modes in Complexes 5a and 5b , geometry optimization calculations were carried out on two isomers. Very small differences of all molecular parameters were found between 5a and 5b isomers. This confirms the reason for obtaining two isomers. Also, theoretical studies are made for all compounds, and excellent agreement is obtained with experimental data. The direct band gap (Eg) values are equal to 2.88, 2.85, and 2.45 eV for Complexes 1 , 2 , and 4 , respectively, revealing a semiconductor nature. The inhibition activity of Complexes 1–3 , 5 , and 8 were evaluated versus the growth of four types of bacteria in vitro. The complexes showed a good activity compared with free ligand and a standard antibiotic.  相似文献   
87.
A novel, fast and sensitive enantioselective HPLC assay with a new core–shell isopropyl carbamate cyclofructan 6 (superficially porous particle, SPP) chiral column (LarihcShell-P, LSP) was developed and validated for the enantiomeric separation and quantification of verapamil (VER) in rat plasma. The polar organic mobile phase composed of acetonitrile/methanol/trifluoroacetic acid/triethylamine (98:2:0.05: 0.025, v/v/v/v) and a flow rate of 0.5 mL/min was applied. Fluorescence detection set at excitation/emission wavelengths 280/313 nm was used and the whole analysis process was within 3.5 min, which is 10-fold lower than the previous reported HPLC methods in the literature. Propranolol was selected as the internal standard. The S-(−)- and R-(+)-VER enantiomers with the IS were extracted from rat plasma by utilizing Waters Oasis HLB C18 solid phase extraction cartridges without interference from endogenous compounds. The developed assay was validated following the US-FDA guidelines over the concentration range of 1–450 ng/mL (r2 ≥ 0.997) for each enantiomer (plasma) and the lower limit of quantification was 1 ng/mL for both isomers. The intra- and inter-day precisions were not more than 11.6% and the recoveries of S-(−)- and R-(+)-VER at all quality control levels ranged from 92.3% to 98.2%. The developed approach was successfully applied to the stereoselective pharmacokinetic study of VER enantiomers after oral administration of 10 mg/kg racemic VER to Wistar rats. It was found that S-(−)-VER established higher Cmax and area under the concentration-time curve (AUC) values than the R-(+)-enantiomer. The newly developed approach is the first chiral HPLC for the enantiomeric separation and quantification of verapamil utilizing a core–shell isopropyl carbamate cyclofructan 6 chiral column in rat plasma within 3.5 min after solid phase extraction (SPE).  相似文献   
88.
The k 0-method of INAA standardization has been implemented using the irradiation facilities of the fast pneumatic rabbit and some selected manually loaded irradiation positions, which designated for short and long irradiation, respectively, at Egypt second research reactor. The neutron flux parameters (f and α) in each site have been determined using Zr–Au sets as neutron flux monitors. The reference materials coal NIST 1632c and IAEA-Soil 7 were analyzed for data validation and good agreement between the experimental values and the certified values was obtained.  相似文献   
89.
[chemical reaction: see text]. Aminomethyl polystyrene resin-bound linkers of p-acetoxybenzyl alcohol were subjected to reactions with diphosphitylating and triphosphitylating reagents to yield the corresponding polymer-bound diphosphitylating and triphosphitylating reagents, respectively. A number of unprotected carbohydrates and nucleosides were reacted with the polymer-bound reagents. Oxidation with tert-butyl hydroperoxide or sulfurization with Beaucage's reagent, followed by removal of cyanoethoxy group with DBU and the acidic cleavage, respectively, afforded only one type of monosubstituted nucleoside and carbohydrate diphosphates, dithiodiphosphates, triphosphates, and trithiotriphosphates with high regioselectivity.  相似文献   
90.
Epoxidation selectivity of a number of 4,4-dimethyl-1,2,3,4,6,8a-hexahydronaphthalenes 4 were examined. Exposure of the isolated α-epoxides 7provided excellent yields (79–92%) or rearranged fused indene-oxetanes 8. Treatment of β-epoxides 5 with BF3·OEt2 also yields oxetanes 8 and related alcohols 9 and 10.  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