首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 23 毫秒
1.
Relative rate coefficients for the reactions of OH with 3‐methyl‐2‐cyclohexen‐1‐one and 3,5,5‐trimethyl‐2‐cyclohexen‐1‐one have been determined at 298 K and atmospheric pressure by the relative rate technique. OH radicals were generated by the photolysis of methyl nitrite in synthetic air mixtures containing ppm levels of nitric oxide together with the test and reference substrates. The concentrations of the test and reference substrates were followed by gas chromatography. Based on the value k(OH + cyclohexene) = (6.77 ± 1.35) × 10?11 cm3 molecule?1 s?1, rate coefficients for k(OH + 3‐methyl‐2‐cyclohexen‐1‐one) = (3.1 ± 1.0) × 10?11 and k(OH + 3,5,5‐trimethyl‐2‐cyclohexen‐1‐one) = (2.4 ± 0.7) × 10?11 cm3 molecule?1 s?1 were determined. To test the system we also measured k(OH + isoprene) = (1.11 ± 0.23) × 10?10 cm3 molecule?1 s?1, relative to the value k(OH + (E)‐2‐butene) = (6.4 ± 1.28) × 10?11 cm3 molecule?1 s?1. The results are discussed in terms of structure–activity relationships, and the reactivities of cyclic ketones formed in the photo‐oxidation of monoterpene are estimated. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 34: 7–11, 2002  相似文献   

2.
The voltammetric behavior of 3‐nitrofluoranthene and 3‐aminofluoranthene was investigated in mixed methanol‐water solutions by differential pulse voltammetry (DPV) at boron doped diamond thin‐film electrode (BDDE). Optimum conditions have been found for determination of 3‐nitrofluoranthene in the concentration range of 2×10?8–1×10?6 mol L?1, and for determination 3‐aminofluorathnene in the concentration range of 2×10?7–1×10?5 mol L?1, respectively. Limits of determination were 3×10?8 mol L?1 (3‐nitrofluoranthene) and 2×10?7 mol L?1 (3‐aminofluoranthene).  相似文献   

3.
This paper describes the development of a new sensor based on an ionic organic film. The amphiphilic molecule, 4‐[(4‐decyloxyphenyl)‐ethynyl]‐1‐methylpyridinium iodide (10PyI), which has liquid‐crystalline properties, was synthesized and applied in the construction of a GCE/10PyI sensor. Analytical parameters for caffeic acid, repeatability (4.8 %), reproducibility (2.8 %), linearity (two ranges: 9.9×10?7 to 3.8×10?5 mol L?1 and 4.7×10?5 to 9.9×10?5 mol L?1) and detection limits (9.0×10?7 mol L?1 and 8.7×10?6 mol L?1), were determined. The method was successfully applied in the determination of total phenolic compounds (TPC) in mate herb extracts.  相似文献   

4.
Amantadine potentiometric detectors were developed, evaluated and incorporated in a SIA‐LOV manifold in order to accomplish the control of pharmaceutical formulations and urine. The electrodes incorporate α‐cyclodextrin as ionophore, dibutyl phthalate or 2‐fluorophenyl 2‐nitrophenyl ether as plasticizers and potassium tetrakis[3,5‐bis‐(trifluoromethyl)phenyl]borate (KTFPB) as cationic additive. The slope increased from 61.2 to 63.8 mV decade?1 and the practical limit of detection from 2.6×10?6 mol L?1 to 2.5×10?5 mol L?1 when the plasticizer was changed from 2‐fluorophenyl 2‐nitrophenyl ether to dibutyl phthalate. When incorporated in the flow‐manifold the membranes composed by dibutyl phthalate or with 2‐fluorophenyl 2‐nitrophenyl ether presented slopes and a practical limit of detection of 69.8 mV decade?1 and 1.5×10?4 mol L?1 or 73.7 mV decade?1 and 5.4×10?5 mol L?1, respectively. The electrode presented stable responses for over a year, and were highly selective concerning the representative species of the two sample matrices assayed as interferents. Comparison of obtained results with those provided by reference methods and recovery assays, revealed adequate accuracy for control assays.  相似文献   

5.
A novel silicon‐based compound, 10‐phenyl‐2′‐(triphenylsilyl)‐10H‐spiro[acridine‐9,9′‐fluorene] (SSTF), with spiro structure has been designed, synthesized, and characterized. Its thermal, electronic absorption, and photoluminescence properties were studied. Its energy levels make it suitable as a host material or exciton‐blocking material in blue phosphorescent organic light‐emitting diodes (PhOLEDs). Accordingly, blue‐emitting devices with iridium(III) bis[(4,6‐difluorophenyl)‐pyridinato‐N,C2′]picolinate (FIrpic) as phosphorescent dopant have been fabricated and show high efficiency with low roll‐off. In particular, 44.0 cd A?1 (41.3 lm W?1) at 100 cd m?2 and 41.9 cd A?1 (32.9 lm W?1) at 1000 cd m?2 were achieved when SSTF was used as host material; 28.1 lm W?1 at 100 cd m?2 and 20.6 lm W?1 at 1000 cd m?2 were achieved when SSTF was used as exciton‐blocking layer. All of the results are superior to those of the reference devices and show the potential applicability and versatility of SSTF in blue PhOLEDs.  相似文献   

6.
A new series of tris(2‐aminoethyl)amine (tren)‐based L ‐alanine amino acid backboned tripodal hexaamide receptors (L1–L5) with various attached moieties based on electron‐withdrawing fluoro groups and lipophilicity have been synthesized and characterized. Detailed binding studies of L1–L5 with different anions, such as halides (F?, Cl?, Br?, and I?) and oxyanions (AcO?, BzO? (Bz=benzoyl), NO3?, H2PO4?, and HSO4?), have been carried out by isothermal titration calorimetric (ITC) experiments in acetonitrile/dimethylsulfoxide (99.5:0.5 v/v) at 298 K. ITC titration experiments have clearly shown that receptors L1–L4 invariably form 1:1 complexes with Cl?, AcO?, BzO?, and HSO4?, whereas L5 forms a 1:1 complex only with AcO?. In the case of Br?, I?, and NO3?, no appreciable heat change is observed owing to weak interactions between these anions and receptors; this is further confirmed by 1H NMR spectroscopy. The ITC binding studies of F? and H2PO4? do not fit well for a 1:1 binding model. Furthermore, ITC binding studies also revealed slightly higher selectivity of this series of receptors towards AcO? over Cl?, BzO?, and HSO4?. Solid‐state structural evidence for the recognition of Cl? by this new category of receptor was confirmed by single‐crystal X‐ray structural analysis of the complex of tetrabutylammonium chloride (TBACl) and L1. Single‐crystal X‐ray diffraction clearly showed that the pentafluorophenyl‐functionalized amide receptor (L1) encapsulated Cl? in its cavity by hydrogen bonds from amides, and the cavity of L1 was capped with a TBA cation through hydrogen bonding and ion‐pair interactions to form a capped‐cleft orientation. To understand the role of the cationic counterpart in solution‐state Cl? binding processes with this series of receptors (L1–L4), a detailed Cl? binding study was carried out with three different tetraalkylammonium (Me4N+, Et4N+, and Bu4N+) salts of Cl?. The binding affinities of these receptors with different tetralkylammonium salts of Cl? gave binding constants with the TBA cation in the following order: butyl>ethyl>methyl. This study further supports the role of the TBA countercation in ion‐pair recognition by this series of receptors.  相似文献   

7.
Rate constants for the reactions of 2‐methoxy‐6‐(trifluoromethyl)pyridine, diethylamine, and 1,1,3,3,3‐pentamethyldisiloxan‐1‐ol with OH radicals have been measured at 298 ± 2 K using a relative rate method. The measured rate constants (cm3 molecule?1 s?1) are (1.54 ± 0.21) × 10?12 for 2‐methoxy‐6‐(trifluoromethyl)pyridine, (1.19 ± 0.25) × 10?10 for diethylamine, and (1.76 ± 0.38) × 10?12 for 1,1,3,3,3‐pentamethyldisiloxan‐1‐ol, where the indicated errors are the estimated overall uncertainties including those in the rate constants for the reference compounds. No reaction of 2‐methoxy‐6‐(trifluoromethyl)pyridine with gaseous nitric acid was observed, and an upper limit to the rate constant for the reaction of 1,1,3,3,3‐pentamethyldisiloxan‐1‐ol with O3 of <7 × 10? 20 cm3 molecule?1 s?1 was determined. Using a 12‐h average daytime OH radical concentration of 2 × 106 molecule cm?3, the lifetimes of the volatile organic compounds studied here with respect to reaction with OH radicals are 7.5 days for 2‐methoxy‐6‐(trifluoromethyl)pyridine, 1.2 h for diethylamine, and 6.6 days for 1,1,3,3,3‐pentamethyldisiloxan‐1‐ol. Likely reaction mechanisms are discussed. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 631–638, 2011  相似文献   

8.
We report an experimental study on the effect of solvents on the model SNAr reaction between 1‐chloro‐2,4‐dinitrobenzene and morpholine in a series of pure ionic liquids (IL). A significant catalytic effect is observed with reference to the same reaction run in water, acetonitrile, and other conventional solvents. The series of IL considered include the anions, NTf2?, DCN?, SCN?, CF3SO3?, PF6?, and FAP? with the series of cations 1‐butyl‐3‐methyl‐imidazolium ([BMIM]+), 1‐ethyl‐3‐methyl‐imidazolium ([EMIM]+), 1‐butyl‐2,3‐dimethyl‐imidazolium ([BM2IM]+), and 1‐butyl‐1‐methyl‐pyrrolidinium ([BMPyr]+). The observed solvent effects can be attributed to an “anion effect”. The anion effect appears related to the anion size (polarizability) and their hydrogen‐bonding (HB) abilities to the substrate. These results have been confirmed by performing a comparison of the rate constants with Gutmann's donicity numbers (DNs). The good correlation between rate constants and DN emphasizes the major role of charge transfer from the anion to the substrate.  相似文献   

9.
Flow injection analysis with amperometric detection (FIA‐AD) at screen‐printed carbon electrodes (SPCEs) in optimum medium of Britton‐Robinson buffer (0.04 mol ? L?1, pH 2.0) was used for the determination of three tumor biomarkers (homovanillic acid (HVA), vanillylmandelic acid (VMA), and 5‐hydroxyindole‐3‐acetic acid (5‐HIAA)). Dependences of the peak current on the concentration of biomarkers were linear in the whole tested concentration range from 0.05 to 100 μmol ? L?1, with limits of detection (LODs) of 0.065 μmol ? L?1 for HVA, 0.053 μmol ? L?1 for VMA, and 0.033 μmol ? L?1 for 5‐HIAA (calculated from peak heights), and 0.024 μmol ? L?1 for HVA, 0.020 μmol ? L?1 for VMA, and 0.012 μmol ? L?1 for 5‐HIAA (calculated from peak areas), respectively.  相似文献   

10.
Weak intermolecular interaction in organic semiconducting molecular crystals plays an important role in molecular packing and electronic properties. Here, four five‐ring‐fused isomers were rationally designed and synthesized to investigate the isomeric influence of linear and angular shapes in affecting their molecular packing and resultant electronic properties. Single‐crystal field‐effect transistors showed mobility order of 5,7‐ICZ (3.61 cm2 V?1 s?1) >5,11‐ICZ (0.55 cm2 V?1 s?1) >11,12‐ICZ (ca. 10?5 cm2 V?1 s?1) and 5,12‐ICZ (ca. 10?6 cm2 V?1 s?1). Theoretical calculations based on density functional theory (DFT) and polaron transport model revealed that 5,7‐ICZ can reach higher mobilities than the others thanks to relatively higher hole transfer integral that links to stronger intermolecular interaction due to the presence of multiple NH???π and CH???π(py) interactions with energy close to common NH???N hydrogen bonds, as well as overall lower hole‐vibrational coupling owing to the absence of coupling of holes to low frequency modes due to better π conjugation.  相似文献   

11.
Protein separations in CZE suffer from nonspecific adsorption of analytes to the capillary surface. Semipermanent phospholipid bilayers have been used to minimize adsorption, but must be regenerated regularly to ensure reproducibility. We investigated the formation, characterization, and use of hybrid phospholipid bilayers (HPBs) as more stable biosurfactant capillary coatings for CZE protein separations. HPBs are formed by covalently modifying a support with a hydrophobic monolayer onto which a self‐assembled lipid monolayer is deposited. Monolayers prepared in capillaries using 3‐cyanopropyldimethylchlorosilane (CPDCS) or n‐octyldimethylchlorosilane (ODCS) yielded hydrophobic surfaces with lowered surface free energies of 6.0 ± 0.3 or 0.2 ± 0.1 mJ m?2, respectively, compared to 17 ± 1 mJ m?2 for bare silica capillaries. HPBs were formed by subsequently fusing vesicles comprised of 1,2‐dilauroyl‐sn‐glycero‐3‐phosphocholine or 1,2‐dioleoyl‐sn‐glycero‐3‐phosphocholine to CPDCS‐ or ODCS‐modified capillaries. The resultant HPB coatings shielded the capillary surface and yielded reduced electroosmotic mobility (1.3–1.9 × 10?4 cm2 V?1s?1) compared to CPDCS‐ and ODCS‐modified or bare capillaries (3.6 ± 0.2 × 10?4 cm2 V?1s?1, 4.8 ± 0.4 × 10?4 cm2 V?1s?1, and 6.0 ± 0.2 × 10?4 cm2 V?1s?1, respectively), with increased stability compared to phospholipid bilayer coatings. HPB‐coated capillaries yielded reproducible protein migration times (RSD ≤ 3.6%, n ≥ 6) with separation efficiencies as high as 200 000 plates/m.  相似文献   

12.
The gas‐phase elimination kinetics of the above‐mentioned compounds were determined in a static reaction system over the temperature range of 369–450.3°C and pressure range of 29–103.5 Torr. The reactions are homogeneous, unimolecular, and obey a first‐order rate law. The rate coefficients are given by the following Arrhenius expressions: ethyl 3‐(piperidin‐1‐yl) propionate, log k1(s?1) = (12.79 ± 0.16) ? (199.7 ± 2.0) kJ mol?1 (2.303 RT)?1; ethyl 1‐methylpiperidine‐3‐carboxylate, log k1(s?1) = (13.07 ± 0.12)–(212.8 ± 1.6) kJ mol?1 (2.303 RT)?1; ethyl piperidine‐3‐carboxylate, log k1(s?1) = (13.12 ± 0.13) ? (210.4 ± 1.7) kJ mol?1 (2.303 RT)?1; and 3‐piperidine carboxylic acid, log k1(s?1) = (14.24 ± 0.17) ? (234.4 ± 2.2) kJ mol?1 (2.303 RT)?1. The first step of decomposition of these esters is the formation of the corresponding carboxylic acids and ethylene through a concerted six‐membered cyclic transition state type of mechanism. The intermediate β‐amino acids decarboxylate as the α‐amino acids but in terms of a semipolar six‐membered cyclic transition state mechanism. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 38: 106–114, 2006  相似文献   

13.
Conjugated molecules with low lying LUMO levels are demanding for the development of air stable n‐type organic semiconductors. In this paper, we report a new A‐D‐A′‐D‐A conjugated molecule ( DAPDCV ) entailing diazapentalene (DAP) and dicyanovinylene groups as electron accepting units. Both theoretical and electrochemical studies manifest that the incorporation of DAP unit in the conjugated molecule can effectively lower the LUMO energy level. Accordingly, thin film of DAPDCV shows n‐type semiconducting behavior with electron mobility up to 0.16 cm2?V?1?s?1 after thermal annealing under N2 atmosphere. Moreover, thin film of DAPDCV also shows stable n‐type transporting property in air with mobility reaching 0.078 cm2?V?1?s?1.  相似文献   

14.
Sunscreen agents and in particular UV filters are compounds added in different cosmetic formulations, that has the function of preventing damage caused by sun exposition. Therefore, this paper proposes the development of a simple, fast and reliable electroanalytical method utilizing square wave voltammetry (SWV) to the determination of Benzophenone‐3 (BZ‐3), camphor 4‐methylbenzylidene (MBC) and 2‐ethylhexyl‐4‐methoxycinnamate (OMC) in cosmetic samples. The electrochemical system consisted of a cell with three electrodes: work – gold electrode modified, reference – Ag/AgCl(sat) and auxiliary – platinum, using as supporting electrolyte 4.0 mL of Britton Robinson Buffer 0.04 mol L?1 (pH=4.0), 1.0 mL of methanol and 5.50×10?4 mol L?1 of cetyltrimethylammonium bromide (CTAB). The method was validated using three commercial sunscreen samples and the results showed recovery values between 83 and 98 %. The average values found for the analysed samples were 3.49 % m/m (728 mg L?1) to BZ‐3, 0.56 % m/m (113 mg L?1) to MBC and 0.99 % m/m (208 mg L?1) to OMC. The detection (DL) and quantification (QL) limits were 0.47 mg L?1 and 1.56 mg L?1 to BZ‐3, 0.77 mg L?1 and 2.58 mg L?1 to MBC and 0.78 mg L?1 and 2.59 mg L?1 to OMC, respectively. The sunscreen protector samples were also evaluated by high‐performance liquid chromatography (HPLC) demonstrating a good correlation between the results and compared the results with allowed concentration.  相似文献   

15.
Two novel larger azaacenes with six or ten N atoms in their backbones, benzannelated 9,11,13,22,24,26‐hexazatetrabenzo[a,c,l,n]heptacene ( HATBH , 1 ) and benzannelated 9,26‐dihydro‐9,11,13,22,24,26‐hexaza‐tetrapyrido[3,2‐a: 2′,3′‐c: 3′′,2′′‐l: 2′′′,3′′′‐n]heptacene ( DHATPH, 2 ), have been successfully synthesized in two steps. The theoretical band gaps estimated through DFT calculations for HATBH ( 1 ) and DHATPH ( 2 ) are 1.949 eV and 2.278 eV, which are close to the experimentally obtained optical band gaps (2.14 eV and 2.39 eV). Interestingly, HATBH ( 1 ) can act as efficient anion sensor for F? and H2PO4?, while DHATPH ( 2 ) selectively responds to F? among the ten different anions used (F?, Cl?, Br?, I?, PF6?, HSO4?, NO3?, BF4?, AcO?, and H2PO4?). Our synthetic strategy could offer a promising and easy way to obtain even larger azaacenes.  相似文献   

16.
An imidazolium‐modified hexa‐peri‐hexabenzocoronene derivative (HBC‐C11‐MIM[Cl?]) was designed and synthesized as a stabilizer to fabricate reduced graphene oxide (RGO). The resulting RGO/HBC‐C11‐MIM[Cl?] hybrid shows excellent dispersivity (5.0 mg mL?1) and stability in water. RGO/HBC‐C11‐MIM[Cl?] was comprehensively characterized by using atomic force microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, thermogravimetric analysis, and Raman spectroscopy, thus revealing that one HBC‐C11‐MIM[Cl?] group can stabilize about 178 carbon atoms on the graphene sheets. The obtained hybrid film exhibits a high conductivity of 286 S m?1. Furthermore, the HBC‐C11‐MIM[Cl?]‐modified RGO sheets can be readily dispersed in polar organic solvents upon exchange of the hydrophilic Cl? ions for hydrophobic bis(trifluoromethylsulfonyl) amide (NTf2?) ions.  相似文献   

17.
Methods to synthesize crystalline covalent triazine frameworks (CTFs) are limited and little attention has been paid to development of hydrophilic CTFs and photocatalytic overall water splitting. A route to synthesize crystalline and hydrophilic CTF‐HUST‐A1 with a benzylamine‐functionalized monomer is presented. The base reagent used plays an important role in the enhancement of crystallinity and hydrophilicity. CTF‐HUST‐A1 exhibits good crystallinity, excellent hydrophilicity, and excellent photocatalytic activity in sacrificial photocatalytic hydrogen evolution (hydrogen evolution rate up to 9200 μmol g?1 h?1). Photocatalytic overall water splitting is achieved by depositing dual co‐catalysts in CTF‐HUST‐A1, with H2 evolution and O2 evolution rates of 25.4 μmol g?1 h?1 and 12.9 μmol g?1 h?1 in pure water without using sacrificial agent.  相似文献   

18.
Two‐dimensional (2D) nanomaterials are one of the most promising types of candidates for energy‐storage applications due to confined thicknesses and high surface areas, which would play an essential role in enhanced reaction kinetics. Herein, a universal process that can be extended for scale up is developed to synthesise ultrathin cobalt‐/nickel‐based hydroxides and oxides. The sodium and lithium storage capabilities of Co3O4 nanosheets are evaluated in detail. For sodium storage, the Co3O4 nanosheets exhibit excellent rate capability (e.g., 179 mA h g?1 at 7.0 A g?1 and 150 mA h g?1 at 10.0 A g?1) and promising cycling performance (404 mA h g?1 after 100 cycles at 0.1 A g?1). Meanwhile, very impressive lithium storage performance is also achieved, which is maintained at 1029 mA h g?1 after 100 cycles at 0.2 A g?1. NiO and NiCo2O4 nanosheets are also successfully prepared through the same synthetic approach, and both deliver very encouraging lithium storage performances. In addition to rechargeable batteries, 2D cobalt‐/nickel‐based hydroxides and oxides are also anticipated to have great potential applications in supercapacitors, electrocatalysis and other energy‐storage‐/‐conversion‐related fields.  相似文献   

19.
A new type anion receptors containing indeno[2′,1′:5,6]pyrido[2,3‐d]pyrimidine have been synthesized via three‐component reaction of aldehyde, 6‐aminopyrimidine‐2,4‐dione, and 1,3‐indanedione in aqueous media. The binding properties of the receptors with anions such as F?, Cl?, Br?, AcO?, HSO4?, and H2PO4? have been investigated by UV–vis spectroscopy methods. The results have shown that receptors have good selectivity to F? and AcO?, and a 1:1 stoichiometry complex has been formed between compounds and anions.  相似文献   

20.
A novel peroxyoxalate chemiluminescence system has been designed for the determination of Triton X‐100 (TX‐100), in which a hydrophobic fluorescent conjugated polymer, poly[2,5‐bisnonyloxy‐1,4‐phenylene‐ethynylene‐9,10‐anthrylene] (PPEA) was employed as a fluorophor. A strong enhanced intensity of chemiluminescence (CL) was observed in the presence of TX‐100, due to the improved emission efficiency of PPEA in the presence of TX‐100. Under optimum conditions, the detection range of Triton X‐100 is between 1.0×10?7 and 1.0× 10?4 mol·L?1, with a detection limit at 6.0×10?8 mol·L?1. The relative standard deviation is 2.4% (n=6) for 1.0×10?6 mol·L?1 Triton X‐100. This method provides satisfying results in the detection of TX‐100 in nature water and biological samples with high sensitivity and wide linear range.  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