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1.
Synthesis and characterization of a novel double-tailed cationic surfactant   总被引:2,自引:0,他引:2  
A novel double-tailed cationic surfactant, N,N′-didodecylacetamidinium bicarbonate, was prepared by reacting dimethylacetamide dimethyl acetal with dodecylamine, followed by reacting with dry ice. MSD, FTIR, 1H NMR, 13C NMR, 2D-NMR were used to confirm its structure. The surfactant reduced the surface tension of pure water to 24.7 mN m−1 and its critical micelle concentration was 8.75 × 10−5 M. Formation of vesicle was also observed.  相似文献   

2.
Pulse radiolysis transient UV–visible absorption spectroscopy was used to study the UV–visible absorption spectrum (225–575 nm) of the phenyl radical, C6H5(), and kinetics of its reaction with NO. Phenyl radicals have a strong broad featureless absorption in the region of 225–340 nm. In the presence of NO phenyl radicals are converted into nitrosobenzene. The phenyl radical spectrum was measured relative to that of nitrosobenzene. Based upon σ(C6H5NO)270 nm=3.82×10−17 cm2 molecule−1 we derive an absorption cross-section for phenyl radicals at 250 nm, σ(C6H5())250 nm=(2.75±0.58)×10−17 cm2 molecule−1. At 295 K in 200–1000 mbar of Ar diluent k(C6H5()+NO)=(2.09±0.15)×10−11 cm3 molecule−1 s−1.  相似文献   

3.
New 1-acyl-1,2,4-triazoles (ATs) with different n-alkyl chain lengths from C2 to C18 were synthesized. ATs with long n-alkyl chains (C12 and larger) are non-charged amphiphilic molecules with a polar triazole head group. The Langmuir isotherms of ATs at the air–water interface with 12 (DoT-C12), 14 (MyT-C14), 16 (PaT-C16) and 18 (StT-C18) carbon atoms in their n-alkyl chains were studied using surface pressure-mean molecular area (π-mmA) measurements. Characteristic for the Langmuir isotherms of PaT-C16 and StT-C-18 was the first sharp increase of the surface pressure at a mmA value of 20 Å2 marking a transition of the ATs from the gaseous state with n-alkyl chains already oriented perpendicular to the water surface to a condensed state. The collapse of the monolayers occurred between 20 and 36 mN m−1 with a typical ‘spike’ in the isotherms of MyT-C14, PaT-C16 and StT-C18 which can be assigned to the buckling and subsequent folding of the monolayer. After the collapse point a pseudo-plateau region of slightly increasing surface pressure appeared for all ATs from C12 to C18 indicating a trilayer formation by the roll-over mechanism for MyT-C14, PaT-C16 and StT-C18. Upon further compression the final collapse occurred at π values between 59 and 67 mN m−1. From reversibility studies it was found that the Langmuir isotherms of the ATs were irreversible. The morphology of Langmuir–Blodgett films of ATs transferred onto silicon wafers was studied by atomic force microscopy.  相似文献   

4.
The hydrogen abstraction reaction of 1,1,1,2-tetrafluoroethane (HFC-134a) by chlorine radical is investigated by theoretical calculations. Equilibrium geometries and harmonic vibrational frequencies of the reactants, transition state, and products are calculated using high-level ab initio methods. Rate constants of forward and backward reactions for the temperatures from 200 to 1000 K are calculated using classical transition state theory with Eckart tunneling correction, fitted in the expressions kf (T) = 1.19 × 10−23T3.93exp (−1110/T), and kb (T) = 8.86 × 10−24T3.32exp (−959/T) cm3 molecule−1 s−1 for forward and backward reactions, respectively, and are in reasonable agreement with the available experimental values.  相似文献   

5.
Room temperature rate coefficients and product distributions are reported for the reactions initiated in D2O with dications of the alkaline-earth metals Mg, Ca, Sr and Ba. The measurements were performed with a selected-ion flow tube (SIFT) tandem mass spectrometer and electrospray ionization (ESI). Mg2+ reacts with water by a fast electron transfer leading to charge separation with a rate coefficient of 1.4 × 10−9 cm3 molecule−1 s−1. Ca2+ reacts with D2O in a first step to form the adduct Ca2+(D2O), with an effective bimolecular rate coefficient of 2.3 × 10−11 cm3 molecule−1 s−1, which then undergoes rapid charge separation by deuteron transfer to form CaOD+ and D3O+ in a second step with k = 7.9 × 10−10 cm3 molecule−1 s−1. The CaOD+ ion reacts further by clustering up to five more D2O molecules. Sr2+ clusters up to eight D2O molecules and Ba2+ up to seven D2O molecules, with the first addition of D2O being rate determining in each case and the last addition being distinctly slower, as might be expected from a transition in the occupation of the added water molecules from an inner to an outer hydration shell.  相似文献   

6.
Enthalpies for the two proton ionizations of the biochemical buffers N-tris(hydroxymethyl)methyl-4-aminobutanesulfonic acid (TABS), N-tris(hydroxymethyl)methyl-3-aminopropanesulfonic acid (TAPS) and 3-[N-tris(hydroxymethyl)methylamino]-2-hyroxypropane sulfonic acid (TAPSO) were obtained in water–methanol mixtures with methanol mole fraction (Xm) from 0 to 0.360. The ionization enthalpy for the first proton (ΔH1) of all three buffers was small and exhibited slight changes upon methanol addition. The ionization enthalpy of the second proton (ΔH2) of TABS increased from 39.6 to 49.8 kJ mol−1 and for TAPS from 40.1 to 43.2 kJ mol−1, with a minimum of 38.2 kJ mol−1 at Xm = 0.059. For TAPSO the increase was from 33.1 to 35.6 kJ mol−1 at Xm = 0.194, with measurements at higher Xm precluded by low solubility of TAPSO in methanol rich solvents. The solvent composition was selected so as to include the region of maximum structure enhancement of water by methanol. The results were interpreted in terms of solvent–solvent and solvent–solute interactions.  相似文献   

7.
Glasses with nominal compositions SrFe10Al2O19+4(SrB2O4+Sr2B2O5) (1) and SrFe9Al3O19+4(SrB2O4+Sr2B2O5) (2) were prepared by rapid quenching of melts. Thermal treatment of glass samples at 600–900 °C resulted in crystallization of the magnetic phase SrFe12−x AlxO19 (x = 1.1±0.1) and strontium borates. Platelet hexaferrite particles with average sizes from (250×60) nm2 to (450×140) nm2 were prepared. The coercive force of glass ceramics is 580 and 475 kA m−1 for glasses 1 and 2, respectively. The coercive force of 580 kA m−1 is the highest known value compared to hexaferrite particles prepared earlier by glass crystallization.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 74–77, January, 2005.  相似文献   

8.
Four multifunctional 8-hydroxyquinoline derivatives were designed and synthesized, their structures were identified by FT-IR, 1H NMR, MS and elemental analysis. Among them are (E)-2-(2-(9-(4-methoxyphenyl)-9H-carbazol-3-yl)vinyl) quinolato-zinc (1), (E)-2-(2-(9-p-tolyl-9H-carbazol-3-yl)vinyl)quinolato-zinc (2), (E)-2-(2-(9H-fluoren-2-yl)vinyl)quinolato-zinc (3), and (E)-2-(2-(phenanthren-9-yl)vinyl)quinolato-zinc (4). The electroluminescence (EL) and hole-transporting characteristics of these materials were investigated on four configurations: (A) ITO/2-TNATA/NPB/1, 2, 3 or 4/Alq3/LiF/Al; (B) ITO/2-TNATA/NPB/1, 2, 3 or 4/LiF/Al; (C) ITO/2-TNATA/1, 2, 3 or 4/Alq3/LiF/Al; and (D) ITO/2-TNATA/1 or 2/NPB/Alq3/LiF/Al. The maximum luminescence and current efficiencies of are 3556 cd m−2 (at 13 V) and 2.17 cd A−1 (at 9 V) for compound 2, 4624 cd m−2 (at 15 V) and 2.1 cd A−1 (at 7 V) for compound 3, and 3164 cd m−2 (at 14 V) and 1.83 cd A−1 (at 13 V) for compound 4 in the configuration D, respectively, indicating that they are good multifunctional materials with strong hole-transporting abilities and luminescence properties.  相似文献   

9.
Plots of surface pressuer (π) vs surface area (A) are taken from mixed monolayers of dipalmitoylphosphatidylcholine (DPPC) and “egg” phosphatidylglycerol (egg PG) with the concentration of egg PG (X) ranging from 0 to 100%, the temperatures (T) from 37 to 41°C, and the compression rate (dA/dt) from −13.6 to −688 mm2s, and at a relative humidity of over 90%. Between limiting values of X, T, and dA/dt the π-A plots of compression show regions of nearly constant π (plateaus) which start at values of π (πpb) of 48 ± 2 mN m−1, and which can be followed by an increase in π until collapse occurs at 70 mN m−1. πpb is independent of X, T, and dA/dt. The plateau is correlated with a loss of molecules from the monolayer, which increases strongly with X and T and decreases with dA/dt. The quantitative results are not in agreement with separate collapse of the components. A model is presented stating that plateaus occur when the transition from the liquid-expanded (LE) to the liquid-condensed phase (LC) is incomplete at πpb. During plateau formation a mixed LE phase is squeezed out at its collapse pressure. The remaining LC phase can be compressed to 70 mN m−1. Results of calculations based on this model are in agreement with the experimental results and predict slight enrichment of the squeezed-out phase with respect to egg PG.  相似文献   

10.
The molecular structures, vibrational frequencies, and electron affinities of the SF5On/SF5On (n = 1–3) species have been examined with four hybrid density functional theory (DFT) methods. The basis set used in this work is of double-ζ plus polarization quality with additional diffuse s- and p-type functions, denoted DZP++. The geometries are fully optimized with each DFT method independently. The SF5On (n = 1–3) species should be potential greenhouse gases. The anion SF5O2 with Cs symmetry has a 3A″ electronic state, and the neutral SF5O3 with 2A″ electronic state has Cs symmetry. The anions SF5O2 and SF5O3 should be regarded as SF5·O2 and SF5O·O2 complexes, respectively. Three different types of the neutral–anion energy separation presented in this work are the adiabatic electron affinity (EAad), the vertical electron affinity (EAvert), and the vertical detachment energy (VDE). The EAad values predicted by the B3PW91 method are 5.22 (SF5O), 4.38 (SF5O2), and 3.61 eV (SF5O3). Compared with the experimental vibrational frequencies, the BHLYP method overestimates the frequencies, and the other three methods underestimate the frequencies. The bond dissociation energies De (SF5On → SF5Onm + Om) for the neutrals SF5On and De (SF5On → SF5Onm + Om and SF5On → SF5Onm + Om) for the anions SF5On are reported.  相似文献   

11.
Recombination of HCO+ and DCO+ ions with electrons was studied in afterglow plasma. The flowing afterglow with Langmuir probe (FALP) apparatus was used to measure the recombination rate coefficients and their temperature dependencies in the range 150–270 K. To obtain a recombination rate coefficient for a particular ion, the dependencies on partial pressures of gases used in the ion formation were measured. The variations of αHCO+(T) and αDCO+(T) seem to obey the power law: αHCO+(T) = (2.0 ± 0.6) × 10−7 (T/300)−1.3 cm3 s−1 and αDCO+(T) = (1.7 ± 0.5) × 10−7 (T/300)−1.1 cm3 s−1 over the studied temperature range.  相似文献   

12.
In this response to the comment by Caupin et al. [1] on our earlier paper, we explain why negative pressure in nanoscale water capillary bridges in AFM experiments is lower than the pressure reported in macroscale and microscale experiments. An estimate shows that for the tip radius of 10 nm, the bridge foundation area (A) is on the order of A = 10−16 m2, and the typical experimental value of the capillary force (Fad) on the order of Fcap = 10 nN corresponds to the negative pressure P = −Fcap/A = −100 MPa.  相似文献   

13.
The basic copper arsenate mineral strashimirite Cu8(AsO4)4(OH)4·5H2O from two different localities has been studied by Raman spectroscopy and complemented by infrared spectroscopy. Two strashimirite mineral samples were obtained from the Czech (sample A) and Slovak (sample B) Republics. Two Raman bands for sample A are identified at 839 and 856 cm−1 and for sample B at 843 and 891 cm−1 are assigned to the ν1 (AsO43−) symmetric and the ν3 (AsO43−) antisymmetric stretching modes, respectively. The broad band for sample A centred upon 500 cm−1, resolved into component bands at 467, 497, 526 and 554 cm−1 and for sample B at 507 and 560 cm−1 include bands which are attributable to the ν4 (AsO43−) bending mode. In the Raman spectra, two bands (sample A) at 337 and 393 cm−1 and at 343 and 374 cm−1 for sample B are attributed to the ν2 (AsO43−) bending mode. The Raman spectrum of strashimirite sample A shows three resolved bands at 3450, 3488 and 3585 cm−1. The first two bands are attributed to water stretching vibrations whereas the band at 3585 cm−1 to OH stretching vibrations of the hydroxyl units. Two bands (3497 and 3444 cm−1) are observed in the Raman spectrum of B. A comparison is made of the Raman spectrum of strashimirite with the Raman spectra of other selected basic copper arsenates including olivenite, cornwallite, cornubite and clinoclase.  相似文献   

14.
The kinetics of phenylalanine (phe) oxidation by permanganate has been investigated in absence and presence of cetlytrimethylammonium bromide (CTAB) using conventional spectrophotometric technique. The rate shows first- and fractional-order dependence on [MnO4] and [phe] in presence of CTAB. At lower values of [CTAB] (≤10.0 × 10−4 mol dm−3), the catalytic ability of CTAB aggregates are strong. In contrast, at higher values of [CTAB] (≥10.0 × 10−4 mol dm−3), the inhibitory effect was observed in absence of H2SO4. We find that anions (Br, Cl and NO3) in the form of sodium salts are strong inhibitors for the CTAB catalyzed oxidation. Kinetic and spectrophotometric evidences for the formation of an intermediate complex and an ion-pair complex between phe and MnO4, CTAB and MnO4, respectively, are presented. A mechanism consistent with kinetic results has been discussed. Complex formation constant (Kc) and micellar binding constant (Ks) were calculated at 30 °C and found to be Kc = 319 mol−1 dm−3 and Ks = 1127 mol−1 dm−3, respectively.  相似文献   

15.
Dynamic interfacial tension between aqueous solutions of 3-dodecyloxy-2-hydroxypropyl trimethyl ammonium bromide (R12HTAB) and n-hexane were measured using the spinning drop method. The effects of the R12HTAB concentration (the concentration below the CMC) and temperature on the dynamic interfacial tension have been investigated; the reason of the change of dynamic interfacial tension with time has been discussed. The effective diffusion coefficient, Da, and the adsorption barrier, a, have been obtained from the experimental data using the extended Word–Tordai equation. The results show that the dynamic interfacial tension becomes smaller while a becomes higher with increasing R12HTAB concentration in the bulk aqueous phase. Da decreases from 5.56 × 10−12 m−2 s−1 to 0.87 × 10−12 m−2 s−1 while a increases from 5.41 kJ mol−1 to 7.74 kJ mol−1 with the increase of concentration in the bulk solution of R12HTAB from 0.5 × 10−3 mol dm−3 to 4 × 10−3 mol dm−3. Change of temperature affects the adsorption rate through altering Da and a. The value of Da increases from 5.56 × 10−12 m−2 s−1 to 13.98 × 10−12 m−2 s−1 while that of a decreases from 5.41 kJ mol−1 to 5.07 kJ mol−1 with temperature ascending from 303 K to 323 K. The adsorption of surfactant from the bulk phase into the interface follows a mixed diffusion–activation mechanism, which has been discussed in the light of interaction between surfactant molecules, diffusion and thermo-motion of molecules.  相似文献   

16.
Removal of the drug Gemfibrozil (GEM), as a target molecule, from aqueous media by using a carrier mediated transport in supported liquid membrane (SLM) and Stagnant Sandwich LM (SSwLM) systems has been investigated. Optimal chemical conditions to use in the transport tests were determined by means of solubility and liquid–liquid extraction tests. The results showed that the best LM phase to realize stable LM systems was tributylphosphate (TBP) 30% (v/v) in n-decane. Transport tests by using the “traditional” SLM system showed an average flux JAV(0–CTT) of 0.421 mmol h−1 m−2 and a system stability of 1410 min. Three different microfiltration membranes, GH-Polypro, FP-Vericel and Supor 200, made of polypropylene, polyvinylidene fluoride and polyethersulphone polymers, respectively, were used to assemble the SSwLM. Contact angle and adsorption measurements evidenced hydrophilic/lypophilic character of the supports. The best results in terms of average flux (0.873 mmol h−1 m−2), permeability coefficient (21.88 L h−1 m−2) and stability (7170 min ≈120 h) were obtained by using the SSwLM made with the Supor 200 support. The overall results showed that the SSwLM made with this type of support achieves both high flux and high stability compared to the SLM. Thus SSwLMs seems very interesting to employ transport in LM for removing molecular species (e.g. drugs) from aqueous solutions.  相似文献   

17.
Wang X  Zhao X  Liu X  Li Y  Fu L  Hu J  Huang C 《Analytica chimica acta》2008,620(1-2):162-169
In this study, a new method was developed for analyzing malathion, cypermethrin and lambda-cyhalothrin from soil samples by using homogeneous liquid–liquid extraction (HLLE) and gas chromatography with electron capture detector (GC–ECD). Acetone was used as extraction solvent for the extraction of target pesticides from soil samples. When the extraction process was finished, the target analytes in the extraction solvent were rapidly transferred from the acetone extract to carbon tetrachloride, using HLLE. Under the optimum conditions, linearity was obtained in the range of 0.05–40 μg kg−1 for malathion, 0.04–10 μg kg−1 for lambda-cyhalothrin and 0.05–50 μg kg−1 for cypermethrin, respectively. Coefficients of correlation (r2) ranged from 0.9993 to 0.9998. The repeatability was carried out by spiking soil samples at concentration levels of 2.5 μg kg−1 for lambda-cyhalothrin, and 10 μg kg−1 for malathion and cypermethrin, respectively. The relative standard deviations (RSDs) varied between 2.3 and 9.6% (n = 3). The limits of detection (LODs), based on signal-to-noise ratio (S/N) of 3, varied between 0.01 and 0.04 μg kg−1. The relative recoveries of three pesticides from soil A1, A2 and A3 at spiking levels of 2.5, 5 and 10 μg kg−1 were in the range of 82.20–91.60%, 88.90–110.5% and 77.10–98.50%, respectively. In conclusion, the proposed method can be successfully applied for the determination of target pesticide residues in real soil samples.  相似文献   

18.
The kinetics of the CCl2 + Br2 and CCl2 + NO2 reactions have been studied at temperatures between 266 and 365 K using laser photolysis/photoionization mass spectrometry. Dichloromethylene biradicals were produced by the pulsed laser photolysis of CCl4. The bimolecular rate coefficients of the CCl2 + Br2 reaction can be described by the Arrhenius expression k1 = (7.05 ± 1.75) × 10−12 exp[(3.52 ± 0.63) kJ mol−1/RT] cm3 molecule−1 s−1. CCl2Br was observed as a primary product of this reaction. Interestingly, the bimolecular rate coefficients of the CCl2 + NO2 reaction were observed to depend weakly on the bath gas density and to possess a negative temperature dependence.  相似文献   

19.
The photochemical, photophysical and photobiological studies of a mixture containing cis-[Ru(H-dcbpy)2(Cl)(NO)] (H2-dcbpy = 4,4′-dicarboxy-2,2′-bipyridine) and Na4[Tb(TsPc)(acac)] (TsPc = tetrasulfonated phthalocyanines; acac = acetylacetone), a system capable of improving photodynamic therapy (PDT), were accomplished. cis-[Ru(H-dcbpy)2(Cl)(NO)] was obtained from cis-[Ru(H2-dcbpy)2Cl2]·2H2O, whereas Na4[Tb(TsPc)(acac)] was obtained by reacting phthalocyanine with terbium acetylacetonate. The UV–Vis spectrum of cis-[Ru(H-dcbpy)2(Cl)(NO)] displays a band in the region of 305 nm (λmax in 0.1 mol L−1 HCl)(π–π*) and a shoulder at 323 nm (MLCT), while the UV–Vis spectrum of Na4[Tb(TsPc)(acac)] presents the typical phthalocyanine bands at 342 nm (Soret λmax in H2O) and 642, 682 (Q bands). The cis-[Ru(H-dcbpy)2(Cl)(NO)] FTIR spectrum displays a band at 1932 cm−1 (Ru–NO+). The cyclic voltammogram of the cis-[Ru(H-dcbpy)2(Cl)(NO)] complex in aqueous solution presented peaks at E = 0.10 V (NO+/0) and E = −0.50 V (NO0/−) versus Ag/AgCl. The NO concentration and 1O2 quantum yield for light irradiation in the λ > 550 nm region were measured as [NO] = 1.21 ± 0.14 μmol L−1 and øOS = 0.41, respectively. The amount of released NO seems to be dependent on oxygen concentration, once the NO concentration measured in aerated condition was 1.51 ± 0.11 μmol L−1 The photochemical pathway of the cis-[Ru(H-dcbpy)2(Cl)(NO)]/Na4[Tb(TsPc)(acac)] mixture could be attributed to a photoinduced electron transfer process. The cytotoxic assays of cis-[Ru(H-dcbpy-)2(Cl)(NO)] and of the mixture carried out with B16F10 cells show a decrease in cell viability to 80% in the dark and to 20% under light irradiation. Our results document that the simultaneous production of NO and 1O2 could improve PDT and be useful in cancer treatment.  相似文献   

20.
The heat capacity and the enthalpy increments of strontium niobate Sr2Nb2O7 and calcium niobate Ca2Nb2O7 were measured by the relaxation time method (2–300 K), DSC (260–360 K) and drop calorimetry (720–1370 K). Temperature dependencies of the molar heat capacity in the form Cpm = 248.0 + 0.04350T − 3.948 × 106/T2 J K−1 mol−1 for Sr2Nb2O7 and Cpm = 257.2 + 0.03621T − 4.434 × 106/T2 J K−1 mol−1 for Ca2Nb2O7 were derived by the least-square method from the experimental data. The molar entropies at 298.15 K, Sm°(298.15 K) = 238.5 ± 1.3 J K−1 mol−1 for Sr2Nb2O7 and Sm°(298.15 K) = 212.4 ± 1.2 J K−1 mol−1 for Ca2Nb2O7, were evaluated from the low-temperature heat capacity measurements.  相似文献   

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