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1.
The five-coordinate mono-halide mononuclear Zn(II) complexes [Zn(tpa)X]+ (tpa = tris(2-pyridylmethyl)amine; X = I ([Zn(tpa)I]I; 1a), Br ([Zn(tpa)Br](ZnBr4)0.5; 2a) and Cl ([Zn(tpa)Cl](ZnCl4)0.5; 3a)) and the six-coordinate mononuclear complex [Zn(tpa)(NCS)2] (4a) have been synthesized and characterized by X-ray crystallography. The [Zn(tpa)X]+ complexes doped with the corresponding [Mn(tpa)X2] complexes (X = I (1b), Br (2b) and Cl (3b)) have been synthesized and their electronic properties investigated by multifrequency high field EPR (HF-EPR) (95–285 GHz). The magnetically diluted conditions allow the determination of the hyperfine coupling constant A (A = 68.10−4 cm−1 for 1b–3b). The zero-field splitting parameters (D and E) found for 1b–3b are comparable to those found for neat samples of the [Mn(tpa)X2] complexes (1b: D = 0.635 cm−1, E/D = 0.189; 2b: D = 0.360 cm−1, E/D = 0.192; 3b: D = 0.115 cm−1, E/D = 0.200). The efficacy of using multifrequency EPR under dilute conditions to precisely determine spin Hamiltonian parameters is discussed.  相似文献   

2.
This work discusses pulsed electric fields (PEF) induced effects in treatment of aqueous suspensions of concentrated yeast cells (S. cerevisiae). The PEF treatment was done using pulses of near-rectangular shape, electric field strength was within E=2-5 kV/cm and the total time of treatment was t(PEF)=10(-4)-0.1 s. The concentration of aqueous yeast suspensions was in the interval of C(Y)=0-22 (wt%), where 1% concentration corresponds to the cellular density of 2x10(8) cells/mL. Triton X-100 was used for studying non-ionic surfactant additive effects. The electric current peak value I was measured during each pulse application, and from these data the electrical conductivity sigma was estimated. The PEF-induced damage results in increase of sigma with t(PEF) increasing and attains its saturation level sigma approximately sigma(max) at long time of PEF treatment. The value of sigma(max) reflects the efficiency of damage. The reduced efficiency of damage at suspension volume concentration higher than phi(Y) approximately 32 vol% is explained by the percolation phenomenon in the randomly packed suspension of near-spherical cells. The higher cytoplasmic ions leakage was observed in presence of surfactant. Experiments were carried out in the static and continuous flow treatment chambers in order to reveal the effects of mixing in PEF-treatment efficiency. A noticeable aggregation of the yeast cells was observed in the static flow chamber during the PEF treatment, while aggregation was not so pronounced in the continuous flow chamber. The nature of the enhanced aggregation under the PEF treatment was revealed by the zeta-potential measurements: these data demonstrate different zeta-potential signs for alive and dead cells. The effect of the electric field strength on the PEF-induced extraction of the intracellular components of S. cerevisiae is discussed.  相似文献   

3.
Physico-chemical properties of the binary system NaHSO4–KHSO4 were studied by calorimetry and conductivity. The enthalpy of mixing has been measured at 505 K in the full composition range and the phase diagram calculated. The phase diagram has also been constructed from phase transition temperatures obtained by conductivity for 10 different compositions and by differential thermal analysis. The phase diagram is of the simple eutectic type, where the eutectic is found to have the composition X(KHSO4) = 0.44 (melting point ≈ 406 K). The conductivities in the liquid region have been fitted to polynomials of the form κ(X) = A(X) + B(X)(T − Tm) + C(X)(T − Tm)2, where Tm is the intermediate temperature of the measured temperature range and X, the mole fraction of KHSO4. The possible role of this binary system as a catalyst solvent is also discussed.  相似文献   

4.
The intensity I3 of ortho-positronium (o-Ps) in a polymer blend system consisting of polyethylene (PE) and ethylene-vinylacetate (EVA, random copolymer with a vinylacetate content of about 14%) was measured as functions of EVA weight content (Φ=0–100%), electric field (E=0–60 kV/cm ), positron irradiation time (t=0–200 h) and temperature (T=100–300 K). It was found that the addition of small amounts of EVA to PE significantly alters the electric field, positron irradiation time and temperature dependence of I3. Positron trapping on polar EVA is suggested to be responsible for the sensitive effects of EVA.  相似文献   

5.
As a step towards the modelling of binary metal alloys we here report on the shape of the phase boundary of two deionized charged sphere colloidal suspensions as a function of mixing ratio and particle density. Their size ratios are r = 0.68 and r = 0.56. Both aqueous suspensions of polystyrene copolymer spheres crystallize in a body-centred cubic structure. Interesting differences in the shape of the phase boundary are observed. In the first case a peaked increase of crystal stability was observed for a mixing ratio of p = 0.2–0.3, which gives the fraction of small spheres. Also in the second case the stability of the crystalline phase is larger than expected for an ideal solid solution but over a more extended range of small p. In addition at p = 0.7–0.8 we find a pronounced suppression of crystallization and furthermore some indications of a precipitation of one species at p = 0.9. While the first phase diagram resembles that of a solid solution with possibly the onset of compound formation, the second more resembles a eutectic.  相似文献   

6.
The structures of 3,3′-dicarbometoxy-2,2′-bipyridine (dcmbpy) complexes with copper(II) and silver(I) cations have been determined using single crystal X-ray-diffraction. The crystals of Cu(dcmbpy)Cl2 are monoclinic, C2/c, a = 16.966(3), b = 18.373(3), c = 13.154(2) Å, β = 126.543(3)°. The crystals of Ag(dcmbpy)NO3 · H2O are also monoclinic, C2/c, a = 16.7547(13), b = 11.0922(9), c = 18.7789(18) Å, β = 100.228(7)°. The results have been compared with the literature data on the complexes of dcmbpy and its precursors: 2,2′-bipyridine (bpy) and 3,3′-dicarboxy-2,2′-bipyridine (dcbpy). Two types of complexes of 3,3′-carboxy derivatives of bpy are distinguished: (1) with metal atom bonded to two N atoms of the same molecule and (2) with metal atom bonded to two N atoms of two different molecules. The Cu(dcmbpy)Cl2 complex belongs to the first type, whereas Ag(dcmbpy)NO3 · H2O belongs to the second type.  相似文献   

7.
For a small volume (of about 10−6 cm3) of NaCl and other electrolyte solutions (C = 0.1 and 1 M) in thin (r = 5/10 μm) single quartz capillaries, dependencies of the column length l of frozen solutions on the temperature t were measured using comparator IZA-2 in a thermostated chamber. At temperatures range t > −4 °C (for C = 0.1 M) and t > −8 °C (for C = 1 M) the l(t) dependencies are reversible and therefore correspond to establishment of an equilibrium between ice-1 and the solution.

From the constants mass condition of the dissolved salt in a frozen column, the l(t) expression was derived, which includes thermodynamic relation between solution concentration in an equilibrium with ice, Cs, and the temperature t for bulk systems. Deviations from the data known for bulk solutions were observed in thin capillaries when temperature t decreased to −3 °C (for 0.1 M NaCl) and to −6 °C for 1 M NaCl solution.

This effect may be a result of strong adhesion of the ice column to capillary walls. In this case, some internal stresses arise in frozen solution resulting in a deviation from thermodynamic equilibrium conditions for bulk systems. When approaching the temperature of ice melting, adhesion forces decrease due to formation of a thin non-freezing water interlayer on the capillary wall. In this temperature range the experimental data are in agreement with the predictions for bulk systems. It was supposed that the observed deviation in thin capillaries may be caused by formation of an amorphous ice phase with higher density as compared with the ice-1 during rapid freezing, or by an effect of ice microlenses formation. Both effects will result in a deviation from the phase diagram corresponding to a bulk solution.  相似文献   


8.
Dialkyl disulfide-linked naphthoquinone, (NQ-Cn-S)2, and anthraquinone, (AQ-Cn-S)2, derivatives with different spacer alkyl chains (Cn: n = 2, 6, 12) were synthesized and these quinone derivatives were self-assembled on a gold electrode. The formation of self-assembled monolayers (SAMs) of these derivatives on a gold electrode was confirmed by infrared reflection-absorption spectroscopy (IR-RAS). Electron transfer between the derivatives and the gold electrode was studied by cyclic voltammetry. On the cyclic voltammogram a reversible redox reaction between quinone (Q) and hydroquinone (QH2) was clearly observed under an aqueous condition. The formal potentials for NQ and AQ derivatives were −0.48 and −0.58 V, respectively, that did not depend on the spacer length. The oxidation and reduction peak currents were strongly dependent on the spacer alkyl chain length. The redox behavior of quinone derivatives depended on the pH condition of the buffer solution. The pH dependence was in agreement with a theoretical value of E1/2 (mV) = E′ − 59pH for 2H+/2e process in the pH range 3–11. In the range higher than pH 11, the value was estimated with E1/2 (mV) = E′ − 30pH , which may correspond to H+/2e process. The tunneling barrier coefficients (β) for NQ and AQ SAMs were determined to be 0.12 and 0.73 per methylene group (CH2), respectively. Comparison of the structures and the alkyl chain length of quinones derivatives on these electron transfers on the electrode is made.  相似文献   

9.
A coordination polymer was synthesized by the reaction of CoCl2 with 1,2,4-triazole-5-one (TO) and charaterized by means of IR and TG–DTG. Single-crystal structure analysis showed that the complex crystallized in the monoclinic space group C2/c: a = 23.105(9) Å, b = 3.5683(2) Å, c = 13.589(6) Å,  = 90°, β = 124.038(4)°, γ = 90°, V = 928.4(7) Å3, Z = 4. The standard molar enthalpy of formation of the complex was determined to be (−1034.28 ± 0.95) kJ mol−1.  相似文献   

10.
Mixtures of dioctadecyldimethylammonium chloride (DODAC) cationic vesicle dispersions with aqueous micelle solutions of the anionic sodium cholate (NaC) were investigated by differential scanning calorimetry, DSC, turbidity and light scattering. Within the concentration range investigated (constant 1.0 mM DODAC and varying NaC concentration up to 4 mM), vesicle → micelle → aggregate transitions were observed. The turbidity of DODAC/NaC/water depends on time and NaC/DODAB molar concentration ratio R. At equilibrium, turbidity initially decreases smoothly with R to a low value (owing to the vesicle–micelle transition) when R = 0.5–0.8 and then increases steeply to a high value (owing to the micelle–aggregate transition) when R = 0.9–1.0. DSC thermograms exhibit a single and sharp endothermic peak at Tm ≈ 49 °C, characteristic of the melting temperature of neat DODAC vesicles in water. Upon addition of NaC, Tm initially decreases to vanish around R = 0.5, and the main transition peak broadens as R increases. For R > 1.0 two new (endo- and exothermic) peaks appear at lower temperatures indicating the formation of large aggregates since the dispersion is turbid. All samples are non-birefringent. Dynamic light scattering (DLS) data indicate that both DODAC and DODAC/NaC dispersions are highly polydisperse, and that the mean size of the aggregates tends to decrease as R increases.  相似文献   

11.
In the present work temperature dependence of heat capacity of cesium tantalum tungsten oxide has been measured first in the range from 7 to 350 K and then between 330 and 630 K, respectively, by precision adiabatic vacuum and dynamic calorimetry. The experimental data were used to calculate standard thermodynamic functions, namely the heat capacity Cp° (T), enthalpy H°(T) − H°(0), entropy S°(T) − S°(0) and Gibbs function G°(T) − H°(0), for the range from T → 0 to 630 K. The structure of CsTaWO6 is refined by the Rietveld method: space group F d3m, Z = 8, a = 10.3793(2) Å, V = 1118.14(4) Å3. The high-temperature X-ray diffraction was used for the determination of temperature of phase transition and coefficient of thermal expansion.  相似文献   

12.
Synthesized hydrated lamellar acidic crystalline magadiite (H2Si14O29·2H2O) nanocompound was used as host for intercalation of polar n-alkylmonoamine molecules of the general formula H3C(CH2)nNH2 (n = 1–6) in aqueous solution. The original interlayer distance (d) of 1500 pm, determined by X-ray powder diffraction patterns, increases after intercalation. The values correlated with the number of aliphatic amine carbon (nc) atoms: d = [(1312 ± 11) + (21 ± 2)]nc. The amount of intercalated amines (Ns), decreased as nc increased: Ns = [(5.82 ± 0.04) − (0.45 ± 0.01)]nc. The acidic layered nanocompound was calorimetrically titrated with the amines and the thermodynamic data gave exothermic values for all guest molecules, as shown by the correlation: ΔintH = −[(24.45 ± 0.49) − (1.91 ± 0.10)]nc and d = [(1576 ± 16) − (10.8 ± 1.0)]ΔintH. The negative values of the Gibbs energies and the positive entropies also presented the correlations: ΔintG = −[(22.8 ± 0.2) − (0.2 ± 0.1)]nc and ΔintS = [(6 ± 1) + (5 ± 1)]nc, respectively.  相似文献   

13.
Reactions of CoX2·6H2O (X = Cl, ClO4) with bis(3,5-dimethylpyrazolyl)methane (dmpzm) and formic acid, acetic acid, benzoic acid, salicylic acid, maleic acid, or fumaric acid under the presence of KOH solution produced a new family of Co(II)/dmpzm complexes, [Co(dmpzm)2L]X·nH2O (1: L = O2CH, X = Cl, n = 2; 2: L = OAc, X = Cl, n = 3; 3: L = benzoate, X = ClO4, n = 1/3; 4: L = salicylate, X = ClO4, n = 1/3) and [Co2(dmpzm)4L](ClO4)2·nSolv (5: L = maleate, n = 3, Solv = H2O; 6: L = fumarate, n = 2, Solv = MeOH). These compounds were structurally characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Compounds 1–4 are mononuclear while 5–6 are binuclear. Each cobalt atom of 1–6 is hexacoordinate, with a distorted octahedral CoN4O2 coordination geometry incorporating two N,N′-bidentate dmpzm ligands and one O,O′-bidentate carboxylate ligand. There are rich intra- and intermolecular hydrogen bonds in the crystals of 1–6, thereby forming either 2D hydrogen-bonded networks (1 and 2) or 3D hydrogen-bonded networks (3–6). In addition, the thermal behaviors of 1–6 were also investigated.  相似文献   

14.
An improved flow-based procedure is proposed for turbidimetric sulphate determination in waters. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. Stable baselines were observed in view of the pulsed flow characteristic of the systems designed with solenoid micro-pumps, thus making the use of washing solutions unnecessary. The nucleation process was improved by stopping the flow prior to the measurement, thus avoiding the need of sulphate addition. When a 1-cm optical path flow cell was employed, linear response was achieved within 20–200 mg L−1, described by the equation S = −0.0767 + 0.00438C (mg L−1), r = 0.999. The detection limit was estimated as 3 mg L−1 at the 99.7% confidence level and the coefficient of variation was 2.4% (n = 20). The sampling rate was estimated as 33 determinations per hour. A long pathlength (100-cm) flow cell based on a liquid core waveguide was exploited to increase sensitivity in turbidimetry. Baseline drifts were avoided by a periodical washing step with EDTA in alkaline medium. Linear response was observed within 7–16 mg L−1, described by the equation S = −0.865 + 0.132C (mg L−1), r = 0.999. The detection limit was estimated as 150 μg L−1 at the 99.7% confidence level and the coefficient of variation was 3.0% (n = 20). The sampling rate was estimated as 25 determinations per hour. The results obtained for freshwater and rain water samples were in agreement with those achieved by batch turbidimetry at the 95% confidence level.  相似文献   

15.
A “genome order index,” defined as S = a2 + c2 + t2 + g2, where a, c, t, and g are the nucleotide frequencies of A, C, T, and G, respectively, was used to suggest that there exist genome-specific constraints on nucleotide composition. We show that the “evidence” for constraint, S < 1/3, is in fact a mathematical property that is always true regardless of data. Moreover, we show that S is strictly equivalent to and derivable from the Shannon H-function and has no advantage over it.  相似文献   

16.
The volatile oil of the roots of Cynanchum stauntonii was examined by gas chromatography–mass spectrometry (GC–MS). Thirty-eight constituents were identified. (E,E)-2,4-Decadienal, 3-efhyl-4-methypentanol, 5-pentyl-3H-furan-2-one, (E,Z)-2,4-decadienal and 2(3H)-furanone,dihydro-5-pentyl were found to be the major components. The volatile oil exhibited the activities against influenza virus in vitro (IC50s = 64 μg/ml). In in vivo experiment, it prevented influenza virus-induced deaths in a dose-dependent manner.  相似文献   

17.
The structure and texture characteristics of the hybrid organic–inorganic adsorbents, which were obtained by using of two-component systems of “structure-forming agent/trifunctional silane”, are compared as follows: the first component is Si(OC2H5)4 or (C2H5O)3Si–A–Si(OC2H5)3, where A = –(CH2)2– or –C6H4–; the second one is alkoxysilane with amine (–NH2, NH, –NH(CH2)2NH2) and thiol (–SH) groups. The adsorbents, derived from TEOS, have more accessible functional groups (2.6–4.2 mmol/g) than xerogels, which are based on bis(triethoxysilanes) (1.0–2.6 mmol/g). On another hand xerogels derived from bis(triethoxysilanes) have a more extended porous structure (Ssp =516–968 m2/g, Vs = 0.418–1.490 cm3/g, d = 2.5–15.0 nm) than those that are based on TEOS (Ssp = 4–631 m2/g, Vs = 0.005–1.382 cm3/g, d = 2.3–17.7 nm). The geometric dimensions of functional groups have a more essential effect on the parameters of porous structure in the case of TEOS-derived xerogels. Using solid-state NMR spectroscopy, it has been shown that in synthesis of xerogels with the use of TEOS, the molecular frame of globules is formed by structural units Qn (n = 2,3,4), and the functional groups exist as structural units of Tn (n = 2,3). The xerogels obtained with using bis(triethoxysilanes) consist only of structural units of Tn-type (n = 1,2,3).  相似文献   

18.
A rapid, sensitive and reliable high performance liquid chromatographic method coupled with tandem mass spectrometry (HPLC–MS/MS) has been developed and validated for the determination of cilnidipine, a relatively new calcium antagonist, in human plasma. The reversed-phase chromatographic system was interfaced with a TurboIonSpray (TIS) source. Nimodipine was employed as the internal standard (IS). Sample extracts following protein precipitation were injected into the HPLC–MS/MS system. The analyte and IS were eluted isocratically on a C18 column, with a mobile phase consisting of CH3OH and NH4Ac (96:4, v/v). The ions were detected by a triple quadrupole mass spectrometric detector in the negative mode. Quantification was performed using multiple reaction monitoring (MRM) of the transitions m/z 491.2 → 122.1 and m/z 417.1 → 122.1 for cilnidipine and for the IS, respectively. The analysis time for each run was 3.0 min. The calibration curve fitted well over the concentration range of 0.1–10 ng mL−1, with the regression equation Y = (0.103 ± 0.002)X + (0.014 ± 0.003) (n = 5), r = 0.9994. The intra-day and inter-day R.S.D.% were less than 12.51% at all concentration levels within the calibration range. The recoveries were between 92.71% and 97.64%. The long-term stability and freeze-thaw stability were satisfying at each level. The present method provides a modern, rapid and robust tool for pharmacokinetic studies of cilnidipine.  相似文献   

19.
Amberlite XAD-16 resin has been functionalized using nitrosonaphthol as a ligand and characterized employing elemental, thermogravimetric analysis and FT-IR spectroscopy. The sorption of Ni(II) and Cu(II) ions onto this functionalized resin is investigated and optimized with respect to the sorptive medium (pH), shaking speed and equilibration time between liquid and solid phases. The monitoring of the influence of diverse ions on the sorption of metal ions has revealed that phosphate, bicarbonate and citrate reduce the sorption up to 10–14%. The sorption data followed Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) isotherms. The Freundlich parameters computed are 1/n = 0.56 ± 0.03 and 0.49 ± 0.05, A = 9.54 ± 1.5 and 6.0 ± 0.5 mmol g−1 for Ni(II) and Cu(II) ions, respectively. D–R isotherm yields the values of Xm = 0.87 ± 0.07 and 0.35 ± 0.05 mmol g−1 and of E = 9.5 ± 0.23 and 12.3 ± 0.6 kJ mol−1 for Ni(II) and Cu(II) ions, respectively. Langmuir characteristic constants estimated are Q = 0.082 ± 0.005 and 0.063 ± 0.003 mmol g−1, b = (4.7 ± 0.2) × 104 and (7.31 ± 0.11) × 104 l mol−1 for Ni(II) and Cu(II) ions, respectively. The variation of sorption with temperature gives thermodynamic quantities of ΔH = −58.9 ± 0.12 and −40.38 ± 0.11 kJ mol−1, ΔS = −183 ± 10 and −130 ± 8 J mol−1 K−1 and ΔG = −4.4 ± 0.09 and −2.06 ± 0.08 kJ mol−1 at 298 K for Ni(II) and Cu(II) ions, respectively. Using kinetic equations, values of intraparticle transport and of first order rate constant have been computed for both the metal ions. The sorption procedure is utilized to preconcentrate these ions prior to their determination in tea, vegetable oil, hydrogenated oil (ghee) and palm oil by atomic absorption spectrometry using direct and standard addition methods.  相似文献   

20.
The interactions occurring in di-urea (NHC(O)NH) cross-linked poly(oxyethylene) (POE)/siloxane hybrids (di-ureasils) doped with zinc triflate (Zn(CF3SO3)2) were investigated by Fourier Transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies. Bonding of the Zn2+ ions to the urea carbonyl oxygen atoms occurs in the entire range of compositions studied (∞ > n ≥ 1, where n, salt content, is the molar ratio of oxyethylene moieties per Zn2+ ion). At n > 20 the incorporation of the guest cations progressively reduces the number of free CO groups. At n = 20 the saturation of the urea cross-links is attained and the Zn2+ ions start to coordinate to the POE chains giving rise to the formation of a crystalline POE/Zn(CF3SO3)2 complex. The latter process occurs at the expense of the destruction of the hydrogen-bonded POE/urea structures of the host di-ureasil structure. New hydrogen-bonded associations, more ordered than the urea–urea aggregates present in the non-doped matrix and including Zn2+OC coordination, emerge in parallel. “Free” and weakly coordinated CF3SO3 ions, present in all the xerogels studied, appear to be the main charge carriers of the conductivity maximum of this family of ormolytes located at n = 60 at 30 °C. In materials with n ≤ 20 contact ion pairs, “cross-link separated” ions pairs and higher ionic aggregates appear. The data reported demonstrate that the behaviour of the di-ureasils doped with triflate salts depends on the type of cation.  相似文献   

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