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1.
We report the synthesis and elementary properties of the Co7Se8−xSx (x=0-8) and Ni7Se8−xSx (x=0-7) solid solutions. Both systems form a NiAs-type structure with metal vacancies. In general, the lattice parameters decrease with increasing x, but in the Ni7Se8−xSx system c increases on going from x=5 to 7. Magnetic susceptibility measurements show that all samples exhibit temperature-independent paramagnetism from 25-250 K. Samples within the Co7Se8−xSx system, as well as Ni7Se8 and Ni7SeS7, were found to be poor metals with resistivities of ∼0.20 and ∼0.06 mΩ cm at 300 K, respectively. The Sommerfeld constant (γ) was determined from specific heat measurements to be ∼13 mJ/molCoK2 and ∼7 mJ/molNiK2 for Co7Se8−xSx and Ni7Se8−xSx, respectively.  相似文献   

2.
The synthesis of a new pigment with a bluish color was obtained from the reaction of methylpyranomalvidin-3-glucoside with sinapaldehyde and its formation mechanism seems to involve a charge-transfer reaction pathway. The structure of this compound was fully characterized by LC/DAD-MS and NMR. Its equilibrium forms present in water at different pH values and the respective ionization constants were determined by UV-visible spectroscopy. The results revealed the presence of three equilibria involving only deprotonation reactions at the 7-OH and 4′-OH positions of the pyranoanthocyanin moiety and at the 4′″-OH of the syringol moiety (pKa1 = 3.64 ± 0.01; pKa2 = 8.02 ± 0.01; pKa3 = 11.19 ± 0.01).  相似文献   

3.
In this paper, we describe the structural and sensing properties of high-k PrYxOy sensing films deposited on Si substrates through reactive co-sputtering. Secondary ion mass spectrometry and atomic force microscopy were employed to analyze the compositional and morphological features of these films after annealing at various temperatures. The electrolyte-insulator-semiconductor (EIS) device incorporating a PrYxOy sensing membrane that had been annealed at 800 °C exhibited good sensing characteristics, including a high sensitivity (59.07 mV pH−1 in solutions from pH 2 to 12), a low hysteresis voltage (2.4 mV in the pH loop 7 → 4 → 7 → 10 → 7), and a small drift rate (0.62 mV h−1 in the buffer solution at pH 7). The PrYxOy EIS device also showed a high selective response towards H+. This improvement can be attributed to the small number of crystal defects and the large surface roughness. In addition, the enzymatic EIS-based urea biosensor incorporating a high-k PrYxOy sensing film annealed at 800 °C allowed the potentiometric analysis of urea, at concentrations ranging from 1 to 16 mM, with a sensitivity of 9.59 mV mM−1.  相似文献   

4.
The anhydrous salt K2B12F12 crystallized from aqueous solution and its structure was determined by single crystal X-ray diffraction. The Ni2In-type structure it exhibits is rare for an A2X ionic compound at 25 °C and 1 atm., consisting of an expanded hexagonal close-packed array of B12F122− centroids (cent?cent distances: 7.204-8.236 Å) with half of the K+ ions filling all of the Oh holes and half of the K+ ions filling all of the D3h trigonal holes in the close-packed layers that are midway between two “empty” Td holes. The structure is also unusual in that the bond-valence sum for the K+ ions in Oh holes is less than or equal to 0.73 (the bond-valence sum for the other type of K+ ion is 1.16). A variation of the Ni2In structure is exhibited by the previously published monohydrate Cs2(H2O)B12F12, for which an improved structure is also reported here. For K2B12F12: monoclinic, C2/c, a = 8.2072(8), b = 14.2818(7), c = 11.3441(9) Å, β = 92.832(5)°, Z = 4, T = 120(2) K. For Cs2(H2O)B12F12: orthorhombic, P212121, a = 9.7475(4), b = 10.2579(4), c = 15.0549(5) Å, Z = 4, T = 110(1) K.  相似文献   

5.
Single crystals of K3RESi2O7 (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were grown from a potassium fluoride flux. Two different structure types were found for this series. Silicates containing the larger rare earths, RE=Gd, Tb, Dy, Ho, Er, Tm, Yb crystallize in a structure K3RESi2O7 that contains the rare-earth cation in both a slightly distorted octahedral and an ideal trigonal prismatic coordination environment, while in K3LuSi2O7, containing the smallest of the rare earths, lutetium is found solely in an octahedral coordination environment. The structure of K3LuSi2O7 crystallizes in space group P63/mmc with a=5.71160(10) Å and c=13.8883(6) Å. The structures containing the remaining rare earths crystallize in the space group P63/mcm with the lattice parameters of a=9.9359(2) Å, c=14.4295(4) Å, (K3GdSi2O7); a=9.88730(10) Å, c=14.3856(3) Å, (K3TbSi2O7); a=9.8673(2) Å, c=14.3572(4) Å, (K3DySi2O7); a=9.8408(3) Å, c=14.3206(6) Å, (K3HoSi2O7); a=9.82120(10) Å, c=14.2986(2) Å, (K3ErSi2O7); a=9.80200(10) Å, c=14.2863(4) Å, (K3TmSi2O7); a=9.78190(10) Å, c=14.2401(3) Å, (K3YbSi2O7). The optical properties of the silicates were investigated and K3TbSi2O7 was found to fluoresce in the visible.  相似文献   

6.
The areas of the fusion and crystallization peaks of K3TaF8 and K3TaOF6 have been measured using the DSC mode of the high-temperature calorimeter (SETARAM 1800 K). On the basis of these quantities and the temperature dependence of the used calorimetric method sensitivity, the values of the enthalpy of fusion of K3TaF8 at temperature of fusion 1039 K: ΔfusHm(K3TaF8; 1039 K) = (52 ± 2) kJ mol−1 and of K3TaOF6 at temperature of fusion 1055 K: ΔfusHm(K3TaOF6; 1055 K) = (62 ± 3) kJ mol−1 have been determined.  相似文献   

7.
Vacuum ultraviolet (VUV) excitation and photoluminescent (PL) properties of Eu3+ and Tb3+ ion-doped aluminate phosphors, GdCaAl3O7:Eu3+ and GdCaAl3O7:Tb3+ have been investigated. X-ray diffraction (XRD) patterns indicate that the phosphor GdCaAl3O7 forms without impurity phase at 900 °C. Field emission scanning electron microscopy (FE-SEM) images show that the particle size of the phosphor is less than 3 μm. Upon excitation with VUV irradiation, the phosphors show a strong emission at around 619 nm corresponding to the forced electric dipole 5D07F2 transition of Eu3+, and at around 545 nm corresponding to the 5D47F5 transition of Tb3+. The results reveal that both GdCaAl3O7:RE3+ (RE=Eu, Tb) are potential candidates as red and green phosphors, respectively, for use in plasma display panel (PDP).  相似文献   

8.
The crystal chemistry and crystallography of the compounds SrR2CuO5 (Sr-121, R=lanthanides) were investigated using the powder X-ray Rietveld refinement technique. Among the 11 compositions studied, only R=Dy and Ho formed the stable SrR2CuO5 phase. SrR2CuO5 was found to be isostructural with the “green phase”, BaR2CuO5. The basic structure is orthorhombic with space group Pnma. The lattice parameters for SrDyCuO5 are a=12.08080(6) Å, b=5.60421(2) Å, c=7.12971(3) Å, V=482.705(4) Å3, and Z=8; and for the Ho analog are a=12.03727(12) Å, b=5.58947(7) Å, c=7.10169(7) Å, V=477.816(9) Å3, and Z=8. In the SrR2CuO5 structure, each R is surrounded by seven oxygen atoms, forming a monocapped trigonal prism (RO7). The isolated CuO5 group forms a distorted square pyramid. Consecutive layers of prisms are stacked in the b-direction. Bond valence calculations imply that residual strain is largely responsible for the narrow stability of the SrR2CuO5 phases with R=Dy and Ho only. X-ray powder reference diffraction patterns for SrDy2CuO5 and SrHo2CuO5 were determined.  相似文献   

9.
A new ternary compound, U3Co2Ge7, has been synthesized from the corresponding elements by a high temperature reaction using molten tin flux. It crystallizes in the orthorhombic La3Co2Sn7-type (Pearson's symbol oC24, space group Cmmm, No. 65) with lattice parameters determined from single-crystal X-ray diffraction as follows: a=4.145(2) Å; b=24.920(7); c=4.136(2) Å, V=427.2(3) Å3. Structure refinements confirm an ordered structure having two crystallographically inequivalent uranium atoms, occupying sites with dissimilar coordination. U3Co2Ge7 orders ferromagnetically below 40 K and undergoes a consecutive magnetic transition at 20 K. These results have been obtained from temperature- and field-dependent magnetization, resistivity and heat-capacity measurements. The estimated Sommerfeld coefficient γ=87 mJ/mol-U K2 suggests U3Co2Ge7 to be a moderately heavy-fermion material.  相似文献   

10.
Low-temperature heat capacities of the compound Na(C4H7O5)·H2O(s) have been measured with an automated adiabatic calorimeter. A solid-solid phase transition and dehydration occur at 290-318 K and 367-373 K, respectively. The enthalpy and entropy of the solid-solid transition are ΔtransHm = (5.75 ± 0.01) kJ mol−1 and ΔtransSm = (18.47 ± 0.02) J K−1 mol−1. The enthalpy and entropy of the dehydration are ΔdHm = (15.35 ± 0.03) kJ mol−1 and ΔdSm = (41.35 ± 0.08) J K−1 mol−1. Experimental values of heat capacities for the solids (I and II) and the solid-liquid mixture (III) have been fitted to polynomial equations.  相似文献   

11.
A novel turn-off fluorescent probe based on coumarin and imidazole moiety for extremely acidic conditions was designed and developed. The probe with pKa = 2.1 is able to respond to very low pH value (below 3.5) with high sensitivity relying on fluorescence quenching at 460 nm in fluorescence spectra or the ratios of absorbance maximum at 380 nm to that at 450 nm in UV–vis spectra. It can quantitatively detect pH value based on equilibrium equation, pH = pKa − log[(Ix − Ib)/(Ia − Ix)]. It had very short response time that was less than 1 min, good reversibility and nearly no interference from common metal ions. Moreover, using 1H NMR analysis and theoretical calculation of molecular orbital, we verified that a two-step protonation process of two N atoms of the probe leaded to photoinduced electron transfer (PET), which was actually the mechanism of the fluorescence quenching phenomenon under strongly acidic conditions. Furthermore, the probe was also applied to imaging strong acidity in bacteria, E.coli and had good effect. This work illustrates that the new probe could be a practical and ideal pH indicator for strongly acidic conditions with good biological significance.  相似文献   

12.
A reagentless signal-on electrochemiluminescence (ECL) biosensor for DNA hybridization detection was developed based on the quenching effect of ferrocene (Fc) on intrinsic cathodic ECL at thin oxide covered glassy carbon (C/CxO1−x) electrodes. To construct the DNA biosensor, molecular beacon (MB) modified with ferrocene (3′-Fc) was attached to a C/CxO1−x electrode via the covalent bound between labeled amino (5′-NH2) and surface functional groups. It was found that the immobilization of the probe on the electrode surface mainly depended on the fraction of surface carbonyl moiety. When a complementary target DNA (cDNA) was present, the stem-loop of MB on the electrode was converted into a linear double-helix configuration due to hybridization, resulting in the moving away of Fc from the electrode surface, and the restoring of the cathodic ECL signal. The restoration of the ECL intensity was linearly changed with the logarithm of cDNA concentration in the range of 1.0 × 10−11 to 7.0 × 10−8 M, and the detection limit was ca. 5.0 pM (S/N = 3). Additionally, single-base mismatched DNA can be effectively discriminated from the cDNA. The great advantage of the biosensor lies in its simplicity and cost-effective with ECL generated from the electrode itself, and no adscititious luminophore is required.  相似文献   

13.
Hydrothermal synthesis in the K-Mo oxide system was investigated as a function of the pH of the reaction medium. Four compounds were formed, including two K2Mo4O13 phases. One is a new low-temperature polymorph, which crystallizes in the orthorhombic, space group Pbca, with Z=8 and unit cell dimensions a=7.544(1) Å, b=15.394(2) Å, c=18.568(3) Å. The other is the known triclinic K2Mo4O13, whose structure was re-determined from single crystal data; its cell parameters were determined as a=7.976(2) Å, b=8.345(2) Å, c=10.017(2) Å, α=107.104(3)°, β=102.885(3)°, γ=109.760(3)°, which are the standard settings of the crystal lattice. The orthorhombic phase converts endothermically into triclinic phase at ca. 730 K with a heat of transition of 8.31 kJ/mol.  相似文献   

14.
Single crystals of SrAl2Si2 were synthesized by reaction of the elements in an aluminum flux at 1000 °C. SrAl2Si2 is isostructural to CaAl2Si2 and crystallizes in the hexagonal space group P-3m1 (90 K, a=4.1834 (2), c=7.4104 (2) Å, Z=1, R1=0.0156, wR2=0.0308). Thermal analysis shows that the compound melts at ∼1020 °C. Low-temperature resistivity on single crystals along the c-axis shows metallic behavior with room temperature resistivity value of ∼7.5 mΩ cm. High-temperature Seebeck, resistivity, and thermal conductivity measurements were made on hot-pressed pellets. The Seebeck coefficient shows negative values in entire temperature range decreasing from ∼−78 μV K−1 at room temperature to −34 μV K−1 at 1173 K. Seebeck coefficients are negative indicating n-type behavior; however, the temperature dependence is consistent with contribution from minority p-type carriers as well. The lattice contribution to the thermal conductivity is higher than for clathrate structures containing Al and Si, approximately 50 mW cm−1 K, and contributes to the overall low zT for this compound.  相似文献   

15.
The supramolecular interaction of a homologous series of cucurbit[n]uril (CB[n], n = 5, 6, 7, 8) hosts and coptisine (COP) was studied by spectrofluorimetry. All of the CB[n]s were found to react with COP to form 1:1 host-guest stable complexes and the fluorescence intensity of the complexes was greatly enhanced. The apparent association constants of the complexes were 1.44 × 104, 1.28 × 104, 1.86 × 104 and 1.26 × 104 L mol−1 for CB[5], CB[6], CB[7] and CB[8], respectively. In addition, CB[5] and CB[7] exhibited a higher fluorescence signal than CB[6] and CB[8]. The fluorescence intensity of the complex with CB[7] was enhanced 70-fold compared to that of the studied drug itself. Based on the significant enhancement of fluorescence intensity of supramolecular complex, a simple, rapid, highly sensitive, and selective spectrofluorimetric method was developed for the determination of COP in aqueous solution in the presence of CB[7]. At the optimum reaction conditions, a linear relationship was obtained in the range from 0.05 to 1700 ng mL−1 with a detection limit of 0.012 ng mL−1. The proposed method was successfully applied for the determination of the drug in urine and serum samples.  相似文献   

16.
The chemical kinetics, studied by UV/Vis, IR and NMR, of the oxidative addition of iodomethane to [Rh((C6H5)COCHCOR)(CO)(PPh3)], with R = (CH2)nCH3, n = 1-3, consists of three consecutive reaction steps that involves isomers of two distinctly different classes of RhIII-alkyl and two distinctly different classes of RhIII-acyl species. Kinetic studies on the first oxidative addition step of [Rh((C6H5)COCHCOR)(CO)(PPh3)] + CH3I to form [Rh((C6H5)COCHCOR)(CH3)(CO)(PPh3)(I)] revealed a second order oxidative addition rate constant approximately 500-600 times faster than that observed for the Monsanto catalyst [Rh(CO)2I2]. The reaction rate of the first oxidative addition step in chloroform was not influenced by the increasing alkyl chain length of the R group on the β-diketonato ligand: k1 = 0.0333 ([Rh((C6H5)COCHCO(CH2CH3))(CO)(PPh3)]), 0.0437 ([Rh((C6H5)COCHCO(CH2CH2CH3))(CO)(PPh3)]) and 0.0354 dmmol−1 s−1 ([Rh((C6H5)COCHCO(CH2CH2CH2CH3))(CO)(PPh3)]). The pKa and keto-enol equilibrium constant, Kc, of the β-diketones (C6H5)COCH2COR, along with apparent group electronegativities, χR of the R group of the β-diketones (C6H5)COCH2COR, give a measurement of the electron donating character of the coordinating β-diketonato ligand: (R, pKa, Kc, χR) = (CH3, 8.70, 12.1, 2.34), (CH2CH3, 9.33, 8.2, 2.31), (CH2CH2CH3, 9.23, 11.5, 2.41) and (CH2CH2CH2CH3, 9.33, 11.6, 2.22).  相似文献   

17.
Hydroboration reactions of 1-octene and 1-hexyne with H2BBr·SMe2 in CH2Cl2 were studied as a function of concentration and temperature, using 11B NMR spectroscopy. The reactions exhibited saturation kinetics. The rate of dissociation of dimethyl sulfide from boron at 25 °C was found to be (7.36 ± 0.59 and 7.32 ± 0.90) × 10−3 s−1 for 1-octene and 1-hexyne, respectively. The second order rate constants, k2, for hydroboration worked out to be 7.00 ± 0.81 M s−1 and 7.03 ± 0.70 M s−1, while the overall composite second order rate constants, k K, were (3.30 ± 0.43 and 3.10 ± 0.37) × 10−2 M s−1, respectively at 25 °C. The entropy and enthalpy values were found to be large and positive for k1, whilst for k2 these were large and negative, with small values for enthalpies. This is indicative of a limiting dissociative (D) for the dissociation of Me2S and associative mechanism (A) for the hydroboration process. The overall activation parameters, ΔH and ΔS, were found to be 98 ± 2 kJ mol−1 and +56 ± 7 J K−1 mol−1 for 1-octene whilst, in the case of 1-hexyne these were found out to be 117 ± 7 kJ mol−1 and +119 ± 24 J K−1 mol−1, respectively. When comparing the kinetic data between H2BBr·SMe2 and HBBr2·SMe2, the results showed that the rate of dissociation of Me2S from H2BBr·SMe2 is on average 34 times faster than it is in the case of HBBr2·SMe2. Similarly, the rate of hydroboration with H2BBr·SMe2 was found to be on average 11 times faster than it is with HBBr2·SMe2. It is also clear that by replacing a hydrogen substituent with a bromine atom in the case of H2BBr·SMe2 the mechanism for the overall process changes from limiting dissociative (D) to interchange associative (Ia).  相似文献   

18.
Changes in structure and dielectric properties at elevated temperatures have been investigated on single-crystals of sodium potassium niobate, Na0.5K0.5NbO3, grown by the flux method. Single-crystal X-ray diffraction studies revealed that the crystals underwent orthorhombic-tetragonal and tetragonal-cubic phase transitions at 465 and 671 K during heating and 446 and 666 K during cooling, respectively. Both transitions were accompanied by volumetric discontinuities of collapse upon heating and expansion upon cooling, suggesting that the transitions were of the first order. The coordination numbers of an Nb showed a decreasing tendency with decreasing temperature, i.e., 6 in cubic, 5+1 in tetragonal and 4+2 in orthorhombic. An Na atom occupied a slightly different position from the K atom in 12-fold coordination, resulting in fewer coordination numbers of 8+4 in cubic and tetragonal and 7+5 in orthorhombic. The spontaneous polarisation (Ps) estimated from the atom positions and formal charges were approximately 0.29 C m−2 in orthorhombic and 0.18 C m−2 in tetragonal. The contribution of the alkaline oxide components to Ps was estimated to be approximately 15% in both ferroelectric forms. The temperature-induced transitions were also confirmed through the dielectric constant and dielectric loss at various frequencies and the differential scanning calorimetry.  相似文献   

19.
Thermoelectric properties of polycrystalline La1−xSrxCoO3, where Sr2+ is substituted in La3+ site in perovskite-type LaCoO3, have been investigated. Sr-doping increases the electrical conductivity (σ) of La1−xSrxCoO3, and also decreases the Seebeck coefficient (S) for 0.01?x?0.40. A Hall coefficient measurement reveals that the increase in electrical conductivity arises from increases in both carrier concentration and the Hall mobility. The decrease in the Seebeck coefficient is caused by a decrease in carrier effective mass as well as increase in carrier concentration. The highest power factor (σS2) is 3.7×10−4 W m−1 K−2 at 250 K for x=0.10. The thermal conductivity (κ) is about 2 W m−1 K−1 at 300 K for 0?x?0.04, and increases for x?0.05 because of an increase in heat transport by conductive carrier. The thermoelectric properties of La1−xSrxCoO3 are improved by Sr-doping, and the figure of merit (Z=σS2 κ−1) reaches 1.6×10−4 K−1 for x=0.06 at 300 K (ZT=0.048). For heavily Sr-doped samples, the thermoelectric properties diminish mainly because of the decrease in the Seebeck coefficient and the increase in thermal conductivity.  相似文献   

20.
In this study, pKa values were determined using the dependence of the retention factor on the pH of the mobile phase for three ionizable substances, namely, enalapril, lercanidipine and ramipril (IS). The effect of the mobile phase composition on the ionization constant was studied by measuring the pKa at different methanol-water mixtures, ranging between 50 and 65% (v/v), using LC-DAD method. Two simple, accurate, precise and fully validated analytical methods for the simultaneous determination of enalapril and lercanidipine in combined dosage forms have been developed. Separation was performed on an X-Terra RP-18 column (250 mm × 4.60 mm ID × 5 μm) at 40 °C with the mobile phase of methanol-water 55:45 (v/v) adjusted to pH 2.7 with 15 mM orthophosphoric acid. Isocratic elution was performed in less than 12 min with a flow rate of 1.2 mL min−1. Good sensitivity for the analytes was observed with DAD detection. The LC method allowed quantitation over the 0.50-20.00 μg mL−1 range for enalapril and lercanidipine. The second method depends on first derivative of the ratio-spectra by measurements of the amplitudes at 219.7 nm for enalapril and 233.0 nm for lercanidipine. Calibration graphs were established for 1-20 μg mL−1 for enalapril and 1-16 μg mL−1 lercanidipine, using first derivative of the ratio spectrophotometric method. Both methods have been extensively validated. These methods allow a number of cost and time saving benefits. The described methods can be readily utilized for analysis of pharmaceutical formulations. The methods have been applied, without any interference from excipients, for the simultaneous determination of these compounds in tablets. There was no significant difference between the performance of the proposed methods regarding the mean values and standard deviations.  相似文献   

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