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1.
An alkali‐soluble polysaccharide, GM5‐1, from the mycelium of Ganoderma tsugae, was fractionated by the nonsolvent addition method. The weight‐average molecular mass (M w) and intrinsic viscosity ([η]) of fractions were studied by laser light scattering and viscometry with dimethylsulfoxide (DMSO) containing 0.25M LiCl (0.25M LiCl/DMSO) as the solvent at 30°C. The dependences of [η] and the radius of gyration (?S 2?z 1/2) on M w were found to be [η]=9.8×10?2 M w 0.57 (cm3g?1) and ?S 2?z 1/2=1.65×10?2 M w 0.58 (nm) in the M w range from 8.6×105 to 2.6×106. The analysis based on current theories for a wormlike chain showed that the chain conformational parameters of GM5‐1 were 4.2 nm for persistence length (q) and 833 nm?1 for linear mass density (ML) with an obvious excluded volume effect. The results suggested the alkali‐soluble polysaccharide behaves like a semiflexible chain in 0.25M LiCl/DMSO at 30°C.  相似文献   

2.
A new candidate laser dye based 1,4-bis[β-(2-naphthothisolyl) vinyl] benzene (BNTVB) were prepared, and characterized in various organic solvents. The center polarity is less sensitive than electronic absorption. A red shift was noticed in the fluorescence spectra (ca. 40 nm) with increment in the solvent’s polarity, this means that BNTVB’s polarity appreciates upon excitation. The dipole moment of ground state (μg) and the excited singlet state dipole moment (μe) are determined from Kawski – Chamma and Bakshiev–Viallet equations using the disparity of Stokes shift with solvent polarity function of ε (dielectric constant) and n (refractive index) of the solvent. The result was found to be 0.019D and 5.13D for ground and exited state, in succession. DFT/TD-DFT manners were used to understand the electronic structures and geometric of BNTVB in other solvents. The experimental and theoretical results showed a good agreement. The photochemical quantum yield (Фc) of BNTVB was calculated in variable organic reagents such as Dioxane, CHCl3, EtOH and MeOH at room temperature. The values of φc were calculated as 2.3?×?10?4, 3.3?×?10?3, 9.7?×?10?5 and 6.2?×?10?5 in Dioxane, CHCl3, EtOH and MeOH, respectively. The dye solutions (2?×?10?4 M) in DMF, MeOH and EtOH give laser emission in the blue-green region. The green zone is excited by nitrogen pulse 337.1 nm. The tuning range, gain coefficient (α) and cross – section emission (σe) of laser were also estimated. Excitation energy transfer from BNTVB to rhodamine-6G (R6G) and N,N-bis(2,6-dimethyphenyl)-3,4:9,10-perylenebis-(dicarboximide) (BDP) was also studied in EtOH to increase the laser emission output from R6G and BDP when excited by nitrogen laser. The dye-transfer power laser system (ETDL) obeys the Foster Power Transmission (FERT) mechanism with a critical transmission distance, Ro of 40 and 32 ? and kET equals 2.6?×?1013 and 1.06?×?1013 M?1 s?1 for BNTVB / R6G and BNTVB / BDP pair, respectively.  相似文献   

3.
A linear β-(1→3)-d-glucan PCM3 (pachyman), a major polysaccharide in Poria cocos mycelia, formed aggregates in aqueous solution or dimethyl sulfoxide (DMSO) with absorbed moisture, thereby considerably complicating its fractionation and study of solution properties. In this work, the pachyman PCM3 having narrow polydispersity (M w/M n = 1.9) was carefully fractionated by a preparative size exclusion chromatography (SEC) using dehydrated DMSO as the mobile phase. The weight-average molecular mass M w and intrinsic viscosity [η] of the fractions were measured by static and dynamic laser light scattering, SEC combined with light scattering, and viscometry in DMSO at 25°C, thus eliminating the aggregation. The Mark-Houwink equation for the pachyman in DMSO is established to be: [η] = 6.79 × 10?4 M w 0.95 (mL/g) in the M w range from 1.2 to 3.5 × 105. The characteristic ratio C of the PCM3 in DMSO at 25°C, from light scattering by using Flory theory, was obtained to be 10.1, thus indicating that it behaves as a relatively expanded, flexible coil. In addition, the M w of the pachyman from Poria cocos mycelia was 1.68 × 105, obviously larger than that from the sclerotium (8.9 × 104).  相似文献   

4.
The melting curves of argon and of methane have been measured in a diamond-anvil cell from 290 to>700 K. Measurements of argon, fit to the equation P?6.9×10?5=0.244[(T/83.805)1.476?1], are in excellent agreement with previously published values up to a temperature of ~ 500 K and thereafter diverge slowly. Measurements of methane, fit to P?1.17×10?5=0.208[(T/90.6941)1.698?1], are in serious disagreement with the only previous studies to extend past 400 K.  相似文献   

5.
The isotopic compositions of carbon compounds in landfill leachate provide insights into the biodegradation pathways that dominate the different stages of waste decomposition. In this study, the carbon geochemistry of different carbon pools, environmental stable isotopes and compound-specific isotope analysis (CSIA) of leachate dissolved organic carbon (DOC) fractions and gases show distinctions in leachate biogeochemistry and methane production between the young area of active waste emplacement and the old area of historical emplacement at the Trail Road Landfill (TRL).

The active area leachate has low DOC concentrations (<200 mg l?1) dominated by fulvic acid (FA=160 mg l?1), and produces CH4 dominantly by CO2 reduction (D? excess=20.6‰). Leachate generated in the area of older waste has high DOC (>4770 mg l?1) dominated by FA (4482 mg l?1) and simple fatty acids (acetic=1008 mg l?1 and propionic=608 mg l?1), and produces CH4 by the acetate fermentation pathway (D? excess=9.8‰). CSIA shows an advanced degradation and a progressive accumulation of 13C of fatty acids in leachate from the older area. The enriched 13C value of FA (?20 and?26‰ for the older and active parts, respectively,) and of low molecular weight DOC (?8 and?27‰) as well as of the bulk DOC (?21 and?25‰) shows more advanced degradation in the older part of the landfill, which is consistent with the shift in the humic/FA ratios (0.05 and 0.18). The 13C enrichment of acetate (?12‰) above the 13C of DOC (?21‰) and of propionic acid (?19‰), in older leachate, suggests that this acetate has not evolved from the simple degradation of larger organic molecules, but by homoacetogenesis from the enriched dissolved inorganic carbon (DIC) pool (8‰) and H2, which produce a more enriched 13C of acetate. In contrast, the 13C of the minor acetate in the active area (?17‰) indicates that CO2-reducing bacteria must be the primary consumers of H2, which has resulted in enriched 13CDIC (10‰) and depleted 13CCH4 (?58‰).  相似文献   

6.
We present a ring-down absorption spectrometer based on a continuous-wave CO laser in the mid-infrared spectral region near λ?=?5 μm. Using a linear ring-down cavity (length: 0.5 m) with high reflective mirrors (R?=?99.988 %), we observed a noise-equivalent absorption coefficient of 3?×?10?10 cm?1Hz?1/2. This corresponds to a noise-equivalent concentration of 800 parts per trillion (ppt) for 14NO and 40 ppt for 15NO in 1 s averaging time. We achieve a time resolution of 1 s which allows time resolved simultaneous detection of the two N isotopes. The δ15N value was obtained with a precision of ±1.2‰ in a sample with a NO fraction of 11 ppm. The simultaneous detection enables the use of 15NO as a tracer molecule for endogenous biomedical processes.  相似文献   

7.
Simultaneous determination of two structurally related ß2 adrenergic receptor agonists namely, Ritodrine HCl (RTH) and Isoxsuprine HCl (ISP) was performed using coupling technique of synchronous fluorimetry and H-point standard addition method. Under optimum conditions, linear determination ranges were 1.48 – 14.80?×?10?6 mol L?1 and 1.54 – 15.44?×?10?6 mol L?1 for ISP and RTH respectively. RTH and ISP could be determined simultaneously without interference from each other when their concentration ratio varies from 5:1 to 1:5 in the mixed sample. The proposed method was applied to the determination of RTH and ISP in synthetic mixture of pharmaceutical samples, the accuracy and precision of the results were satisfactory.  相似文献   

8.
The sensitization of the excited triplet state of a novel symmetrical Bis(dialkylamino)phenoxazinium salt was developed in the presence of Hg2+. This effect was used to determine the concentration of Hg2+ in different water samples. The phenoxazinium salt sensor was characterized by different spectroscopic tools such as: UV, FTIR, NMR and fluorescence spectra. The sensor has an emission band at 347 nm in DMSO. Hg2+ in DMSO at pH 5.6 can remarkably quench the fluorescence intensity of the sensor at 347 nm and a new band was appeared at 436 nm due to the strong complex formation between Hg2+ and sensor. The quenching of the band intensity at 347 and the enhancement of the intensity of the new band at 436 were used to determine the Hg2+ in different waste water samples. The dynamic range found for the determination of Hg2+ concentration is 8.7?×?10-10 – 1.4?×?10-6 mol L?1 with a detection limit of 5.8?×?10?10 mol L?1 and quantification detection limit of 1.8?×?10-9 mol L-1.  相似文献   

9.
In order to establish the mechanism and to determine the parameters of lithium transport in electrodes based on lithium-vanadium phosphate (Li3V2(PO4)3), the kinetic model was designed and experimentally tested for joint analysis of electrochemical impedance (EIS), cyclic voltammetry (CV), pulse chronoamperometry (PITT), and chronopotentiometry (GITT) data. It comprises the stages of sequential lithium-ion transfer in the surface layer and the bulk of electrode material’s particles, including accumulation of lithium in the bulk. Transfer processes at both sites are of diffusion nature and differ significantly, both by temporal (characteristic time, τ) and kinetic (diffusion coefficient, D) constants. PITT data analysis provided the following D values for the predominantly lithiated and delithiated forms of the intercalation material: 10?9 and 3 × 10?10 cm2 s?1, respectively, for transfer in the bulk and 10?12 cm2 s?1 for transfer in the thin surface layer of material’s particles. D values extracted from GITT data are in consistency with those obtained from PITT: 3.5–5.8 × 10?10 and 0.9–5 × 10?10 cm2 s?1 (for the current and currentless mode, respectively). The D values obtained from EIS data were 5.5 × 10?10 cm2 s?1 for lithiated (at a potential of 3.5 V) and 2.3 × 10?9 cm2 s?1 for delithiated (at a potential 4.1 V) forms. CV evaluation gave close results: 3 × 10?11 cm2 s?1 for anodic and 3.4 × 10?11 cm2 s?1 for cathodic processes, respectively. The use of complex experimental measurement procedure for combined application of the EIS, PITT, and GITT methods allowed to obtain thermodynamic E,c dependence of Li3V2(PO4)3 electrode, which is not affected by polarization and heterogeneity of lithium concentration in the intercalate.  相似文献   

10.
Under an aid of ultrasonic, tetraoxalyl ethylenediamine melamine resin-coated multiwalled carbon nanotubes were prepared for Ni(II) sensing in aqueous solution. The processes involved the fabrication of tetraoxalyl ethylenediamine melamine resin by one pot way, the coating of tetraoxalyl ethylenediamine melamine resin at multiwalled carbon nanotubes (MWCNTs), and the determination of Ni(II). The present materials were carefully examined by Fourier transform infrared spectroscopy, field emission scanning electron microscope, and electrochemistry techniques. A great deal of amorphous microsphere could be observed for tetraoxalyl ethylenediamine melamine resin with an average diameter of 1.2 μm, and MTE could evenly adhere at the surface of MWCNTs by the ultrasonic. Tetraoxalyl ethylenediamine melamine resin-coated multiwalled carbon nanotube-modified paraffin-impregnated graphite electrode was successfully used for the determination of Ni(II) by differential pulse adsorptive anodic stripping voltammetry. The current responses (?0.3 V) were linearly increased depending on the concentration from 1?×?10?11 to 3?×?10?10 M (i (μA)?=?11.1?+?7.9 c (1?×?10?12 M); R?=?0.9901, 3σ?=?7?×?10?12 M).  相似文献   

11.
The morphological and hydrodynamic properties of three series of anionic polyacrylonitrile fractions (105<M w< 5 × 106) have been studied in dilute dimethylformamide (DMF) solution. All the observed values of the molecular parameters (M w, S 2 w A2, [η], S) are consistent with a trifunctional randomly branched structure characterized by a decrease of branching density with molecular weight. The sample obtained in a strongly dipolar solvent (DMF, ?70°C, diphenylmethylsodium) shows a unimodal molecular weight distribution and higher branching densities (2.5 × 10?2 to 10?1); on the other hand, the sample obtained in a nonpolar solvent (toluene, ?70°C, n-butyllithium) shows a binodal molecular weight distribution and smaller branching densities (10?4 to 1.4 × 10?3). These characteristic branched structures may be explained by transfer to polymer as the main branching process, taking into account the polarity of the medium and its thermodynamic quality for the polymer.  相似文献   

12.
Isotope effects of cerium were observed in malate and lactate complex formations during the long-distance displacement chromatographic processes at 313 K. Heavier isotopes were found fractionated in the frontal edges of the Ce adsorption bands in both the systems, registering a preference of the heavier isotopes for the Ce(III) complexes in the solution phase over the simply hydrated Ce(III) ions in the resin phase. The fractionation coefficients ? for the 136Ce/140Ce, 138Ce/140Ce and 142Ce/140Ce isotopic pairs were 7.1 × 10?6, 5.2 × 10?6 and ?2.1 × 10?6 for the malate system, and 4.8 × 10?6, 4.5 × 10?6 and?2.6×10?6 for the lactate system, respectively. They all show the mass-dependent law if the deviation of ? for the 138Ce/140Ce pair was considered merely due to the isobaric interference in Ce isotopic ratio measurements, suggesting the molecular vibration, rather than the nuclear field shift, mainly contributes to the Ce isotope effects in the complex formation systems. The absolute values of ? between the two systems are comparable, suggesting no instinct difference in structural properties between Ce malate and lactate complexes involved.  相似文献   

13.
Abstract

The effects of three systems on the chemiluminescence (CL) intensity have been studied in this paper, such as leucogen–potassium permanganate–rhodamine B, leucogen–cerium (IV)–rhodamine B, and leucogen–luminol–hydrogen peroxide (called system 1, system 2, and system 3, respectively). The mechanism of these reactions is also discussed. Surfactant (CTMAB) has a remarkably sensitive effect on these systems mentioned above. Therefore, three new flow injection chemiluminescence methods for the determination of leucogen have been established. For system 1, the linear range is 8.0×10?8 to 4.0×10?5 g mL?1, with limits of detection 2×10?8 g mL?1; the relative standard deviation is 2.5% (n=11, Cs=4.0×10?6 g mL?1). For system 2, the linear range is 1.0×10?8 to 5.0×10?6 g mL?1, with limits of detection 3×10?9 g mL?1; the relative standard deviation is 5.1% (n=11, Cs=1.0×10?6 g mL?1). For system 3, the linear range is 4.0×10?8 to 2.0×10?6 g mL?1, with limits of detection 1×10?8 g mL?1; the relative standard deviation is 1.3% (n=11, Cs=1.0×10?7 g mL?1). Compared with the three methods above, system 3 is confirmed as the best method. This method has been applied to the determination of leucogen with satisfactory results.  相似文献   

14.
The high-pressure and high-temperature behaviors of LiF and NaF have been studied up to 37 GPa and 1000 K. No phase transformations have been observed for LiF up to the maximum pressure reached. The B1 to B2 transition of NaF at room temperature was observed at ~28 GPa, this transition pressure decreases with temperature. Unit-cell volumes of LiF and NaF B1 phase measured at various pressures and temperatures were fitted using a P–V–T Birch–Murnaghan equation of state. For LiF, the determined parameters are: α0 = 1.05 (3)×10?4 K?1, dK/dT = ?0.025 (2) GPa/K, V 0 = 65.7 (1) Å3, K 0 = 73 (2) GPa, and K′ = 3.9 (2). For NaF, α0 = 1.34 (4)×10?4 K?1, dK/dT = ?0.020 (1) GPa/K, V 0 = 100.2 (2) Å3, K 0 = 46 (1) GPa, and K′ = 4.5 (1).  相似文献   

15.
The most widely used method to determine the level of tritium in humans is testing urine. Tritium concentrations in urine samples of 100 persons aged 18–66 years selected randomly from a pilot region in Turkey were analysed. The average activity concentration of urine samples was 4.66?±?1.94?Bq?L?1 and the maximum activity concentration was 27.91?Bq?L?1. The minimum detectable activity was 2.38?Bq?L?1. The annual effective dose from tritium was also evaluated on the basis of the measurement results and reference values recommended by the International Commission on Radiological Protection. The effective doses for males and females were 4.56 and 3.54?nSv, respectively. These results were lower than the permissible annual effective dose for members of the public.  相似文献   

16.
Pressure-dependent thermodynamic properties of the ambient and high pressure phases of aluminum nitride (w-AlN and rs-AlN) were calculated from first principles in order to determine their phase boundary in the p? T phase diagram. These predictions were checked by static HP/HT experiments, using a multianvil press and an Al/N/H precursor with low decomposition temperature as educt. The experimental data show that at temperatures between 1000 and 2000 K, the boundary line between the two phases is situated between 11 and 12 GPa, which is ~1.3 GPa lower than the theoretical result and generally lower than previously assumed. The hardness of rs-AlN – measured for the first time – is ~30 GPa (Knoop indenter at loads of 25–50 g), twice as hard as w-AlN. Shock wave recovery experiments on nano w-AlN allowed testing of the chemical and thermal stability of rs-AlN, and determination of its infrared absorption and 27Al NMR data. The shock wave technique will eventually enable the synthesis of larger amounts of rs-AlN, making it available for technological use. Finally, implications on the high pressure stability of phases in the Si–Al–O–N system are discussed in the light of thermoelastic properties of AlN.  相似文献   

17.
A Nd3+:Na2La4(WO4)7 crystal with dimensions of ? 17 × 30 mm3 was grown by the Czochralski method. The thermal expansion coefficients of Nd3+:Na2La4(WO4)7 crystal are 1.32 × 10?5 K?1 along c-axis and 1.23 × 10?5 K?1 along a-axis, respectively. The spectroscopic characteristics of Nd3+:Na2La4(WO4)7 crystal were investigated. The Judd–Ofelt theory was applied to calculate the spectral parameters. The absorption cross sections at 805 nm are 2.17 × 10?20 cm2 with a full width at half maximum (FWHM) of 15 nm for π-polarization, and 2.29 × 10?20 cm2 with a FWHM of 14 nm for σ-polarization. The emission cross sections are 3.19 × 10?20 cm2 for σ-polarization and 2.67 × 10?20 cm2 for π-polarization at 1,064 nm. The fluorescence quantum efficiency is 67 %. The quasi-cw laser of Nd3+:Na2La4(WO4)7 crystal was performed. The maximum output power is 80 mW. The slope efficiency is 7.12 %. The results suggest Nd3+:Na2La4(WO4)7 crystal as a promising laser crystal fit for laser diode pumping.  相似文献   

18.
We have measured the thermal diffusivity of eclogite and majorite with a model MORB composition at pressures of 3 and 15 GPa, respectively. Both phase assemblages show inverse dependences of their thermal diffusivities on temperature: D eclogite=9(10)×10?10+7(1)×10?4/T(K) m 2/s and D majorite=6.2(5)×10?7+3.0(5)×10?4/T(K) m 2/s. The values for majorite are in good agreement with previous measurements for other garnets and are considerably lower than thermal diffusivities of wadsleyite and ringwoodite, which are the main components of the mantle transition zone. We discuss the implications of the low thermal conductivity of subducted oceanic crust in the transition zone for the triggering of deep seismicity.  相似文献   

19.
Abstract

Three new bands of the B 2Σ+X 2Σ+ system of 12C17O+ have been investigated using conventional spectroscopic techniques. The spectra were observed in a graphite hollow‐cathode lamp by discharging molecular oxygen (enriched in about 45% of the 17O2 isotope) under 1.0 Torr pressure. The rotational analysis of the 2–4, 2–5, and 2–6 bands was performed with the effective Hamiltonian of Brown (Brown et al., J. Mol. Spectrosc. 1979; 74: 294–318). Molecular constants were derived from a merge calculation, including both the current wavenumbers and the spectroscopic data published by the authors previously. The principal equilibrium constants for the ground state of 12C17O+ are ωe=2185.9658(84), ωe x e = 14.7674(11), B e=1.927001(38), αe=1.8236(22)×10?2, γe=?0.331(28)×10?4, D e=6.041(12)×10?6, βe=0.100(31)×10?7 cm?1, and the equilibrium constants for the excited state are σe=45876.499(15), ωe=1712.201(12), ωe x e=27.3528(39), B e=1.754109(35), αe=2.8706(57)×10?2, γe = ?1.15(19)×10?4, D e=7.491(20)×10?6, βe=2.13(12)×10?7, γe = 2.0953(97)×10?2, and αγe=?9.46(59)×10?4 cm?1, respectively. Rydberg–Klein–Rees potential energy curves were constructed for the B 2Σ+ and X 2Σ+ states of this molecule, and Franck–Condon factors were calculated for the vibrational bands of the BX system.  相似文献   

20.
Polycarbonate (Makrofol‐N) thin films were irradiated with protons (3 MeV) under vacuum at room temperature with the fluence ranging from 1×1014 to 1×1015 protons cm?2. The change in surface morphology, optical properties, degradation of the functional groups, and crystallinity of the proton‐irradiated polymers were investigated with atomic force microscopy (AFM), UV‐VIS, and Fourier‐transform infrared (FTIR) spectroscopy, and X‐ray diffraction (XRD) techniques, respectively. AFM shows that the root mean square (RMS) roughness of the irradiated polycarbonate surface increases with the increment of ion fluence. The UV‐VIS analysis revealed that in Makrofol‐N the optical band gap decreased by 30% at highest fluence of 1×1015 protons cm?2. The band gap can be correlated to the number of carbon atoms, M, in a cluster with a modified Robertson's equation. The cluster size in the proton‐irradiated Makrofol‐N increased from 112 to 129 atoms with the increase of fluence from 1×1014 to 1×1015 protons cm?2. FTIR spectra of proton (3 MeV) irradiated Makrofol‐N showed a strong decrease of almost all absorption bands at about 1× 1014 protons cm?2. However, beyond a higher critical dose an increase in intensity of almost all characteristic bands was noticed. The appearance of a new peak at 3,500 cm?1 (‐OH groups) was observed at the higher fluences in the FTIR spectra of proton‐irradiated polycarbonate. XRD measurements showed an increase of full width at half maximum (FWHM) and the average intermolecular spacing of the main peak, which may be due to the increase of chain scission and the introduction of ‐OH groups in the proton irradiated polycarbonate.  相似文献   

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