Tris(dithiocarbamato)iron(III) complexes as precursors for iron sulfide nanocrystals and iron sulfide-hydroxyethyl cellulose composites

Iron(III) complexes of dimethyldithiocarbamate and imidazolyl dithiocarbamate were synthesized and characterized by elemental analyses, FTIR, UV–VIS and the ligands by NMR spectroscopy. The complexes were thermolysed as single molecule precursors at 180°C to prepare octadecylamine (ODA) capped iron sulfide nanocrystals and iron sulfide-hydroxyethyl cellulose (HEC) composites. UV–VIS, PL, FTIR, P-XRD, HRTEM, FESEM and EDS were used to characterize the iron sulfide nanocrystals and corresponding HEC nanocomposites. XRD confirmed iron sulfide nanocrystal (NP1) from dimethyldithiocarbamate to be hexagonal pyrrhotite-5H, Fe₉S₁₀ crystalline phase while iron sulfide nanocrystals (NP2) from imidazolyl dithiocarbamate is in pyrrhotite, Fe₁₁S₁₂ crystalline phase. TEM images show that the iron sulfide nanocrystals have particle sizes in the range 24–32?nm for NP1 and 18–25?nm for NP2 iron sulfide nanocrystals. The optical band gaps of the iron sulfide nanocrystals obtained from Tauc plots are 3.83 and 4.16?eV for NP1 and NP2, respectively. IR spectra, FESEM surface morphology and EDS spectra of iron sulfide/HEC composites confirmed dispersion of the iron sulfide nanocrystals within the hydroxyethyl cellulose (HEC) matrix.     

Synthesis and Characterization of Tetravalent Cerium Complexes with p-Tert-butylcalix[ n ] arenes （ n = 4, 6, 8）

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Cationic Peptides and Their Cu(II) and Ni(II) Complexes: Coordination and Biological Characteristics

Antimicrobial peptides are a promising group of compounds used for the treatment of infections. In some cases, metal ions are essential to activate these molecules. Examples of metalloantibiotics are, for instance, bleomycin and dermcidin. This study is focused on three new pseudopeptides with potential biological activity. The coordination behavior of all ligands with Cu(II) and Ni(II) ions has been examined. Various analytical methods such as potentiometric titration, UV-Vis and CD spectroscopies, and mass spectrometry were used. All compounds are convenient chelators for metal ion-binding. Two of the ligands tested have histidine residues. Surprisingly, imidazole nitrogen is not involved in the coordination of the metal ion. The N-terminal amino group, Dab side chains, and amide nitrogen atoms of the peptide bonds coordinated Cu(II) and Ni(II) in all the complexes formed. The cytotoxicity of three pseudopeptides and their complexes was evaluated. Moreover, their other model allowed for assessing the attenuation of LPS-induced cytotoxicity and anti-inflammatory activities were also evaluated, the results of which revealed to be very promising.     

Experimental ionization cross-sections of phosphorus and calcium by electron spectroscopic imaging

The absolute partial electron scattering cross-section for the phosphorus L_2,3-shell ionization was measured by electron spectroscopic imaging using poliovirus as a primary standard. The equivalent calcium cross-section was obtained in relation to phosphorus using the stoichiometric ratio for these two elements in hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂. At 80kcV, the partial cross-section of phosphorus was 2.26 times 10^?20 and 2.68 × 10^?20cm²/atom for poliovirus and hydroxyapatite, respectively, at 150eV loss for a 15-cV energy window and an acceptance angle of 15 mrad. Under the same conditions the calcium cross-section was 0.49 × 10^?20 cm²/atom at 360 eV loss. The experimental values are slightly higher than the theoretical cross-sections calculated either by hydrogenic or Hartree—Slater approaches.     

Theoretical study of the VUV spectroscopy of Ce3+ and Tb3+ in BaBPO5 crystal using an empirical-ab initio hybrid method

The f-d transition of Ce3+and Tb3+in BaBPO5 was studied theoretically using the parametric Hamiltonian model.In order to overcome the difficulty in determining many of the parameter values,we adopted the model-space effective Hamiltonian method to determine the crystal-field parameters and spin-orbit parameters values.The method made use of the energies and eigenvectors,which were obtained from an ab initio calculation using the relativistic self-consistent discrete variational Slater software package(DV-Xα).Other parameters,which were less dependent on host crystals,were taken from published data.The calculated values of parameters were reasonable,and the energy-levels and f-d transition spectra agreed reasonably well with the measured excitation spectra of 5d-4f emission.     

温度对P110钢在水泥挤出液中钝化膜性能的影响

目的 探究P110套管钢在不同温度下生成的钝化膜的性能差异,找到能使P110套管钢生成最稳定钝化膜的温度,同时了解该温度下氯离子对钝化膜的破坏规律。方法 利用极化曲线、交流阻抗谱（EIS）和Mott-Schottky测试,研究了P110套管钢材料在pH值为13.0的水泥挤出液中浸泡4 d的钝化行为,讨论了在低、中、高（40、65、90 ℃）三种温度下生成的钝化膜的稳定性,并用扫描电子显微镜（SEM）对各试样表面微观形貌进行观察。最后在溶液中加入不同浓度的氯离子,通过测试极化曲线了解氯离子对钝化膜的破坏规律。结果 试样在40、65、90 ℃下的腐蚀电流密度分别为2.2727×10?6、4.0452×10?7、1.7081× 10?5 A/cm2,膜电阻分别为100 100、238 200、5480 Ω?cm2。40、65 ℃下所生成的钝化膜呈p型半导体特征,而90 ℃下呈双极型半导体特征。65 ℃下,随着氯离子浓度的增加,试样的腐蚀电位负移,耐蚀性逐渐降低,腐蚀速率增大,当浓度达到0.1 mol/L时,钝化膜的膜层结构已被破坏。结论 P110套管钢在pH值为13.0的水泥挤出液中浸泡4 d,表面能够生成钝化膜。在65 ℃溶液中生成的钝化膜耐蚀性最好,膜层结构更加致密,40 ℃次之,90 ℃最差。氯离子对钝化膜有侵蚀作用,高浓度的氯离子可以直接导致稳定钝化膜的破坏。     

Predicting and optimizing the physical and spectroscopic properties of phosphate laser glasses using a phase diagram approach

Despite the significant technological applications of laser glasses, the quantitative prediction and optimization of their properties, particularly the spectroscopic properties, remain challenging. Here we address this problem by regarding the nearest-neighboring congruently melting compounds as the “component and structural motifs” based on the phase diagram approach. The composition–structure–property (CSP) relationships of Nd³⁺-doped ternary phosphate glasses are investigated. Spectroscopic properties are quantitatively predicted with an error of less than 10% compared to the experimental results. In particular, the fluorescence lifetime (τ_m) can be accurately calculated using the phase diagram approach, which is difficult to be predicted previously. Furthermore, the CSP databases with over 1000 compositions are established for the optimization of commercial laser glasses. This study enriches the CSP database of traditional laser glass and provides guiding significance for future research.     

Dielectric response and polarization mechanism of alkali silicate glasses in gigahertz to terahertz frequency range

Oxide glasses are dielectric materials with potential applications in high-frequency communications; hence, their dielectric properties in the gigahertz to terahertz frequency range should be investigated. In this study, the dielectric properties of silica glass and five single alkali silicate glasses were measured at 0.5–10 THz using terahertz time-domain spectroscopy and far-infrared spectroscopic ellipsometry. At 0.5–10 THz, the silica glass exhibited low dielectric dispersion with a low dielectric constant and loss. By contrast, the alkali silicate glasses exhibited high dielectric dispersion, and the dielectric constant and loss were higher than those of the silica glass. The shape of the dielectric dispersion profile depended on the alkali-metal ions; it was broader for lighter ions such as Li ions and sharper for heavier ions such as Cs ions. The peak dielectric loss shifted toward a lower frequency as the weight of the alkali-metal ions in the alkali-silicate glass increased. To understand the dielectric dispersion, the complex permittivity was calculated using molecular dynamics simulations. The theoretical results qualitatively agreed with the experimental data. Ion dynamics analysis revealed that alkali-metal ions vibrate and migrate under an applied electric field, which affects the dielectric constant and loss of alkali-silicate glasses at gigahertz to terahertz frequencies. To fabricate filter devices at low temperatures, alkali metals should be added to silicate glass; therefore, a minimum amount of light alkali metals should be used to minimize the dielectric loss of the glass materials while maintaining productivity.     

Quantitative electron spectroscopic diffraction analyses of the crystal formation in dentine

Newly formed apatitic crystallites of different hard tissues consist, according to our investigations, of chains composed of nanometre-sized particles (islands, dots) arising at nucleating sites of the collagenous and noncollagenous matrix macromolecules. In dentine these islands coalesce rapidly in longitudinal direction to form needle-like crystallites which further coalesce to ribbon-like crystallites. We have concluded that the centre-to-centre distances between these islands represent the distances between the nucleating sites of the matrix macromolecules. We have applied energy-filtering transmission electron microscopy in the selected area electron diffraction mode at different stages of crystal formation in dentine and have obtained quantitative information of the degree of crystal disorder on the basis of the paracrystal theory. The fluctuation of the lattice plane distances in c -axis direction decreases, proceeding from the region near the dentine/predentine border to the dentine/enamel border.     

Electrochemical Impedance Spectroscopic Analysis of Sensitization-Based Solar Cells

Electrochemical impedance spectroscopy (EIS) is a very powerful tool for elucidation of charge transfer and transport processes in sensitization-based solar cells (e.g., dye-sensitized solar cells [DSSCs], quantum dot-sensitized solar cells [QDSSCs], and perovskite solar cells [PSCs]). EIS measures the electrochemical response to small amplitude AC signals over a wide range of frequencies. Analysis of the EIS response provides information about the corresponding parameters of the cells. Here, we review the fundamentals of EIS, charge transport kinetic processes, and equivalent circuit models of sensitization-based solar cells and use these concepts to explain the EIS spectra of DSSCs, QDSSCs, and PSCs. This review will be very useful for understanding the fundamental charge transfer and transport processes in different sensitization-based solar cells and the use of an equivalent circuit model to interpret the observed charge transfer and reactions.