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Perfluorinated porphyrazines
摘要： Nucleophilic substitution of fluorine atoms in the phenyl rings by alkoxy groups was performed in perfluorosubstituted zinc(II) octaphenylporphyrazine [ZnPAF40]. Up to 12 fluorine atoms are substituted in the reaction with sodium butoxide in boiling butanol leading to the formation of [ZnPAF40–n(OBu)n] (n = 6—12). Up to eight monosaccharide groups are introduced in the reaction with 1,2:3,4-di-O-isopropylidene-α-D-galactopyranose (Gal′) in toluene in the presence of sodium hydride leading to the formation of [ZnPaF(40–n)(Gal′)n] (n = 6—8). It was possible to obtain a water-soluble glycoconjugated zinc(II) porphyrazine [ZnPaF(40–n)(Gal)n] after removal of the isopropylidene protecting groups by treatment with trifluoroacetic acid. Substitution products are characterized by electron absorption spectroscopy, NMR spectroscopy, and mass spectrometry. Substituting the fluorine atoms with monosaccharide residues leads to an increase in the fluorescence quantum yield from ФF = 0.19 for [ZnPAF40] to 0.29 for [ZnPA(Gal′)nF40–n] (n = 6—8).
关键词： galactose,perfluorinated porphyrazines,water soluble porphyrazines,nucleophilic aromatic substitution
更新于2025-11-19 16:46:39
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A development of new red phosphor based on europium doped as well as substituted Barium Lanthanum Aluminate (BaLaAlO4: Eu3+)
摘要： New red emitting Eu3+ doped and substituted BaLaAlO4 phosphor powders were synthesized by simple modified solid state reaction method. BaLaAlO4 crystal phase formation studied through powder X-ray diffraction (XRD) analysis. Fourier Transform - Infra Red (FT-IR) analysis was performed to study the formation of the host with respect to temperature increment and metal-oxygen bond vibrations of BaLaAlO4 host lattice. Morphology of the phosphor was appeared as irregular in shapes with agglomeration. Photoluminescence (PL) analysis was performed to study the PL excitation and emission characteristics of the phosphor. It dictates that synthesized phosphors exhibited a strong red emission at 626 nm. Substitution effect of Eu3+ in BaLaAlO4 with various compositions such as Ba(1-x)LaAlO4: Eux3+, BaLa(1-y)AlO4: Euy3+ and BaLaAl(1-z)O4: Euz3+ were studied for PL enhancement. Luminescence decay time of the phosphors was also determined. PL thermal quenching and Commission Internationale de l'Eclairage (CIE) chromaticity analysis were carried out to find thermal stability and colour purity of the phosphor sample respectively. The Judd- Ofelt parameters (Ω2 & Ω4) obtained from the emission spectra of Eu3+ ions in BaLaAlO4 host lattice were evaluated and discussed.
关键词： BaLaAlO4,Eu3+,Red phosphor,Substitution effect,Solid state reaction
更新于2025-11-14 15:13:28
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Extended analysis of FTIR high resolution spectra of HD32S and HD34S in the region of the ν2 band: Positions and strengths of individual lines
摘要： The high resolution infrared spectra of deuterated hydrogen sulfide HDS were recorded with a Bruker IFS125HR Fourier transform infrared spectrometer (Zurich prototype ZP2001) and analyzed in the ν2 fundamental band region, 690–1510 cm?1. 2684 transitions with maximum values of the quantum numbers Jmax.=25 and Kmax.a=17 were assigned in the experimental spectra to the ν2 band (compared to Jmax.=22 and Kmax.a=10 in the preceding analogous studies) of HD32S. On this basis, 415 upper ro–vibrational energies were obtained, which were used then in the weighted fit of the Watson Hamiltonian parameters. 33 parameters obtained from the fit reproduce the 415 initial energy values with a root mean square deviation drms=1.1×10?? cm?1. An analysis of 418 experimental ro–vibrational line intensities of the ν2 band of HD32S was made using the Hartmann–Tran profile of individual lines, and results were applied in the fit of parameters of the effective dipole moment operator. Isotopic relations for the dipole moment parameters were derived and used for the fit procedure. The obtained 'model' parameters reproduce the initial line strengths with the drms=4.7%. A list of 2684 experimental transitions of HDS is generated together with the presentation of their individual line strengths predicted on the basis of the obtained effective dipole moment parameters. An analogous analysis was fulfilled for the ν2 band of the HD3?S isotopologue.
关键词： HD32S,isotopic substitution,FTIR,ν2 band,line positions,HD34S,high resolution spectra,line strengths,spectroscopic parameters
更新于2025-09-23 15:23:52
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Synthesis of a MoS <i> <sub/>x</sub></i> -O-PtO <i> <sub/>x</sub></i> Electrocatalyst with High Hydrogen Evolution Activity Using a Sacrificial Counter-Electrode
摘要： Water splitting is considered to be a very promising alternative to greenly produce hydrogen, and the key to optimizing this process is the development of suitable electrocatalysts. Here, a sacrificial-counter-electrode method to synthesize a MoSx/carbon nanotubes/Pt catalyst (0.55 wt% Pt loading) is developed, which exhibits a low overpotential of 25 mV at a current density of 10 mA cm?2, a low Tafel slope of 27 mV dec?1, and excellent stability under acidic conditions. The theory calculations and experimental results confirm the high hydrogen evolution activity that is likely due to the fact that the S atoms in MoSx can be substituted with O atoms during a potential cycling process when using Pt as a counter-electrode, where the O atoms act as bridges between the catalytic PtOx particles and the MoSx support to generate a MoSx–O–PtOx structure, allowing the Pt atoms to donate more electrons thus facilitating the hydrogen evolution reaction process.
关键词： sacrificial-counter-electrodes,O substitution,MoSx,hydrogen evolution reaction,PtOx
更新于2025-09-23 15:23:52
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Exploration of new birefringent crystals in bismuth d0 transition metal selenites
摘要： The first examples of bismuth fluoride selenites with d0-TM/Te(VI) polyhedrons, namely, Bi4TiO2F4(SeO3)4 (1), Bi4NbO3F3(SeO3)4 (2), Bi4TeO4F2(TeO3)2(SeO3)2 (3), Bi2F2(MoO4)(SeO3) (4) and Bi2ZrO2F2(SeO3)2 (5) have been successfully synthesized under hydrothermal reactions by aliovalent substitution. The five new compounds feature three different types of structures. Compounds 1-3, containing Ti(IV), Nb(V) and Te(VI) respectively, are isostructural, exhibiting a new 3D framework composed of 3D bismuth oxyfluoride architecture with intersecting tunnels occupied by d0-TM/Te(VI) octahedrons and selenite/tellurite groups. Compound Bi4TeO4F2(TeO3)2(SeO3)2 (3) is the first structure containing Se(IV) and mixed-valent Te(IV)/Te(VI) cations simultaneously. Compound 4 features a new 3D structure formed by 3D bismuth oxyfluoride network with MoO4 tetrahedrons and selenites groups embeded in the 1D tunnels. Compound 5 displays a novel pillar-layered 3D open framework consisted of 2D bismuth oxide layers bridged by the [ZrO2F2(SeO3)2]6- polyanions. Theoretical calculations revealed that the five compounds displayed very strong birefringence. The birefringence values of compounds 1-3, especially, are above 0.19 at 1064 nm, which are bigger than the mineral calcite. Based on the structure and property analysis, we found that the asymmetric SeO3 groups (and TeO3 in compound 3) displayed the largest anisotropy compared with the bismuth cations and the d0 TM/Te polyhedrons, which is beneficial to the birefringence.
关键词： metal selenites,d0 transition metals,aliovalent substitution,hydrothermal reactions,birefringent crystals
更新于2025-09-23 15:23:52
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Combined experimental and theoretical investigation on modulation of multiferroic properties in BiFeO3 ceramics induced by Dy and transition metals co-doping
摘要： Multiferroic Dy and transition metals (Cr, Mn, Ni) co-doped BiFeO3 ceramics were successfully synthesized by a solid-state method, and the influence on the magnetic and ferroelectric properties were investigated. Compared with Bi0.95Dy0.05Fe0.95Mn0.05O3, Bi0.95Dy0.05Fe0.95Cr0.05O3 and Bi0.95Dy0.05Fe0.95Ni0.05O3 ceramics can significantly improve the magnetic properties. The significant enhancement of magnetic properties should be related to the local ferromagnetic coupling from Cr ions (Ni ions) and Fe ions, which have already been proved by first-principles calculations. Meanwhile, both experimental and theoretical studies reveal the Dy substitution can effectively enhance the ferroelectric properties of BiFeO3. Leakage current and conduction mechanism analyses reveal that the improved ferroelectric properties are mainly attributed to the reduced oxygen vacancies.
关键词： Magnetic property,Ferroelectric property,BiFeO3,Substitution
更新于2025-09-23 15:23:52
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A Facile Route for NLO Materials: Three-Site Alivolent Substitution Involving One Cation and Two Anions
摘要： Two mixed-metal gallium iodate fluorides, namely, α- and β-Ba2[GaF4(IO3)2](IO3) (1 and 2) have been obtained by the aliovalent substitutions of α- and β-Ba2[VO2F2(IO3)2](IO3) (3 and 4) involving one cationic and two anionic sites. Both of them display large SHG signals (~6 × KDP), large energy bandgaps (4.61 and 4.35 eV), wide transmittance ranges (~0.27-12.5 μm), and large relevant LDTs (29.7 × and 28.3 × AgGaS2, respectively), which indicates that 1 and 2 are potential second-order NLO materials in ultraviolet to mid-infrared. Our studies propose that three-site aliovalent substitution is a facile route for the discovery of good NLO materials.
关键词： aliovalent substitution,hydrothermal synthesis,NLO material,mixed-metal iodate fluoride,theoretical calculations
更新于2025-09-23 15:23:52
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[Methods in Molecular Biology] Autophagy Volume 1880 (Methods and Protocols) || Correlative Light and Electron Microscopy to Analyze LC3 Proteins in Caenorhabditis elegans Embryo
摘要： In this chapter, we present a protocol to perform correlative light and electron microscopy (CLEM) on Caenorhabditis elegans embryos. We use a specific fixation method which preserves both the GFP fluorescence and the structural integrity of the samples. Thin sections are first analyzed by light microscopy to detect GFP-tagged proteins, then by transmission electron microscopy (TEM) to characterize the ultrastructural anatomy of cells. The superimposition of light and electron images allows to determine the subcellular localization of the fluorescent protein. We have used this method to characterize the roles of autophagy in the phagocytosis of apoptotic cells in C. elegans embryos. We analyzed in apoptotic cell and phagocytic cell the localization of the two homologs of LC3/GABARAP proteins, namely, LGG-1 and LGG-2.
关键词： LC3-associated phagocytosis,High-pressure freezing,Freeze substitution,LGG-2,Green fluorescent protein,GMA resin,LGG-1
更新于2025-09-23 15:22:29
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Constituent substitution in hot wall deposition of Bi2S3 films by reaction with substrates
摘要： Replacement of a constituent in the overgrown layers with the materials provided by the substrates is investigated when Bi2S3 films are deposited on III-V compound semiconductors and transition metals using a hot wall epitaxy method. The substitution caused by the S atoms is stronger than that by the Se and Te atoms in deposition of Bi2Se3 and Bi2Te3 films. Mere exposure to Bi2S3 vapor of In-containing compounds (InP and InAs) and Ga-containing compounds (GaAs and GaSb) at epitaxial growth temperatures results in a capping of their surfaces by In2S3 and GaS, respectively. A temperature window is revealed to exist for the GaAs case where growth of Bi2S3 microcrystals occurs within the temperature range for the sulfide formation. The sulfurization by the material substitution is thus demonstrated to be not always identical with that using elemental sulphur. We examine furthermore the sulfides synthesized on the surfaces of Cu, Ag, Ni, Mo, and W. The sulfides produced on Cu and Ag undergo material alterations when they are irradiated by a laser light.
关键词： X-ray crystallography,Hot wall epitaxy,Material substitution,Raman spectroscopy,Bi2S3,Sulfides
更新于2025-09-23 15:22:29
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Elucidating Spray Dried Dispersion Dissolution Mechanisms with Focused Beam Reflectance Measurement: Contribution of Polymer Chemistry and Particle Properties to Performance
摘要： Amorphous spray dried dispersions (SDDs) are a key enabling technology for oral solid dosage formulations, used to improve dissolution behaviour and clinical exposure of poorly-soluble active pharmaceutical ingredients (APIs). Appropriate assessment of amorphous dissolution mechanisms is an ongoing challenge. Here we outline the novel application using Focused Beam Reflectance Measurement (FBRM) to analyse particle populations orthogonal to USP 2 dissolution. The relative impact of polymer substitution and particle attributes on 25% BMS-708163/HPMC-AS SDD dissolution was assessed. Dissolution mechanisms for SDDs were categorized into erosion versus disintegration. Beyond an initial mixing period, FBRM particle counts diminish slowly and particles are detectable until the point where API dissolution is complete. There is correlation between FBRM particle count decay rate, representing loss of SDD particles in the dissolution media, and UV dissolution rate, measuring dissolved API. For the SDD formulation examined, the degree of succinoyl substitution for HPMC-AS, SDD particle size and surface area all had an impact on dissolution. These data indicate the SDD displayed an erosion mechanism and that FBRM is capturing a rate-limiting step. From this screening tool, the mechanistic understanding and measured impact of polymer chemistry and particle properties can inform a risk-assessment and control strategy for this compound.
关键词： HPMC-AS,FBRM,SDD,substitution,dissolution-mechanism,amorphous,surface area,erosion,dispersion,particle-size
更新于2025-09-23 15:22:29