Spectral Studies on Cyclic Chromotropic Acid Tetramers and Their Interaction with Metal Ions

Abstract

With comparable molar quantities, chromotropic acid reacts with compounds containing aldehyde groups -CHO e.g. with formadehyde or glyoxylic acid to form cyclic compounds with rings containing four chromotropic acid fragments — cyclotetrachromotropylene derivatives. The cyclic compounds, due to the presence of a cavity in the molecule, can play the part of host and complex smaller molecules, which has been confirmed on the basis of triethylamine by the ¹H-NMR measurements. Using spectrophotometric method the stability constant of 1:1 complex formed between Ti(IV) and cyclic compound chromotropic acid with formaldehyde has been determined - K = (9,0 ± 0,1) 10⁴.     

基于石墨相氮化碳量子点直接荧光猝灭法检测碘离子的研究

石墨相氮化碳(g-C₃N₄)荧光纳米材料具有原料便宜、制备容易、荧光量子产率高、光学稳定性好、毒性低等优点,并且避免有机荧光染料复杂的合成步骤或者金属半导体量子点对环境潜在的危害,这些优点使得g-C₃N₄纳米材料成为新兴的荧光探针用于检测金属离子。最近,已有文献报道重金属汞离子能够高灵敏高选择性地猝灭g-C₃N₄量子点的荧光,加入碘离子能够提取被键合的汞离子形成碘化汞(HgI₂)进而恢复g-C₃N₄量子点的荧光,从而建立一种高灵敏检测碘离子的荧光传感器。然而,该方法依然需要重金属汞离子的参与,限制了该方法的推广应用。通过硝酸氧化块体g-C₃N₄并结合水热法处理制备了一种水溶性好、荧光强度高的g-C₃N₄量子点。该量子点的荧光发射波长位于368 nm,且其荧光发射波长不随激发波长的改变而改变,表明该量子点的尺寸比较均一。笔者发现碘离子在220 nm处有一个较强的吸收峰,与该量子点的激发光谱(中心波长245 nm)具有较大的重叠,从而产生内滤效应引起该量子点的荧光发生猝灭。利用这一性质,构建了一种选择性检测碘离子的新型荧光传感器。在最优检测条件下,g-C₃N₄量子点的荧光猝灭强度(ΔF)与碘离子浓度(X,μmol·L-1)在10～400 μmol·L-1之间具有良好的线性关系,线性方程为ΔF=0.325 79X+6.039 05(R2=0.999 5),检出限为5.0 μmol·L-1。通过“混合即检测”并且不需要借助与重金属离子的配位作用就能够检测碘离子,因此该方法具有快速、环保以及操作简便等优点。     

摩擦点火Ti-V-Cr阻燃钛合金燃烧产物的组织特征

采用摩擦氧浓度实验方法, 结合原位观察、扫描电镜、能谱仪和X-射线衍射分析, 系统研究Ti-V-Cr 阻燃钛合金燃烧产物的微观组织形貌、燃烧反应过程的合金元素分布规律及微观机理. 结果表明: Ti-V-Cr 阻燃钛合金燃烧过程发出闪亮耀眼的白光, 具有典型金属燃烧的火焰特征. 燃烧产物主要有TiO₂, V₂O₅和Cr₂O₃三种氧化物, 该混合氧化物以分散颗粒和致密连续体存在. 分散颗粒为规则的球形; 致密连续燃烧产物的微观组织具有分区特征, 从合金基体至燃烧表面依次为过渡区、热影响区、熔凝区和燃烧区. 其中, 过渡区存在一些微小的颗粒状凸起, 且有一定方向性; 热影响区中形成大量V基固溶体相和少量的Ti基固溶体相, V基固溶体相上存在Ti的含量远高于基体的针状析出物; 熔凝区中, 大量的Ti基固溶体中存在少量的V基固溶体; 燃烧区主要为Ti, V和Cr的氧化物混合物. 热影响区的V基固溶体相降低了Ti元素向熔凝区的迁移速率, 减慢了燃烧区Ti与O的优先反应; 燃烧区形成的TiO₂, V₂O₅和Cr₂O₃混合氧化物和熔凝区O在Ti中大量固溶共同终止了O向合金基体的继续扩散, 从而使Ti-V-Cr阻燃钛合金表现出优异的阻燃功能性.     

Visible Light Photocatalytic Functional TiO2/PVDF Nanofibers for Dye Pollutant Degradation

The photodegradation of poly(vinylidene fluoride) (PVDF)/titanium oxide (TiO₂) nanofibers under visible light is described, something that has not been previously reported in the literature. Visible light photocatalytic electrospun PVDF/TiO₂ nanofiber webs with anatase TiO₂ concentration varying from 0% to 20% (0%, 1%, 3%, 5%, 10%, and 20%) are produced, and their ability to degrade a toxic pollutant, Rhodamine B (RhB), is studied. Photodegradation study using UV–vis spectroscopy on PVDF/TiO₂ nanofiber webs (with TiO₂ concentration of 20%) shows that 80% of RhB is degraded within 6 h at the wavelength of 546 nm, which clearly falls within the visible spectra. The color of RhB solvent catalyzed by PVDF/TiO₂ nanofiber webs gradually changes from red to orange, then to yellow, further to light yellow till colorless, which suggests the complete photodegradation of RhB under visible light. To estimate the rate of photodegradation, the reaction constant k is calculated. Based on the k value, PVDF/TiO₂ nanofiber webs with 20% TiO₂ concentration show the highest degradation rate compared to other PVDF/TiO₂ nanofiber webs and pure TiO₂ nanoparticles. This study proves the viability of TiO₂‐based nanofibers to have catalytic capabilities under low‐energy visible light.     

Mössbauer studies of ɛ-Fe3−x Ni x N and γ′-Fe4−y Ni y N nanoparticles

Nanocrystalline ?-Fe_3?x Ni _x N (0.0?≤?×?≤?0.8) particles are synthesized by precursor technique and nitridation of decomposed products in NH₃ (g) in the temperature range 673 K-823 K. For x?=?0.1–0.4 compositions, single phase ?-Fe_3?x Ni _x N hexagonal structure with space group P6₃/mmc is formed, while for x?=?0.5–0.8, fcc γ′-Fe_4?y Ni _y N phase is also precipitated. The room temperature Mössbauer spectrum for all the compositions shows the presence of superparamagnetic doublet, which is attributed to ?-Fe_3?x Ni _x N phase. For x?=?0.5–0.8 compositions, two additional sextets are observed corresponding to two different iron sites, the corner position (Fe^c) and the fcc position (Fe^f), in γ′-Fe_4?y Ni _y N. The added Ni atoms preferentially substitute the corner Fe^c positions. The isomer shift, quadrupole splitting and hyperfine field values are found to change with the Ni content.     

Influence of Cu electroplating solutions on boron carbon nitride (BCN) film

Cu electroplating is required for the fabrication of Cu/low-k interconnections. The permeation of a plating solution into low-k films during Cu electroplating is a serious challenge for 45-nm nodes and more complex devices. We investigated the influence of Cu electroplating solutions on boron carbon nitride (BCN) as a low-k film. After dipping it into a Cu electroplating solution that contained additives, the BCN film's hydrophilic surface changed to a hydrophobic surface, and the incorporation of water into the BCN film was suppressed by surfactant adsorption. Sulfuric residue was detected on the BCN sample by thermal desorption spectroscopy after treatment in the Cu electroplating solution with additives; however, it was found through electrical measurements that this solution did not affect the leakage current or the dielectric constant of the BCN film. We successfully fabricated an electroplating Cu layer on a BCN film with good adhesion, and we believe that this BCN film is a sufficiently useful material for Cu/BCN integration in LSI.     

Microstructure and strain films using in-plane grazing analysis of GaN epitaxial incidence x-ray diffraction

This paper investigates the major structural parameters, such as crystal quality and strain state of （001）-oriented GaN thin films grown on sapphire substrates by metalorganic chemical vapour deposition, using an in-plane grazing incidence x-ray diffraction technique. The results are analysed and compared with a complementary out-of-plane x- ray diffraction technique. The twist of the GaN mosaic structure is determined through the direct grazing incidence t of （100） reflection which agrees well with the result obtained by extrapolation method. The method for directly determining the in-plane lattice parameters of the GaN layers is also presented. Combined with the biaxial strain model, it derives the lattice parameters corresponding to fully relaxed GaN films. The GaN epilayers show an increasing residual compressive stress with increasing layer thickness when the two dimensional growth stage is established, reaching to a maximum level of-0.89 GPa.     

A study of GaN MOSFETs with atomic-layer-deposited Al2O3 as the gate dielectric

Accumulation-type GaN metal-oxide-semiconductor field-effect transistors (MOSFETs) with atomic-layer-deposited Al₂O₃ gate dielectrics are fabricated. The device, with atomic-layer-deposited Al₂O₃ as the gate dielectric, presents a drain current of 260 mA/mm and a broad maximum transconductance of 34 mS/mm, which are better than those reported previously with Al₂O₃ as the gate dielectric. Furthermore, the device shows negligible current collapse in a wide range of bias voltages, owing to the effective passivation of the GaN surface by the Al₂O₃ film. The gate drain breakdown voltage is found to be about 59.5 V, and in addition the channel mobility of the n-GaN layer is about 380 cm²/Vs, which is consistent with the Hall result, and it is not degraded by atomic-layer-deposition Al₂O₃ growth and device fabrication.     

Electronic properties of anatase TiO2 doped by lanthanides: A DFT+U study

The effects of mono-doping of 4f lanthanides with and without oxygen vacancy defect on the electronic structures of anatase TiO₂ have been studied by first-principles calculations with DFT+U (DFT with Hubbard U correction) to treat the strong correlation of Ti 3d electrons and lanthanides 4f electrons. Our results revealed that dopant Ce is easy to incorporate into the TiO₂ host by substituting Ti due to its lower substitutional energy (∼−2.0 eV), but the band gap of the system almost keeps intact after doping. The Ce 4f states are located at the bottom of conduction band, which mainly originates from Ti 3d states. The magnetic moment of doped Ce disappears due to electron transfer from Ce to the nearest O atoms. For Pr and Gd doping, their substitutional energies are similar and close to zero, indicating that both of them may also incorporate into the TiO₂ host. For Pr doping, some 4f spin-down states are located next to the bottom of the conduction band and narrow the band gap of the doping system. However, for Gd doping, the 4f states are located in deep valence band and there is no intermediate band in the band gap. The magnetic moment of dopant Gd is close to the value of isolated Gd atom (∼7 μB), indicating no overlapping between Gd 4f with other orbitals. For Eu, it is hard to incorporate into the TiO₂ host due to its very higher substitutional energy. The results also indicated that oxygen vacancy defect may enhance the adsorption of the visible light in Ln-doped TiO₂ system.     

A density functional theory study on parameters fitting of ultra long armchair （n, n） single walled boron nitride nanotubes

Armchair(n,n) single walled boron nitride nanotubes with n = 2-17 are studied by the density functional theory at the B3LYP/3-21G(d) level combined with the periodic boundary conditions for simulating the ultra long model.The results show that the structure parameters and the formation energies bear a strong relationship to n.The fitted analytical equations are developed with correlation coefficients larger than 0.999.The energy gaps of(2,2) and(3,3) tubes are indirect gaps,and the larger tubes(n = 4-17) have direct energy gaps.Results show that the armchair boron nitride nanotubes(n = 2-17) are insulators with wide energy gaps of between 5.93 eV and 6.23 eV.