Synthesis and characterization of dimeric μ-oxidovanadium complexes as the functional model of vanadium bromoperoxidase

Two vanadium (IV) complexes [V^IVO(Haeae-sal)(MeOH)]⁺ ( 1 ) and [V^IVO(Haeae-hyap)(MeOH)]⁺ ( 2 ) were prepared by reacting [VO(acac)₂] with ligands [H₂aeae-sal] ( I ) and [H₂aeae-hyap] ( II ) respectively. Condensation of 2-(2-aminoethylamino)ethanol with salicylaldehyde and 2-hydroxyacetophenone produces the ligands ( I ) and ( II ) respectively. Both vanadium complexes 1 and 2 are sensitive towards aerial oxygen in solution and rapidly convert into vanadium(V) dioxido species. Vanadium(V) dioxido species crystalizes as the dimeric form in the solid-state. Single-crystal XRD analysis suggests octahedral geometry around each vanadium center in the solid-state. To access the benefits of heterogeneous catalysis, vanadium(V) dioxido complexes were anchored into the polymeric chain of chloromethylated polystyrene. All the synthesized neat and supported vanadium complexes have been studied by a number of techniques to confirm their structural and functional properties. Bromoperoxidase activity of the synthesized vanadium(V) dioxido complexes 3 and 4 was examined by carrying out oxidative bromination of salicylaldehyde and oxidation of thioanisole. In the presence of hydrogen peroxide, 3 shows 94.4% conversion ( TOF value of 2.739 × 10² h⁻¹) and 4 exhibits 79.0% conversion (TOF value of 2.403 × 10² h⁻¹) for the oxidative bromination of salicylaldehyde where 5-bromosalicylaldehyde appears as the major product. Catalysts 3 and 4 also efficiently catalyze the oxidation of thioanisole in the presence of hydrogen peroxide where sulfoxide is observed as the major product. Covalent attachment of neat catalysts 3 and 4 into the polymer chain enhances substrate conversion (%) and their catalytic efficiency increases many folds, both in the oxidative bromination and oxidation of thioether. Polymer supported catalysts 5 displayed 98.8% conversion with a TOF value of 1.127 × 10⁴ h⁻¹ whereas catalyst 6 showed 95.7% conversion with a TOF value of 4.675 × 10³ h⁻¹ for the oxidative bromination of salicylaldehyde. These TOF values are the highest among the supported vanadium catalysts available in the literature for the oxidative bromination of salicylaldehyde.     

Nonstoichiometric laser materials: Designer wavelengths in neodymium-doped garnets

The tunable nature of lasers provides for a wide range of applications. Most applications rely on finding available laser wavelengths to meet the needs of the research. This article presents the concept of compositional tuning, whereby the laser wavelength is designed by exploiting nonstoichiometry. For research where precise wavelengths are required, such as remote sensing, this is highly advantageous. A theoretical basis for the concept is presented and experimental results in spectroscopic measurements support the theoretical basis. Laser operation nicely demonstrates the validity of the concept of designer lasers.     

796 nm二极管泵浦连续波1.88 W Tm∶LYF激光器

用坩埚下降法生长了Tm³⁺掺杂浓度分别为0.8%和1.3%的优质大尺寸LiYF₄(LYF)单晶体。测定了单晶体的吸收光谱、发射光谱,并计算了³F₄能级的的最大吸收截面与最大发射截面分别为0.25×10^-20 cm²和0.33×10^-20 cm²。以796 nm半导体激光器(LD)为泵浦源,采用短平板腔结构模型研究了Tm掺杂LYF单晶体在～2.0μm波段的激光输出性能。当LD泵浦功率为3.4 W时,Tm∶YLF晶体的最大激光输出功率为1.88 W,相应的光光转换效率和斜率效率分别为51%和57%。使用半导体可饱和吸收镜抽运Tm掺杂LYF单晶体,测试其在～2.0μm波段连续波锁模激光运转。当最大抽运功率为3.5 W时,获得锁模激光的最大平均输出功率为200 mW,此时锁模脉冲宽度～20 ps,对应的重复频率63.86 MHz,中心谱线为1.88μm。结果表明,Tm掺杂LYF单晶体是一种具有较好物理性能的～2μm波段超...     

微顺序注射-分光光度法快速测定海水中总磷

基于微顺序注射-阀上实验室,采用磷钼蓝分光光度法测定了海水中总磷,对实验参数进行了优化,并选取了海水中主要成分离子进行了干扰实验。结果表明,海水中总磷质量浓度在0.009~1mg/L范围内与吸光度呈线性关系(r=0.9995),方法的检出限为0.003mg/L。该法测定秦皇岛黄金海岸表层海水中总磷浓度为0.090mg/L,与国标法测定结果0.088mg/L无显著性差异;测定含磷浓度为0.20mg/L的人工海水,相对标准偏差(RSD)为2.4%,样品加标回收率为94.4%~95.7%;海水中主要离子对本实验方法测定产生的干扰在5%以内。     

亚纯函数的Valiron亏函数

对于开平面内有穷级的超越亚纯函数f(z),本文主要讨论其Valiron亏函数问题,得到f(z)的Valiron亏函数的F_δ-集合必为μ-集合的结论,去掉了陈怀惠等对f(z)的极点的要求。最后指出对于无穷级的情形,也有相应的结论。     

Iwasawa μ-invariants of elliptic curves and their symmetric powers

In an earlier paper we considered the effects that finite submodules can have on μ-invariants of Selmer groups. In this paper we examine some of the consequences of that theory to elliptic curves and their symmetric powers. One main result is the construction of an isogeny class of elliptic curves, all of which have positive μ-invariants. A second result is a connection between the behaviors of μ-invariants associated with the symmetric powers of an elliptic curve over , and the behavior of the μ-invariant of that elliptic curve over different extensions of .     

The absorption spectrum of phosphine (PH3) between 2.8 and 3.7 μm: Line positions, intensities, and assignments

Over 8000 line positions and intensities of phosphine (PH₃) at 3 μm have been measured at 0.0115 cm⁻¹ resolution with the McMath-Pierce Fourier Transform spectrometer at Kitt Peak. The observed line intensities ranged from 4.13 × 10⁻⁶ to 4.69 × 10⁻² cm⁻² atm⁻¹ at 296 K, for line positions between 2724.477 and 3601.652 cm⁻¹. This region spans eight interacting vibrational states: 3ν₂ (2940.8 cm⁻¹), 2ν₂ + ν₄ (3085.6 cm⁻¹), ν₂ + 2ν₄ (3214.9 cm⁻¹), ν₁ + ν₂ (3307.6 cm⁻¹), ν₂ + ν₃ (3310.5 cm⁻¹), 3ν₄ (∼3345 cm⁻¹), ν₁ + ν₄ (3426.9 cm⁻¹), and ν₃ + ν₄ (3432.9 cm⁻¹). Assignments have been determined for all the bands except 3ν₄ (a weak band in a highly congested area) for a total of 4232 transitions. The total integrated intensity for this region is 5.70 cm⁻² atm⁻¹ near 296 K, and assigned lines account for 79% of the observed absorption. The two strongest bands in the region are ν₁ + ν₄ and ν₃ + ν₄ with band strengths at 296 K of 1.61 and 2.01 cm⁻² atm⁻¹, respectively. An empirical database of PH₃ line parameters (positions, intensities, and assignments) is now available. Lower state energies (corresponding to assignments from this study) and line widths from the literature are included; default values are used for unassigned features.     

N(2,2,0)代数的(∈,∈Vq_(λ,μ))-模糊关联理想若干性质

对N(2,2,0)代数(∈,∈∨q_((λ,μ)))-模糊关联理想若干性质进行了详细的研究.首先,运用点态化的方法证明了(∈,∈∨q_((λ,μ)))-模糊关联理想的同态像与同态原像的基本性质;其次,研究了(∈,∈∨q_((λ,μ)))-模糊关联理想的直积;最后,讨论了(∈,∈∨q_((λ,μ)))-模糊关联理想的直积的投影子集.     

一类小缺陷码的链条件

利用射影几何方法在小缺陷码中,NMDS码是链条件码;给出k维NμMDS(0μk-2)码满足链条件的一个充要条件与一些易判断的充分条件.     

基于模糊值Choquet积分定义集函数的S性与PGP性

针对模糊测度空间上已建立的模糊值Choquet积分,将这种积分整体看成可测空间上取值于模糊数的集函数,当模糊测度满足一般S性和PGP性时,研究了这种模糊值集函数所保持的遗传性质.