基于气体浓度定量的嗅觉刺激器优化设计

现有的基于磁共振测量的嗅觉刺激器，通过调节嗅剂液体浓度的方法可以实现不同浓度的嗅觉刺激，但随着实验进行，受到嗅剂挥发以及实验环境（温度、湿度、气流量）变化的影响，很难确保输送至鼻腔的嗅剂气体浓度的稳定性，进而影响实验结果的准确性．本研究对本实验室前期开发的嗅觉刺激装置进行改进，实现了气体浓度精确定量．改进后的嗅觉刺激器主要分为三个部分：控制系统、反馈系统和气路系统．控制系统主要实现气路系统的送气控制和嗅剂气体浓度调节；反馈系统则负责对气体浓度进行测量；气路系统则在原有基础上添加活性炭装置，降低无关因素干扰．装置改进之后，不同气路切换时间为75.2 ms，比原装置减少了1 s，有效提高刺激精度．实验结果显示，气体浓度调节前，300 s内乙醇、吡啶、乙酸戊酯嗅剂气体浓度分别下降6.7%、71.4%、79.2%，嗅剂气体浓度短时间内发生较大改变．加入气体浓度调节功能后，当气体浓度下降至目标浓度的90%时，可通过调节气泵电压改变嗅剂气流与空气气流比例，从而调节嗅剂气体浓度至目标值，其中吡啶、乙酸戊酯用时13 s．     

Highly Stable Univalent Copper of a Cu@Al/SBA-15 Nanocomposite Catalyzes the Synthesis of Fluorescent Aminobenzotriazoles Derivatives

With the development of green chemistry, it is still a challenge to maintain the unstable valence state of the metal in heterogeneous catalysts and realize new catalytic synthesis methods. In this paper, it is reported that an univalent copper nanocomposite (Cu@Al/SBA-15) can efficiently catalyze the formation of novel amino-containing benzotriazoles with great fluorescence properties in a new synthetic strategy. Subsequently, its application is further verified by an acylation reaction to produce a series of novel benzotriazoles derivatives with high yield. It is worth noting that the Cu@Al/SBA-15 nanocomposites not only enable the reaction completed with high yield in a short time, but can also be recycled many times without a significant reduction in activity, and the leaching of copper and aluminum species in reaction system is negligible. Finally, the detailed and feasible reaction mechanism is also provided.     

Novel synthesis of sensor for selective detection of Fe+3 ions under various solvents

Naked-eye colored chemo dosimeter based on vanilline based conjugated sensor was synthesized and characterized. The main point of this paper is that the solvent also affects on selectivity of metals. Vanilline based conjugate sensor exhibited high selectivity and sensitivity for detection of Ferric ions (Fe⁺³) in all (both polar and nonpolar) solvents according to absorbance which can be observed by naked eye. The selectivity was more prominent in nonpolar or less polar solvent due to solubility factor of ions and sensor but not for polar. The detection of limit of the synthesized probes was shown up to 0.84 ppm. The dielectric constant of solvents affected on the complex formation of ligand with transition metal ions. A filter paper strip system was used for rapid monitoring of detection by color variation.     

基于2,5-二溴对苯二甲酸配体的锌/钴配合物合成、晶体结构及性质

将有机物2,5-二溴对苯二甲酸(H₂L₁)和2,2′-联吡啶(L₂)作为双配体,使用溶剂热法和七水合硫酸锌(ZnSO₄·7H₂O)、六水合硝酸钴(Co(NO₃)₂·6H₂O)分别反应,得到配合物[Zn(L₁)(L₂)(H₂O)]_n(1)和配合物[Co(L₁)(L₂)(H₂O)]_n(2)。采用单晶X射线衍射、元素分析、红外光谱、紫外光谱、荧光光谱、热重分析等测试方法对这两种物质进行分析研究。单晶测试结果表明配合物1是单斜晶系,以Zn²⁺配位连接L^2-₁与L₂形成一维链状结构,各条链在分子间氢键和π…π共轭作用下有规律地堆叠形成三维网络结构。配合物2是三斜晶系,Co1离子和Co1ⁱ离子由H₂L₁上的羧酸氧原子O4和O4ⁱ连接,形成双齿螯合的配位结构单元,以Co²⁺配位连接 L^2-₁和L₂形成二维网格结构,各层在O—H…O分子间氢键和范德瓦耳斯力作用下有规律的堆叠形成三维网络结构。配合物1和2均含有芳香杂环、羧基杂环和氮杂环,具有良好的荧光性质和热稳定性,最大发射波长分别为345 nm和333 nm。     

Benchmarking of Density Functionals for the Description of Optical Properties of Newly Synthesized π-Conjugated TADF Blue Emitters

Computational modeling of the optical characteristics of organic molecules with potential for thermally activated delayed fluorescence (TADF) may assist markedly the development of more efficient emitting materials for organic light-emitting diodes. Recent theoretical studies in this area employ mostly methods from density functional theory (DFT). In order to obtain accurate predictions within this approach, the choice of a proper functional is crucial. In the current study, we focus on testing the performance of a set of DFT functionals for estimation of the excitation and emission energy and the excited singlet-triplet energy gap of three newly synthesized compounds with capacity for TADF. The emitters are designed specifically to enable charge transfer by π-electron conjugation, at the same time possessing high-energy excited triplet states. The functionals chosen for testing are from various groups ranging from gradient-corrected through global hybrids to range-separated ones. The results show that the monitored optical properties are especially sensitive to how the long-range part of the exchange energy is treated within the functional. The accurate functional should also be able to provide well balanced distribution of the π-electrons among the molecular fragments. Global hybrids with moderate (less than 0.4) share of exact exchange (B3LYP, PBE0) and the meta-GGA HSE06 are outlined as the best performing methods for the systems under study. They can predict all important optical parameters correctly, both qualitatively and quantitatively.     

湿法消解-原子荧光法测定全血中硒

以全血样品为原料,探讨湿法消解-原子荧光法测定全血中的硒含量。血样经硝酸-高氯酸消解后,用硼氢化钠将硒还原成硒化氢,由氩气载入原子化器,产生的原子荧光强度与试液中硒元素含量在一定范围内呈正比,外标法定量。以消解效率为指标,优化样品的消解条件,测定血中硒在0-10μg/L范围内线性情况良好,相关系数为0.9992,最低检出限为0.143μg/L,相对标准偏差为1.51%-1.58%,平均加标回收率为90.86%-104.62%。血中硒的原子荧光测定法灵敏度高,精密度和稳定性好,可应用于血中硒的生物监测。     

高居里温度铁电单晶PIN-PT的机电性能

弛豫铁电单晶Pb(In_1/2Nb_1/2)O₃-PbTiO₃(PIN-PT)相较于常用的Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃(PMN-PT)具有更高的居里温度,在高稳定性、高性能的传感器、换能器方面具有应用前景。本工作采用谐振法研究了[001]方向极化的0.66PIN-0.34PT铁电单晶的全矩阵机电性能参数。0.66PIN-0.34PT 单晶的三方-四方相变温度(T_RT)约为160 ℃,居里温度(T_C)约为260 ℃,室温压电系数d₃₃、d₃₁、d₁₅分别为1 340 pC/N、-780 pC/N、321 pC/N,介电常数ε^T₃₃、ε^S₃₃、ε^T₁₁、ε^S₁₁分别为2 700、905、2 210、1 927,机电耦合系数 k₃₃、k₃₁、k₁₅、k_t分别为 87%、58%、38%、61%。其纵向压电常数(d₃₃)和纵向机电耦合系数(k₃₃)小于 PMN-PT 单晶,但是横向压电性能(d₃₁)和剪切压电性能(d₁₅)都略高于PMN-PT单晶。另外,研究了机电耦合性能随温度的变化趋势,发现0.66PIN-0.34PT单晶在150 ℃以下有较好的温度稳定性。     

1,3,5-三(羧基甲氧基)苯镍配位聚合物的合成、晶体结构及性质研究

采用溶剂热法,1,3,5-三(羧基甲氧基)苯为定向配体和乙酸镍反应构筑了一个新型的金属配位聚合物[Ni(TB)₂(H₂O)₂]_n·2H₂O,其中H₃TB=1,3,5-三(羧基甲氧基)苯,通过元素分析、IR及X射线单晶衍射对配合物结构进行表征,并研究其荧光性质、热稳定性及Hirshfeld表面作用力。单晶结构分析表明,该配合物属于三斜晶系,空间群$P \overline{1}$,配合物中心离子Ni(Ⅱ)分别与来自两个水分子上的氧原子及四个不同1,3,5-三(羧基甲氧基)苯配体的羧酸氧原子配位,形成六配位的NiO₆八面体构型,并通过与1,3,5-三(羧基甲氧基)苯配体的氧原子配位不断延伸形成具有孔洞结构的一维链状构型。配合物具有良好的荧光性能和热稳定性。Hirshfeld表面作用分析表明配合物分子中O…H/H…O作用占主导且占比为39.0%,而H…H的作用力占比为25.9%,O…O的作用力占比为13.6%。     

Sensitivity improvement of aluminum-based far-ultraviolet nearly guided-wave surface plasmon resonance sensor

An aluminum (Al) based nearly guided-wave surface plasmon resonance (NGWSPR) sensor is investigated in the far-ultraviolet (FUV) region. By simultaneously optimizing the thickness of Al and dielectric films, the sensitivity of the optimized Al-based FUV-NGWSPR sensor increases from 183°/RIU to 309°/RIU, and its figure of merit rises from 26.47 RIU^-1 to 32.59 RIU^-1 when the refractive index of dielectric increases from 2 to 5. Compared with a traditional FUV-SPR sensor without dielectric, the optimized FUV-NGWSPR sensor can realize simultaneous improvement of sensitivity and figure of merit. In addition, the FUV-NGWSPR sensor with realistic materials (diamond, Ta₂O₅, and GaN) is also investigated, and 137.84%, 52.70%, and 41.89% sensitivity improvements are achieved respectively. This work proposes a method for performance improvement of FUV-SPR sensors by exciting nearly guided-wave, and could be helpful for the high-performance SPR sensor in the short-wavelength region.     

Label-Free Fluorescent Kinase and Phosphatase Enzyme Assays with Supramolecular Host-Dye Pairs

The combination of the macrocyclic hosts p-sulfonatocalix[4]arene and cucurbit[7]uril with the fluorescent dyes lucigenin and berberine affords two label-free enzyme assays for the detection of kinase and phosphatase activity by fluorescence monitoring. In contrast to established assays, no substrate labeling is required. Since phosphorylation is one of the most important regulatory mechanisms in biological signal transduction, the assays should be useful for identification of inhibitors and activators in high-throughput screening (HTS) format for drug discovery.