1,2-Dihydro-1-hydroxy-2,3,1-benzodiazaborine Bearing an Acridine Moiety as a Circular Dichroism Probe for Determination of Absolute Configuration of Mono-Alcohols

A new chiral probe molecule for mono-alcohols is developed by using 1,2-dihydro-1-hydroxy-2,3,1-benzodiazaborine (DAB) bearing an acridine moiety 1 . In the presence of mono-alcohols, DAB 1 forms borate 2 by boronic ester formation, followed by coordination of the acridine moiety to the boron atom. Borate 2 has a chiral center on the boron atom and works as a stereodynamic circular dichroism (CD) probe molecule for chiral mono-alcohols based on the π–π interaction between the acridine moiety and the carbon–carbon unsaturated moiety on mono-alcohols.     

温度对AZO薄膜红外辐射性能的影响

随着全球资源的减少和环境的恶化，节能减排已成为人们关注的焦点，具有保温隔热功能的低辐射玻璃成为研究的热点。提高玻璃保温隔热性能最有效的方法就是在其表面涂覆低辐射率层。原材料丰富、导电性能好、可见光透过率高等优势使得Al掺杂ZnO (AZO)薄膜成为最具潜力的低辐射率层。系统研究了温度对AZO薄膜红外辐射性能的影响，分析了变化机理。首先研究了在一定的温度下持续一段时间后，AZO薄膜的红外比辐射率的变化情况。然后研究了在变温环境中红外比辐射率的变化情况。采用直流磁控溅射法在室温下玻璃基片上沉积500 nm厚的AZO薄膜，将薄膜放到马弗炉中进行热处理，在100～400 ℃空气气氛下保温1 h，随炉冷却。采用X射线衍射仪对AZO薄膜进行物相分析，采用扫描电子显微镜观察薄膜表面形貌变化。利用四探针测试法测量AZO薄膜的电阻率，采用红外比辐射率测试仪测试薄膜红外比辐射率, 可见分光光度计测量可见光谱。测试的结果表明，薄膜热处理前后均为六角纤锌矿结构，(002)择优取向。300 ℃及以下热处理1 h后，(002)衍射峰增强，半高宽变窄，晶粒尺寸长大。随着热处理温度的升高，薄膜的电阻率先减小后增大，200 ℃热处理后的薄膜具有最小的电阻率(0.9×10-3 Ω·cm)。热处理温度升高，晶粒长大使得薄膜电阻率降低。热处理温度过高，薄膜会从空气中吸收氧，电阻率下降。薄膜的红外比辐射率变化趋势和电阻率的一致，在200 ℃热处理后获得最小值(0.48)。自由电子对红外光子有较强的反射作用，当电阻率低，自由电子浓度高的时候，更多的红外光子被反射，红外辐射作用弱，红外比辐射率小。薄膜的可见光透过率随着热处理温度的升高先减小后增大，200 ℃热处理后的薄膜的可见光透过率最小，但仍高达82%。这种变化是由于自由电子浓度变化引起的，自由电子对可见光有很强的反射作用。选取未热处理和200 ℃热处理后的样品进行变温红外比辐射率的测量，将样品放在可加热的样品台上，位置固定，在室温到350 ℃的升温和降温过程中每隔25 ℃测量一次红外比辐射率，结果表明，在室温到350 ℃的温度范围内，AZO薄膜的红外比辐射率在升温过程中随着温度的上升而增大，在降温过程中减小，经过整个升、降温过程后，薄膜的红外比辐射率增大。     

Development of three novel benzothiazole-based ratiometric fluorescent chemosensor for detecting of hydrazine in serum and gas phase via ESIPT process and different recognition sites

In this article, we have successfully designed and synthesized three novel ratiometric fluorescent probes BTP-LA, BTP-LB and BTP-LN for detection of hydrazine based on benzothiazole-derived fluorophores and different recognition sites. The probes BTP-LA, BTP-LB and BTP-LN displays a good fluorescence ratio emission signals, high selectivity and large emission shifts (>100 nm) toward hydrazine. The three probes BTP-LA, BTP-LB and BTP-LN can be used not only to detect hydrazine in serum, but also to detect gaseous hydrazine in air. More importantly, compared with probes BTP-LB and BTP-LN, BTP-LA has lower saturation concentration (200 µM) and detection limits (1.22 × 10^?7 M) to hydrazine.     

Fluorometric analysis of borohydrides based on reductive aldehyde-to-alcohol conversion of arylaldehydes

Fluorometric analysis of borohydride (BH₄^–) species by the reduction of arylaldehydes to the corresponding arylmethanols was investigated. 9-Anthracenecarboxaldehyde (9-AA) exhibited pronounced ratiometric fluorescence signaling behavior toward borohydride in alkaline aqueous media. The borohydride-selective signaling of 9-AA was unaffected by the presence of commonly encountered metal ions and anions. 1-Pyrenecarboxaldehyde (1-PA) also showed comparable borohydride signaling behavior. The detection limit was found to be 7.4?μM (0.11?ppm) for 9-AA and 15.7?μM (0.23?ppm) for 1-PA. The utility of the probe with μPAD as a convenient tool for the determination of borohydrides was demonstrated.     

Highly sensitive perylene tetra-(alkoxycarbonyl) based colorimetric and ratiometric probes for fluorine detection

Fluoride anion (F^?) affects environmental, biological, and chemical processes significantly. Therefore, its detection has received increasing attention, and sensitive, effective, and convenient probes for F^? detection need to be developed urgently. In this work, two perylene tetra-(alkoxycarbonyl) (PTAC) based colorimetric and ratiometric probes, P1 and P2, were developed for the detection of F^?. The interactions between F^? and these two probes were investigated by absorption, electrochemistry, ¹H NMR, and density functional methods. Both the two probes were complexed with F^? with a ratio of 1:1. The detection limits of P1 and P2 were 0.22 μM and 0.87 μM, respectively. It was worth noting that the absorption peak of P1 showed a 190 nm red shift when sensing F^?, and P1 is the largest red shift value reported in F^? probes based on PTAC derivatives. This phenomenon was resulted from the unique configuration and deprotonation of P1 that can promote the intramolecular charge transfer (ICT). This strategy provides an example for the development of other ion probes based on D-A type ICT mechanism.     

The effect of probe-Ohmic environment coupling type and probe information flow on quantum probing of the cutoff frequency

This work aims to compare results of dissipating and pure dephasing single-qubit probes in characterizing the cutoff frequency of a harmonic reservoir Ohmic spectral density. In particular, we proved that a dissipating single-qubit improves the estimation precision of the cutoff frequency estimator. The information backflow and outflow of the dissipating and the dephasing single-qubit are compared. The relation between the quantum Fisher information and the information outflow and backflow of the probe is obtained. The results show that difference between the values of information outflow and backflow of a dissipating single-qubit is larger than a dephasing single-qubit. So, a single-qubit probe extracts more information from an Ohmic reservoir by increasing the difference between the values of information outflow and backflow of the probe.     

Infrared spectroscopy of closed s-shell gas-phase M+(N2O)n (M = Li,Al) ion-molecule complexes*

ABSTRACT

We present the results of a combined experimental and computational study of the structures of gas-phase M⁺(N₂O)_n (M?=?Li, Al) complexes. Infrared spectra were recorded in the region of the N₂O asymmetric (N?=?N) stretch using photodissociation spectroscopy employing the inert messenger technique. Unlike in our previous studies on M⁺(N₂O)_n (M?=?Cu, Ag, Au and M?=?Co, Rh, Ir) complexes, N– and O–bound isomers in this case are near isoenergetic and are not distinguished spectroscopically at this resolution. In the case of Li⁺ complexes, there is, however, evidence for the presence of bound N₂ moieties, indicating the presence of inserted, OLi⁺N₂(N₂O)_n–type structures. The weak N₂ band lies to the blue of the signature of molecularly N– and O–bound ligands and is well–reproduced in the simulated spectra of energetically low-lying structures computed from density functional theory. No such inserted isomers are observed in the case of Al⁺(N₂O)_n complexes whose infrared spectra can be understood on the basis of molecularly-bound N₂O ligands. The differences in M⁺(N₂O)_n structures observed for these closed–shell, ns², metal centres relative to other metal cations are discussed in terms of the likely bonding motifs.     

Probing molecular environments with a fictitious isotopic dipole

A HD-like (HD: mono-deuterated hydrogen molecule) isotopic dipole moment is proposed as a sensible probe for molecular environments, in particular for electrostatic fields and polarizable (reactive) sites of molecules. Fictitious nuclear masses are chosen in order to yield a rigid dipole with a small appropriate magnitude. Upon subtracting the Born-Oppenheimer energy, the interaction is reduced to field-dipole-like and dipole-polarizability-like terms, the last one being particularly informative since connected to potentially reactive sites. Possible asymmetries of this term appear as signatures of charged sites in the molecule. The field strength and orientation are easily obtained by identifying the minimum field-dipole energy configuration and flipping the dipole from it. Tests with hydrogen, water, benzene, and chlorobenzene molecules confirm the good performance of the method. In an application to test the present models for hydrogen activation by a frustrated Lewis pair, the full potential of the method is assessed.     

[Co(CO2)n]+团簇的红外解离光谱实验和理论研究

本文利用红外光解离光谱研究了一价钴阳离子与二氧化碳之间的相互作用. 通过密度泛函理论计算得到[Co(CO₂)_n]⁺团簇的几何结构，并且模拟了它们的振动光谱与实验数值进行比较. 研究结果表明，在[Co(CO₂)_n]⁺(n=2∽6)团簇中，钴阳离子通过电四极矩静电作用以端点结合的方式与二氧化碳中的氧原子结合在一起. 团簇的红外光谱都集中在二氧化碳反对称伸缩的波数附近，并且随着团簇尺寸的变化出现蓝移，最后把[Co(CO₂)_n]⁺的红外光解离光谱与稀有气体贴附的[Co(CO₂)_n]⁺-Ar的红外光解离光谱进行了比较.     

矿物药炉甘石煅制前后锌、铅元素的赋存形态及分布特征研究

采用X射线衍射(XRD)技术和电子探针微区分析(EPMA)技术针对中药炉甘石煅制前后锌、铅元素的赋存形态及分布特征进行了研究，探明了煅制对炉甘石中锌、铅元素赋存状态及分布的改变，为后续水飞减除铅元素的机理研究提供了理论依据。测试结果显示：21批次炉甘石(生品)中的锌元素以主矿物水锌矿[Zn₅(CO₃)₂(OH)₆]和杂质矿物异极矿[Zn₄(OH)₂(H₂O)(Si₂O₇)]为主要赋存形态，偶见菱锌矿(ZnCO₃)；炉甘石(生品)的背散射电子图谱及元素分布数据显示：Zn和Pb元素同时分布的区域为水锌矿，Zn和Si元素同时分布的区域为异极矿，Ca和Mg元素同时分布的区域为白云石，Ca元素单独分布区域为方解石。在炉甘石(生品)中，Pb主要分布于水锌矿中且分布相对均匀，Pb元素的分布与水锌矿中的Zn元素密切相关。大量水锌矿的微区点位的电子探针定量分析结果显示：各不同点位中的ZnO/PbO含量的比值趋于定值，Pb在水锌矿中呈统计式均匀分布，说明Pb在水锌矿中主要以类质同象混入物的形式存在。但是炉甘石(生品)中的异极矿、方解石及白云石等杂质矿物中铅元素含量极低甚至检测不到。炉甘石煅烧后水锌矿晶格中的Zn和Pb分别生成了ZnO和PbO。Zn元素在炉甘石煅制品中主要以氧化锌(ZnO)形式存在，少部分以杂质矿物硅酸锌(Zn₂SiO₄)形式存在，呈较连续状态分布。Pb元素在炉甘石煅制品中主要以氧化铅(PbO)的形式存在，呈星点状分布，与Zn元素的分布未呈现相关性，说明Pb在炉甘石煅制品中是以独立矿物形式存在的。煅烧破坏了水锌矿的晶格结构，在改变锌、铅化合物形态的同时，更改变了锌、铅的分布特征，打破了炉甘石中锌、铅的共生状态，使水飞减除铅元素成为可能。