新型非对称二苯并[b,f][1,5]二氮杂环辛四烯的合成

以两种不同取代的2-氨基二苯甲酮为原料,氯苯为溶剂,BF3-Et2O为脱水剂,通过分子间脱水一步环化缩合制备非对称二苯并[b,f][1,5]二氮杂环辛四烯衍生物。运用HPLC监控反应过程,优化合成工艺,得到最佳反应条件为:等物质的量的两种不同取代2-氨基二苯甲酮和BF3-Et2O,在氯苯中回流反应12 h。化合物4a^4c为新化合物,其结构经1H NMR,13C NMR和MS(ESI)表征。     

Dynamical Analysis of a New Chaotic Fractional Discrete-Time System and Its Control

This article proposes a new fractional-order discrete-time chaotic system, without equilibria, included two quadratic nonlinearities terms. The dynamics of this system were experimentally investigated via bifurcation diagrams and largest Lyapunov exponent. Besides, some chaotic tests such as the 0–1 test and approximate entropy (ApEn) were included to detect the performance of our numerical results. Furthermore, a valid control method of stabilization is introduced to regulate the proposed system in such a way as to force all its states to adaptively tend toward the equilibrium point at zero. All theoretical findings in this work have been verified numerically using MATLAB software package.     

Multifunctional Sulfur-Hyperdoped Silicon Nanoparticles with Engineered Mid-Infrared Sulfur-Impurity and Free-Carrier Absorption

Si nanoparticles (NPs), which are innovative promising light-harvesting components of thin-film solar cells and key-enabling biocompatible theranostic elements of infrared-laser and radiofrequency hyperthermia-based therapies of cancer cells in tumors and metastases, are significantly advanced in their near/mid-infrared band-to-band and free-carrier absorption via donor sulfur-hyperdoping during high-throughput facile femtosecond-laser ablative production in liquid carbon disulfide. High-resolution transmission electron microscopy and Raman microscopy reveal their mixed nanocrystalline/amorphous structure, enabling the extraordinary sulfur content of a few atomic percents and very minor surface oxidation/carbonization characterized by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. A 200-nm thick layer of the nanoparticles exhibits near−mid-infrared absorbance, comparable to that of the initial 380-micron thick n-doped Si wafer (phosphor-dopant concentration ≈10¹⁵ cm⁻³), with the corresponding extinction coefficient for the hyperdoped NPs being 4–7 orders higher over the broadband spectral range of 1–25 micrometers. Such ultimate, but potentially tunable mid-IR structured, multi-band absorption of various sulfur-impurity clusters and smooth free-carrier absorption are break through advances in mid-infrared (mid-IR) laser and radiofrequency (RF) hyperthermia-based therapies, as envisioned in the RF-heating tests, and in fabrication of higher-efficiency thin-film and bulk photovoltaic devices with ultra-broad (UV−mid-IR) spectral response.     

原子分子光子系统的耗散相互作用和退相干

原子分子系统与量子化的电磁场或光子模式耦合的系统是非相对论量子力学理论研究和实验研究的主要对象和模型. 现实系统必然与外界环境耦合，且即便原子隔绝较好、光学腔壁品质因子足够高，原子系统也不等价于少数几个能级构成的简单模型：它仍然有不为零的几率跃迁到不可控的能级空间、与原子相互作用的自由空间真空场的量子效应也必须考虑. 本文将结合开放量子系统理论的基本要素与原子光子的基本模型，对原子分子系统在电磁场中发生的耗散以及量子退相干过程做简单综述，并重点介绍描述量子系统退相干过程的主流理论工具——主方程.     

氨基酸官能团的太赫兹振动模式研究

对比于氨基酸的红外分析法,太赫兹波的电子能量更低,可实现无损检测。氨基酸分子内原子振动、分子间氢键的作用、以及晶体中晶格的低频振动均处于太赫兹波段,使其在太赫兹波段具有吸收峰,且不同的氨基酸分子太赫兹吸收峰不同,故可用氨基酸在太赫兹波段的这种“指纹特性”实现氨基酸类物质的定性分析。量子化学分析方法可以应用量子力学的基本原理和方法,研究稳定和不稳定分子的结构、性能及其之间的关系,还可以针对分子与分子间的相互作用、相互碰撞及相互反应等问题进行研究。通过量子化学计算方法计算氨基酸分子的太赫兹吸收谱,可以为氨基酸分子的太赫兹吸收峰匹配分子振动模式,对氨基酸定性分析有一定参考性与指向性,并为实验获取的样品太赫兹时域光谱提供理论支撑,在实验获得太赫兹吸收谱的基础上进行量子化学计算,还能为实验结果进行验证。首先利用太赫兹时域光谱技术获取了谷氨酰胺、苏氨酸、组氨酸的太赫兹吸收谱,分别构建这三种氨基酸样品在实物中以两性离子形式存在的单分子构型,利用量子化学计算方法在完成结构优化后进行太赫兹吸收谱模拟计算。计算结果表明三种氨基酸单分子的太赫兹吸收谱计算结果与实验获取的太赫兹吸收谱差异较大,但在高频段吸收峰峰位基本吻合。通过GaussView分别查看了这三种氨基酸分子在太赫兹段内的吸收峰对应频率处的振转情况,发现在高频段内三种氨基酸分子官能团均只发生转动而未见振动,并且转动模式基本一致。通过对氨基酸官能团的太赫兹吸收谱进行量子化学计算,将官能团在高频段内吸收峰对应频率处的振转模式与三种氨基酸分子在该段内吸收峰对应频率处的振转模式做了对比。研究表明,在氨基酸单分子构型下由量子化学方法计算所得的太赫兹吸收谱中,高频段内计算得出的模拟吸收峰与实验获取的太赫兹吸收峰基本吻合;振转模式分析发现,谷氨酰胺、苏氨酸、组氨酸在太赫兹高频段内的氨基酸官能团振转模式相同,三种氨基酸分子在高频段内的吸收峰主要来源于氨基酸官能团。因此,结合量子化学计算与太赫兹吸收谱可以实现氨基酸类物质的定性分析。     

Dinuclear gold (I)-di-N-heterocyclic carbene complexes: syntheses,structure, density functional theory calculation and photoluminescence study

The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, ¹H- and ¹³C-NMR data. The ¹³C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]₂·2PF₆ is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λ_em = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm.     

Controlled synthesis of ZnO nanoparticles from a Zn(II) coordination polymer: Structural characterization,optical properties and photocatalytic activity

A zinc coordination polymer derived from pyridine-2,6-dicarboxylate (PDC), {[Zn₂(PDC)₂]}_n, was successfully prepared via conventional, sonication and microwave-irradiation methods. The composition and characteristics of the obtained coordination polymers (CPs) were investigated by elemental analysis, TGA/DTA, X-ray diffraction and spectroscopic techniques. The so obtained CPs were heat-treated in the air at 600 °C for 2 h to produce ZnO of nanosized particles (NPs). It is of interest to note that the synthesis approach of the precursor greatly affects both the nanoparticle size and the structure of the resulting ZnO NPs. Moreover, the smallest particle size was associated with the sample derived from the ultrasonically prepared precursor. TEM analysis revealed that all samples have sphere-like morphologies. Structural analysis of the prepared ZnO samples was conducted and compared using Rietveld analysis of their PXRD patterns. Optical band gap calculations based on analysis of the UV–vis spectra of ZnO samples using Tauc's power law were achieved. The highest band gap of 3.63 eV was observed for ZnO sample obtained from the ultrasonically prepared precursor. Furthermore, the photocatalytic activity of ZnO NPs for the removal of Eosin Y color was monitored. The highest removal efficiency was recorded for ZnO originated from the ultrasonically synthesized precursor. Enhancement of removal efficiency that reached 98% was attained in only a period of 8 min. Its recycling test showed that it can be reused without structural changes over four cycling experiments.     

Optimization of extraction and quantification technique for phenolics content of garlic (Allium sativum): An application for comparative phytochemical evaluation based on cultivar origin

A range of conventional, i.e. maceration, percolation, ultrasonic assisted, Soxhlet and Soxtec extraction (STE), to advanced extraction techniques of accelerated solvent extraction (ASE) was utilized for the first time in order to optimize the extract yield and recovery of phenolics—gallic acid (GA), rutin (RT) and quercetin (QT)—quantified via ultra-high performance liquid chromatography with diode array detector (UHPLC–DAD). The effect of solvents (n-hexane, dichloromethane and methanol) and temperature (60, 80 and 100°C) upon extraction yield, phenolic content and antioxidant activity (DPPH, ABTS and DPPH) was studied, and the method was validated in commercial food samples from Saudi Arabia, China and India. A high extract yield with percentage recovery was observed for STE (1221.10 mg/5 g; 24.42%) and ASE techniques (91.50 mg/1 g; 9.15%) in methanol at 100°C. UHPLC–DAD showed retention times (min) of 0.67, 1.93 and 1.90 for GA, RT and QT, respectively in the shortest runtime of 3 min. The yield for phenolics was higher for STE/ASE (ppm): 15.27/15.29 (GA), 85.24/37.56 (RT) and 52.20/33.40 (QT), respectively. In terms of antioxidant activities, low IC₅₀ values (μg/ml) of 1.09/1.18 (DPPH), 2.11/5.32 (ABTS) and 4.35/7.88 (phenazine methosulfate–nicotinamide adenine dinucleotide) were observed for STE and ASE, respectively. Multivariate analysis for STE showed a significant (P = 0.000) correlation for extraction type vs. extract yield and phenolics content; however, there was no significance for antioxidant activities vs. extraction type. ASE showed a positive correlation for solvent vs. extraction yield, phenolics and antioxidant activity; however, there was no correlation for extraction yield and DPPH activity. Principal component analysis for STE showed a major variability (52.02%) for extraction yield and phenolics in PC1 followed by PC2 (38.30%) for antioxidant activities. For ASE, PC1 (48.68%) showed a positive correlation for solvent vs. extraction yield and phenolics while PC2 (33.12%) showed a positive correlation for temperature and antioxidant activities. STE and ASE were the optimized extraction techniques for the garlic food sample while a significant effect of solvent and temperature was observed upon extraction yield, phenolics and antioxidant activity.     

A molecular fluorophore in citric acid/ethylenediamine carbon dots identified and quantified by multinuclear solid-state nuclear magnetic resonance

The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by ¹³C, ¹³C{¹H}, ¹H─¹³C, ¹³C{¹⁴N}, and ¹⁵N solid-state nuclear magnetic resonance (NMR) experiments. ¹³C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. ¹⁵N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved ¹³C NMR peaks, including an unusual ═CH signal at 84 ppm (¹H chemical shift of 5.8 ppm) and ═CN₂ at 155 ppm, and two distinctive ¹⁵N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a ¹H─¹³C HETCOR spectrum with brief ¹H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative ¹³C and ¹⁵N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in ¹³C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation.     

Complementarity between micro-micro and micro-macro entanglement in a Bose–Einstein condensate with two Rydberg impurities

We theoretically study complementarity between micro-micro and micro-macro entanglement in a Bose–Einstein condensate with two Rydberg impurities. We investigate quantum dynamics of micro-micro and micro-macro entanglement in the micro-macro system. It is found that strong micro-macro entanglement between Rydberg impurities and the BEC can be generated by the use of initial micro-micro entanglement between two Rydberg impurities, which acts as the seed entanglement to create micro-macro entanglement. We demonstrate a curious complementarity relation between micro-micro and micro-macro entanglement, and find that the complementarity property can be sustained to some extent even though in the presence of the BEC decoherence.