Effect of bromine substituent on optical properties of aryl compounds

Substituents significantly affect optical properties of organic compounds. In this study, a series of organic compounds were synthesized. Ultraviolet‐visible and cyclic voltammetry spectra were determined. The relationships between the number of π electron in an aryl ring and the redshift (and molecular orbital energy levels) were studied. To investigate mechanisms of the bromine substituent effects, theoretical calculations were carried out. Ultraviolet‐visible spectra of bromine‐containing compounds exhibit obvious redshifts (0.04‐0.17 eV) of the maximal absorption wavelengths and enhanced absorbance (11%‐57%) compared with corresponding reference compounds. The lowest unoccupied and highest occupied molecular orbital energy levels of compounds containing bromine substituents are 0.05 to 0.60 and 0.02 to 0.40 eV lower than that of corresponding reference compounds. On the whole, the redshifts and the reduced molecular orbital energy levels caused by bromine substituent decrease with the increase in the number of π electron in an aryl ring. The effects would be attributed to strong p‐π conjugation between p electron in the bromine substituent and π electrons in aryl rings. Therefore, this paper suggests a useful way for tuning optical absorption and molecular orbital energy levels of aryl compounds.     

Anilinolysis of O‐butyl phenyl phosphonochloridothioate in acetonitrile: Synthesis,characterization, kinetic study,and reaction mechanism

This paper describes a simple optimized method for the synthesis of O‐butyl phenyl phosphonochloridothioate ( 4 ) under mild conditions. The target compounds were characterized by ¹H‐nuclear magnetic resonance (NMR), ¹³C‐NMR, and ³¹P‐NMR spectroscopy, as well as mass spectroscopy. The apparent structure of 4 was confirmed by optimization using the B3LYP/6‐311 + G(d,p) level in the Gaussian 09 program in acetonitrile. The nucleophilic substitution reactions of 4 with X‐anilines (XC₆H₄NH₂) and deuterated X‐anilines (XC₆H₄ND₂) were investigated kinetically in acetonitrile at 55.0°C. The free energy relationship with X in the anilines looked biphasic concave upwards with a break region between X = H and X = 3‐MeO, giving large negative ρ_X and small positive β_X values. The deuterium kinetic isotope effects were secondary inverse (k_H/k_D < 1: 0.789‐0.995) and the magnitudes, (k_H/k_D), increased when the nucleophiles were changed from weakly basic to strongly basic anilines. A concerted S_N2 mechanism is proposed on the basis of the selectivity parameters and the variation trend of the deuterium kinetic isotope effects with X.     

Chitosan loaded with silver nanoparticles,CS‐AgNPs,using thymus syriacus,wild mint,and rosemary essential oil extracts as reducing and capping agents

The present study describes the green method for the preparation of chitosan loaded with silver nanoparticles (CS‐AgNPs) in the presence of 3 different extracted essential oils. The essential oils play dual roles as reductant and capping agents. The reducing power and DPPH (2,2‐diphenyl‐1‐picrylhydrazyl) assay for the 3 essential oils—Thymus syriacus (T), wild mint (M), and rosemary (R)—have been reported. The preparation of CS‐AgNPs was performed by 2 steps. The 3 previously extracted essential oils have been used as reducing and capping agent in the first step, while in the second step, silver nanoparticles were integrated in chitosan. The integration of AgNPs in the structure of chitosan was confirmed by ultraviolet‐visible, Fourier transform infrared spectroscopy, scanning electron microscopy techniques, and energy dispersive X‐ray. Surface plasmon resonance confirmed the formation of CS‐AgNPs with maximum absorbance at λ_max between 405 ‐ 410 and 410 ‐ 430 nm for colloidal and films of CS‐AgNPs, respectively. The intensity of bands at 3408 cm^?1 in the fourier transform infrared spectroscopy measurements was decreased substantially and shifted slightly to lower frequency (?υ = 43 cm^?1). Scanning electron microscopy shows a spherical morphology of AgNPs with size of 62 nm for both colloidal and film samples, and energy dispersive X‐ray analysis shows peaks confirming AgNPs formation.     

Strategy of improving the stability and detonation performance for energetic material by introducing the boron atoms

A novel stable energetic compound (E)‐1,2‐diamino‐1,2‐dinitrodiboron (DANB) was theoretically designed based on the structure of 1,1‐diamino‐2,2‐dinitroethene (FOX‐7). Atomization method in combination with Hess' law was used to predict the heat of formation. The detonation velocity (D) and detonation pressure (P) of DANB were approximatively estimated by using Kamlet–Jacobs equations. As a result, DANB has huge heat of formation (2013.5 kJ/mol) and specific enthalpy of combustion (?26.4 kJ/g). Furthermore, DANB possesses high crystal density (1.85 g/cm³) and heat of detonation (5476.0 cal/g), which lead to surprising detonation performance (D = 10.72 km/s, P = 51.9 GPa) that is greater than those of FOX‐7 (D = 8.63 km/s, P = 34.0 GPa) and CL‐20 (D = 9.62 km/s, P = 44.1 GPa). More importantly, DANB is very stable because its bond dissociation energy of the weakest bond (BDE = 357.8 kJ/mol) is larger than those of the most common explosives, such as FOX‐7 (BDE = 200.4 kJ/mol), CL‐20(BDE = 209.2 kJ/mol), HMX(BDE = 165.7 kJ/mol), and RDX (BDE = 161.4 kJ/mol). Therefore, our results show that DANB is a promising candidate for stable and powerful energetic material.     

Photochromism of new unsymmetrical diarylethenes with a quinoline moiety

Three unsymmetrical diarylethenes with a 6‐membered quinoline moiety were synthesized to investigate the effects of the substituents on their photochromism, and fluorescence, and the structure of one diarylethene was determined by single crystal X‐ray diffraction analysis. Quinoline was connected directly to the central perfluorocyclopentene ring as an aryl moiety and available to participate in photoisomerization reaction in solution, amorphous films, and crystalline phase. These diarylethenes exhibited good photochromism with excellent thermal stability and obvious fatigue resistance. The electron‐donating methoxy group could enhance the absorption maxima of closed‐ring isomers and the quantum yields of cyclization and cycloreversion, but the electron‐withdrawing trifluoromethyl had an opposite effect. In addition, they functioned as notable fluorescence switches in both solution and polymethylmethacrylate films, and the trifluoromethyl group and the methoxy group both increased the emission intensity. The results revealed that the quinoline moiety and substituents played a vital role in the process of photoisomerization reactions for these diarylethenes.     

Targeting Upconversion Nanoprobes for Magnetic Resonance Imaging of Early Colon Cancer

Colon cancer (CC) is one of the most common intestinal malignancies and is difficult to detect in its early stage by magnetic resonance imaging (MRI) with currently used contrast agents (CAs). The development of targeted CAs contributes to the early diagnosis of CC and thereby enables early intervention and timely therapy. Considering the outstanding performance of upconversion nanoprobes (UCNPs) in high‐performance MR and fluorescence imaging, a new type of nanoprobes with considerably enhanced imaging performance is developed herein. Carcinoembryonic antigen (CEA) antibody is conjugated onto the surface of UCNPs to achieve the targeted imaging of early CC tumors, which overexpress CEA. Both toxicity tests and histological/hematological examinations demonstrate the excellent biocompatibility of these CC‐targeting nanoprobes, which possess great potential for clinical application in the early diagnosis of CC.     

Renal Clearable Luminescent WSe2 for Radioprotection of Nontargeted Tissues during Radiotherapy

High‐energy ionizing radiation is widely used in medical diagnosis and cancer radiation therapy. However, high‐energy radiation can also impose significant damages in healthy tissues during medical treatments via direct DNA damages and indirect damages from production of reactive oxygen species (ROS). Therefore, it is urgent to develop highly effective radioprotectants with low toxicities that can meet the increasing needs for alleviating the adverse effects from cancer radiation therapy and nuclear emergency. In this work, strongly catalytic ultrasmall (sub‐5 nm) cysteine‐protected WSe₂ dots are employed to protect healthy tissues against radiation via diminishing radiation‐induced free radicals. The WSe₂ dots with high surface activities can recover radiation‐induced DNA damages and eliminate the excessive ROS generated from radiation. In vivo experiments confirm that the survival rate of mice treated with WSe₂ dots is significantly elevated with radiation damages postponed under exposure to high‐dose ionizing radiation. Furthermore, the free radicals in major organs and hematological system can be appreciably omitted, suggesting their unique role as free radical scavengers. These WSe₂ dots in ultrasmall size show rapid renal clearance of ≈74% injection dose via urine excretion in 24 h and do not cause any apparent toxicity in vivo for up to 30 d.     

Numerical study of InGaN tandem solar cells with intermediate bands

Theoretical investigations of InGaN tandem solar cells with intermediate bands (IBs) have been conducted through calculating the diode equation taking into account the radiative and nonradiative recombination currents. The calculated maximum ef?ciencies of the double‐junction cell with one IB in each subcell are 57.85% and 68.37% under AM1.5G one‐sun and 46000‐sun illuminations, respectively. It has also been observed that the combined device with the top‐cell bandgaps of 2.9–3.4 eV (2.6–3.4 eV for full concentration) may have an opportunity to realize the application of over 50% efficiency. We suggest that the optimized width of the IB layer be designed in the range of 1–6 μm if its absorption coefficient is 10⁴–10⁵ cm^–1 in the IB region.     

基于面积灰关联相对贴近度模型的长三角制造业产业升级研究

借助“制造业高级化”产业升级理论, 从结构优度、价值链高度、环境保护程度三个维度构建制造业产业升级评价指标体系。根据TOPSIS思想, 以被评价对象数列和理想方案指标数列两相邻点间围成图形的面积来表征关联系数, 同时采用标准差修正G1组合赋权原理对指标赋权并进一步计算灰关联相对贴近度; 通过引入时间变量并赋予时间序列权重以实现对长三角制造业产业升级动态评价。研究结果显示:2010至2016年间, 上海市排名最高, 江苏省略高于浙江省, 安徽省最低; 安徽省是长三角制造业产业升级的短板。基于上述结论, 给出长三角制造业产业升级的政策建议。