Access to Trifluoromethylketones from Alkyl Bromides and Trifluoroacetic Anhydride by Photocatalysis

Aliphatic trifluoromethyl ketones are a type of unique fluorine-containing subunit which play a significant role in altering the physical and biological properties of molecules. Catalytic methods to provide direct access to aliphatic trifluoromethyl ketones are highly desirable yet remain underdeveloped, partially owing to the high reactivity and instability of trifluoroacetyl radical. Herein, we report a photocatalytic synthesis of trifluoromethyl ketones from alkyl bromides with trifluoroacetic anhydride. The reaction features dual visible-light and halogen-atom-transfer catalysis, followed by an enabling radical-radical cross-coupling of an alkyl radical with a stabilized trifluoromethyl radical. The reaction provides straightforward access to aliphatic trifluoromethyl ketones from readily available and cost-effective alkyl halides and trifluoroacetic anhydride (TFAA).     

一种LED灯阵光控系统的设计与实现

针对在大功率LED灯阵光控系统中,需采用专门的恒流源进行驱动控制造成的设计复杂且制造成本较高的缺点,提出了一种集中控制式LED光控系统。系统以PIC单片机为控制中心,通过PWM脉宽调制和检测模块实现对LED灯阵发光亮度、闪烁频率及通信链路的精确控制。阐述了系统的设计方案及组成原理,并描述了系统的软硬件设计及实现方法。系统方便实现对LED单灯的通断、亮度等控制,能显著降低LED光控系统产品设计、生产以及用户的使用成本。该光控系统设计具有光能利用率高、成本价格低廉、节能减排效果显著等优势,可以推广到其它大型LED照明系统智能化控制等领域。     

用溶胶-凝胶光学干涉膜改善白炽灯的发射光谱

叙述了为交通照明开发的卤钨白炽灯.这种灯涂有多层干涉膜,可用于雾灯、高色温灯、信号灯等给出了膜系设计,介绍了涂有这种膜的灯的特性和实验结果.     

Efficient Suzuki-Miyaura mono-arylation of symmetrical diiodo(hetero)arenes

A reliable protocol for converting 1,4-diiodo-2,3,5,6-tetrafluorobenzene into 1-(hetero)aryl-4-iodo-2,3,5,6-tetrafluorobenzene derivatives has been lacking in the literature. We have identified optimal conditions to achieve this conversion in good yields and have minimized formation of the bis-coupling product. The newly identified protocol involving the use of a syringe pump has been extended to other symmetrical diiodo(hetero)arenes.     

Flame retardant challenges for textiles and fibres: New chemistry versus innovatory solutions

Almost 50 years ago, the 1950-1960 period witnessed the development of the chemistry underlying most of today’s successful and durable flame retardant treatments for fibres and textiles. In today’s more critical markets in terms of environmental sustainability, chemical toxicological acceptability, performance and cost, many of these are now being questioned. “Are there potential replacements for established, durable formaldehyde-based flame retardants such as those based on tetrakis (hydroxylmethyl) phosphonium salt and alkyl-substituted, N-methylol phosphonopropionamide chemistries for cellulosic textiles?” is an often-asked question. “Can we produce char-forming polyester flame retardants?” and “Can we really produce effective halogen-free replacements for coatings and back-coated textiles?” are others.These questions are addressed initially as a historical review of research undertaken in the second half of the twentieth century which is the basis of most currently available, commercialised flame retardant fibres and textiles. Research reported during the first decade of the twenty first century and which primarily addresses the current issues of environmental sustainability and the search for alternative flame retardant solutions, the need to increase char-forming character in synthetic fibres and the current interest in nanotechnology is critically discussed. The possible roles of micro- and nano-surface treatments of fibre surfaces and their development using techniques such as plasma technology are also reviewed.     

运用核物理教学实验测量和分析照明光源的辐射

用盖革—谬勒计数器对日光灯、白炽灯、LED等光源进行测量,发现日光灯发射高能光子,它能穿透包封感光胶片的黑纸。用能谱分析仪测量日光灯发射光子能谱显示,日光灯发射峰值能量为83 keV。因辐射对视网膜神经组织伤害较大,长期使用日光灯时要利用射线在空气中衰减很快的特性,应保持眼睛距日光灯50 cm以外。     

N−X⋅⋅⋅O−N Halogen Bonds in Complexes of N-Haloimides and Pyridine-N-oxides: A Large Data Set Study

N−X⋅⋅⋅⁻O−N⁺ halogen-bonded systems formed by 27 pyridine N-oxides (PyNOs) as halogen-bond (XB) acceptors and two N-halosuccinimides, two N-halophthalimides, and two N-halosaccharins as XB donors are studied in silico, in solution, and in the solid state. This large set of data (132 DFT optimized structures, 75 crystal structures, and 168 ¹H NMR titrations) provides a unique view to structural and bonding properties. In the computational part, a simple electrostatic model (SiElMo) for predicting XB energies using only the properties of halogen donors and oxygen acceptors is developed. The SiElMo energies are in perfect accord with energies calculated from XB complexes optimized with two high-level DFT approaches. Data from in silico bond energies and single-crystal X-ray structures correlate; however, data from solution do not. The polydentate bonding characteristic of the PyNOs’ oxygen atom in solution, as revealed by solid-state structures, is attributed to the lack of correlation between DFT/solid-state and solution data. XB strength is only slightly affected by the PyNO oxygen properties [(atomic charge (Q), ionization energy (I_s,min) and local negative minima (V_s,min)], as the σ-hole (V_s,max) of the donor halogen is the key determinant leading to the sequence N-halosaccharin>N-halosuccinimide>N-halophthalimide on the XB strength.     

Creating an Amyloid ‘Kaleidoscope’ Using Short Iodinated Peptides

Amyloid fibrils formed by peptides with different sequences exhibit diversified morphologies, material properties and activities, making them valuable for developing functional bionanomaterials. However, the molecular understanding underlying the structural diversity of peptide fibrillar assembly at atomic level is still lacking. In this study, by using cryogenic electron microscopy, we first revealed the structural basis underlying the highly reversible assembly of ¹GFGGNDNFG⁹ (referred to as hnRAC1) peptide fibril. Furthermore, by installing iodine at different sites of hnRAC1, we generated a collection of peptide fibrils with distinct thermostability. By determining the atomic structures of the iodinated fibrils, we discovered that iodination at different sites of the peptide facilitates the formation of diverse halogen bonds and triggers the assembly of entirely different structures of iodinated fibrils. Finally, based on this structural knowledge, we designed an iodinated peptide that assembles into new atomic structures of fibrils, exhibiting superior thermostability, that aligned with our design. Our work provides an in-depth understanding of the atomic-level processes underlying the formation of diverse peptide fibril structures, and paves the way for creating an amyloid “kaleidoscope” by employing various modifications and peptide sequences to fine-tune the atomic structure and properties of fibrillar nanostructures.     

土壤悬浮液中双酚A的光降解研究

实验研究了双酚A在土壤表面的吸附特征及在土壤悬浮液中的光降解.研究结果表明,双酚A在土壤表面的吸附为单分子的化学吸附,用Langmuir模型或Freundlich模型拟合时相关性较好.在高压汞灯(λ=300nm)照射下,双酚A在土壤悬浮液中能快速降解,降解速度随酸度的增大而加快.在此体系中双酚A光降解动力学遵循Langmuir-Hinshelwood(H-L)方程,在土壤量不超过10g/L的条件下,降解率随土壤量增加而增加,加入腐殖酸可以促进双酚A的光解,同时增大光照强度有利于双酚A的降解.