Excited-State Dynamics of Proflavine after Intercalation into DNA Duplex

Proflavine is an acridine derivative which was discovered as one of the earliest antibacterial agents, and it has been proven to have potential application to fields such as chemotherapy, photobiology and solar-energy conversion. In particular, it is well known that proflavine can bind to DNA with different modes, and this may open addition photochemical-reaction channels in DNA. Herein, the excited-state dynamics of proflavine after intercalation into DNA duplex is studied using femtosecond time-resolved spectroscopy, and compared with that in solution. It is demonstrated that both fluorescence and the triplet excited-state generation of proflavine were quenched after intercalation into DNA, due to ultrafast non-radiative channels. A static-quenching mechanism was identified for the proflavine-DNA complex, in line with the spectroscopy data, and the excited-state deactivation mechanism was proposed.     

Expanding new chemistry of aza-boracyclophanes with unique dipolar structures,AIE and redox-active open-shell characteristics

π-Conjugated macrocycles involving electron-deficient boron species have received increasing attention due to their intriguing tunable optoelectronic properties. However, most of the reported B(sp²)-doped macrocycles are difficult to modify due to the synthetic challenge, which limits their further applications. Motivated by the research of non-strained hexameric bora- and aza-cyclophanes, we describe a new class of analogues MC-BN5 and MC-ABN5 that contain charge-reversed triarylborane (Ar₃B) units and oligomeric triarylamines (Ar₃N) in the cyclics. As predicted by DFT computations, the unique orientation of the donor–acceptor systems leads to an increased dipole moment compared with highly symmetric macrocycles (M1, M2 and M3), which was experimentally represented by a significant solvatochromic effect with large Stokes shifts up to 12 318 cm⁻¹. Such a ring-structured design also allows the easy peripheral modification of aza-boracyclophanes with tetraphenylethenyl (TPE) groups, giving rise to a change in the luminescence mechanism from aggregation-caused quenching (ACQ) in MC-BN5 to aggregation-induced emission (AIE) in MC-ABN5. The open-shell characteristics have been chemically enabled and were characterized by UV-Vis-NIR spectroscopy and electron paramagnetic resonance (EPR) for MC-BN5. The present study not only showed new electronic properties, but also could expand the research of B/N doped macrocycles into the future scope of supramolecular chemistry, as demonstrated in the accessible functionalization of ring systems.

We have achieved the synthesis of new B/N doped macrocycles by stitching oligoarylamine pentamers using arylborane acceptor segments. They exhibit open-shell radical species and AIE under ambient conditions.     

Surface differences of oxide nanocrystals determined by geometry and exogenously coordinated water molecules

Determining the different surfaces of oxide nanocrystals is key in developing structure–property relations. In many cases, only surface geometry is considered while ignoring the influence of surroundings, such as ubiquitous water on the surface. Here we apply ¹⁷O solid-state NMR spectroscopy to explore the facet differences of morphology-controlled ceria nanocrystals considering both geometry and water adsorption. Tri-coordinated oxygen ions at the 1^st layer of ceria (111), (110), and (100) facets exhibit distinct ¹⁷O NMR shifts at dry surfaces while these ¹⁷O NMR parameters vary in the presence of water, indicating its non-negligible effects on the oxide surface. Thus, the interaction between water and oxide surfaces and its impact on the chemical environment should be considered in future studies, and solid-state NMR spectroscopy is a sensitive approach for obtaining such information. The work provides new insights into elucidating the surface chemistry of oxide nanomaterials.

Both atomic geometry and the influence of surroundings (e.g., exogenously coordinated water) are key issues for determining the chemical environment of oxide surfaces, whereas the latter is usually ignored and should be considered in future studies.     

“Click handle”-modified 2′-deoxy-2′-fluoroarabino nucleic acid as a synthetic genetic polymer capable of post-polymerization functionalization

The functions of natural nucleic acids such as DNA and RNA have transcended genetic information carriers and now encompass affinity reagents, molecular catalysts, nanostructures, data storage, and many others. However, the vulnerability of natural nucleic acids to nuclease degradation and the lack of chemical functionality have imposed a significant constraint on their ever-expanding applications. Herein, we report the synthesis and polymerase recognition of a 5-(octa-1,7-diynyl)uracil 2′-deoxy-2′-fluoroarabinonucleic acid (FANA) triphosphate. The DNA-templated, polymerase-mediated primer extension using this “click handle”-modified FANA (cmFANA) triphosphate and other FANA nucleotide triphosphates consisting of canonical nucleobases efficiently generated full-length products. The resulting cmFANA polymers exhibited excellent nuclease resistance and the ability to undergo efficient click conjugation with azide-functionalized molecules, thereby becoming a promising platform for serving as a programmable and evolvable synthetic genetic polymer capable of post-polymerization functionalization.

Polymerase-mediated incorporation of a “click handle”-modified fluoroarabinonucleic acid (cmFANA) triphosphate produces a new class of nuclease-resistant, evolvable genetic polymers that can be functionalized with azide-containing molecules.     

Energy Analysis of Precooling Air Compressor System

Energy saving is one of the main technique routes for net zero carbon emissions. Air compressor systems take up a large part of energy consumption in the industrial field. A pre-cooling air compressor system was proposed for energy saving by cooling the air before it flows in a compressor. The energy efficiency of the proposed system was analyzed. As additional energy consumption is required for air cooling, the feasibility of the pre-cooling method for energy saving was analyzed. As the efficiency of the pre-cooling air compressor system is mainly influenced by the environment temperature and humidity, applicability of the system in different regions and at different seasons was discussed. A pilot project was performed to verify the technical feasibility and economics of the proposed system. When the precooling temperature of the pilot system was set to 2 °C, the annual pneumatic-electrical ratio of the system can be increased by approximately 2% in several regions of China. This paper shows the pre-cooling air compressor system is feasible for energy saving.     

Recent Progress in Type I Aggregation-Induced Emission Photosensitizers for Photodynamic Therapy

In modern medicine, precision diagnosis and treatment using optical materials, such as fluorescence/photoacoustic imaging-guided photodynamic therapy (PDT), are becoming increasingly popular. Photosensitizers (PSs) are the most important component of PDT. Different from conventional PSs with planar molecular structures, which are susceptible to quenching effects caused by aggregation, the distinct advantages of AIE fluorogens open up new avenues for the development of image-guided PDT with improved treatment accuracy and efficacy in practical applications. It is critical that as much of the energy absorbed by optical materials is dissipated into the pathways required to maximize biomedical applications as possible. Intersystem crossing (ISC) represents a key step during the energy conversion process that determines many fundamental optical properties, such as increasing the efficiency of reactive oxygen species (ROS) production from PSs, thus enhancing PDT efficacy. Although some review articles have summarized the accomplishments of various optical materials in imaging and therapeutics, few of them have focused on how to improve the phototherapeutic applications, especially PDT, by adjusting the ISC process of organic optics materials. In this review, we emphasize the latest advances in the reasonable design of AIE-active PSs with type I photochemical mechanism for anticancer or antibacterial applications based on ISC modulation, as well as discuss the future prospects and challenges of them. In order to maximize the anticancer or antibacterial effects of type I AIE PSs, it is the aim of this review to offer advice for their design with the best energy conversion.     

HIMM回旋加速器控制系统中连锁保护功能设计与实现

在HIMM医用重离子加速器（Heavy Ion Medical Machine）中,回旋加速器的连锁保护功能针对离子源、高频、真空、电源、冷却水等子系统的连锁要求,设计实现了设备+PLC+软件三层结构的连锁系统,并保证连锁功能在系统断电、线缆连接故障、数据传输异常等情况下的正常工作。连锁系统可实现硬连锁毫秒级、软连锁次秒级别的反应速度。整体功能在回旋调试过程中得到验证,保障了整个加速器的顺利供束。     

多级孔芳香骨架材料的合成及固载硫脲催化剂的研究

合成了一种多级孔芳香骨架材料(PAF-70); 使用由氨基修饰过的单体, 应用该合成策略得到了同样具有窄分布介孔的含有氨基活性位点的PAF材料, 并通过硫脲单体与其氨基活性位点的反应, 将硫脲基团引入PAF-70材料中, 获得了含有硫脲催化位点的材料(PAF-70-thiourea). 氮气吸附-脱附测试结果显示, PAF-70存在孔径分布较窄的介孔, 介孔孔径为3.8 nm, 与模拟计算值(约3.7 nm)吻合. 热重分析结果表明, PAF-70具有很高的热稳定性. PAF-70在大多数溶剂中可以稳定存在, 具有良好的化学稳定性. 将PAF-70-thiourea作为催化剂, 应用在N-溴代琥珀酰亚胺(NBS)氧化醇类的反应中, 其表现出较高的催化活性、 较高的稳定性和广泛的底物适用性. 与含有相同硫脲催化位点的金属有机框架(MOF)材料(IRMOF-3-thiourea)作为催化剂对比, 进一步证实PAFs材料非常适合作为催化有机反应的固载平台.     

激光加载下铝材料的冲击温度测量

利用神光Ⅱ装置上搭建的用于激光冲击波实验的温度诊断系统（该系统包括高时空分辨的扫描高温计和谱时分辨的扫描高温计）,以强激光加载铝材料冲击温度的测量,获得了铝材料冲击高温辐射发光谱的高时空分辨信号图像,结合灰体辐射理论模型,计算得到了冲击波速度19.06 km/s时铝材料的冲击温度达2.95 eV,该温度与SESAME库中冲击温度接近。研究结果表明采用该测温系统能够有效诊断金属材料的冲击温度,为后续进一步获取金属材料冲击温度数据奠定了基础。     

频率搅拌嵌套混响室场分布的统计特性

为明确频率搅拌方式下嵌套混响室内的场分布,在混响室电磁统计特性的基础上,对嵌套小室内外的场分布进行了理论研究,重点对小混响室开窗大小对场分布的影响进行了分析。当窗口为电大尺寸时,小混响室内外均服从瑞利分布;为电小尺寸时,参考车-车链路通信的统计特性,小混响室内部应满足双瑞利分布。在某大型混响室内,借助矢量网络分析仪,通过测试收、发天线间的散射参数S21,实现了样本数据的快速采集,并将样本数据与理论分布模型进行了拟合优度检验（KS检验）,检验结果证明了假设分布的正确性。