Tiara[5]arenes: Synthesis,Solid‐State Conformational Studies,Host–Guest Properties,and Application as Nonporous Adaptive Crystals

Tiara[5]arenes (T[5]s), a new class of five‐fold symmetric oligophenolic macrocycles that are not accessible from the addition of formaldehyde to phenol, were synthesized for the first time. These pillar[5]arene‐derived structures display both unique conformational freedom, differing from that of pillararenes, with a rich blend of solid‐state conformations and excellent host–guest interactions in solution. Finally we show how this novel macrocyclic scaffold can be functionalized in a variety of ways and used as functional crystalline materials to distinguish uniquely between benzene and cyclohexane.     

Late-Stage Modification of Aminoglycoside Antibiotics Overcomes Bacterial Resistance Mediated by APH(3’) Kinases

The continuous emergence of antimicrobial resistance is causing a threat to patients infected by multidrug-resistant pathogens. In particular, the clinical use of aminoglycoside antibiotics, broad-spectrum antibacterials of last resort, is limited due to rising bacterial resistance. One of the major resistance mechanisms in Gram-positive and Gram-negative bacteria is phosphorylation of these amino sugars at the 3’-position by O-phosphotransferases [APH(3’)s]. Structural alteration of these antibiotics at the 3’-position would be an obvious strategy to tackle this resistance mechanism. However, the access to such derivatives requires cumbersome multi-step synthesis, which is not appealing for pharma industry in this low-return-on-investment market. To overcome this obstacle and combat bacterial resistance mediated by APH(3’)s, we introduce a novel regioselective modification of aminoglycosides in the 3’-position via palladium-catalyzed oxidation. To underline the effectiveness of our method for structural modification of aminoglycosides, we have developed two novel antibiotic candidates overcoming APH(3’)s-mediated resistance employing only four synthetic steps.     

固相萃取高效液相色谱-质谱法测定动物组织中硝基呋喃代谢产物

研究了对动物组织中4种硝基呋喃类代谢产物AOZ、AMOZ、SEM和AHD的自动固相萃取HPLC-MS分析方法，分别以2-氯苯甲醛和2-硝基苯甲醛作为衍生化试剂，分别用AMOZ-d5、AOZ-d4作内标，用ENSPE柱进行提取，以乙腈-0．1％甲酸为流动相，采用梯度洗脱，可在15min内将4种代谢产物完全分离并进行测定。回收率为85％-90％；检出限可达0．5μg／kg。采用两种衍生化方法可获得较多的定性确证信息。采用本方法研究了硝基呋喃在鸡饲养过程中的残留规律。     

液相色谱/串联质谱线性组合法测定动物组织中硝基呋喃代谢产物

研究了对动物组织中4种硝基呋喃类代谢产物AMOZ、AHD、SEM、AOZ的同位素稀释HPLC—MS／MS线性组合分析方法,以2-基苯甲醛作为衍生化试剂,AMOZ—d5、AOZ-4作内标,用乙酸乙脂提取,用自制的净化试剂净化,以乙腈-0．1％甲酸为流动相,采用梯度洗脱,可适应不同种类的动物组织样品前处理,15min可将4种代谢产物完全分离并测定。提出了HPLC—MS／MS多重反应监测线性组合法的原理并进行了验证,回收率为85％-118％;定量限（LOQ）为0．1μg／kg;检出限（LOD）为0．03μg／kg。     

TiO2纳米粒子膜表面性质的研究

ＴｉＯ_２纳米粒子膜在光催化降解大气和水中的污染物［１］、光电转换［２］、光致变色［３］等方面有广阔的应用前景,近年来受到了科学界的高度重视．研究表明,膜的表面性质对如上应用有着重要影响．本文采用等离子体化学气相沉积法（ＰＥＣＶＤ法）［４］制备了ＴｉＯ２的纳米粒子膜,分别采用ＴｉＣｌ４等离子体或Ｏ２等离子体处理膜表面,获得两种不同表面性质的ＴｉＯ２纳米粒子膜;并利用表面光电压谱（ＳＰＳ）和电场诱导表面光电压谱（ＥＦＩＳＰＳ）技术对膜的表面性质进行具体分析,探讨了其在光催化领域的可能应用．１实验部…     

自然冷却和遇水冷却后高温花岗岩力-声特性试验研究

以松辽盆地露天花岗岩为研究对象,对自然冷却和遇水冷却后高温花岗岩进行单轴压、拉和声波测定试验.研究不同方式冷却后花岗岩温度(100℃、200℃、300℃、400℃、500℃、600℃、700℃、800℃,以下简称100℃-800℃)与表观形态、纵、横波波速、弹性模量、泊松比、抗压强度、抗拉强度间关系,并将纵、横波波速与抗压强度、弹性模量建立联系.同时考虑遇水冷却后静置过程对花岗岩力-声性质影响.研究表明:(1)静置0h-2h是质量损失、纵波波速下降主要时段,静置6h后变化率可以忽略;自由水损失量与力-声特性损失量存在一定线性关系;(2)温度升高,自然冷却后花岗岩纵、横波波速、弹性模量、抗压强度、抗拉强度呈线型下降,遇水冷却后呈凹线型下降;高于300℃,自然冷却后花岗岩力-声参数均大于遇水冷却,泊松比变化率与其相反,600℃时冷却方式不同对花岗岩纵、横波波速、弹性模量、抗压强度影响达到最大,遇水冷却比自然冷却分别低33.33%、31.88%、53.33%、31.74%,700℃-800℃时冷却方式对花岗岩力声特性影响减小;(3)温度变化,花岗岩纵、横波波速与抗压强度、弹性模量呈良好相关性.所得结论可以提高花岗岩力-声特性测量准确性,为力学特性预测提供一个可行方法,并为岩体工程安全稳定性评估提供依据.     

Fibrous TiO2-SiO2 nanocomposite photocatalyst

The electrospinning method is employed to prepare a fibrous TiO2-SiO2 (Ti : Si = 1 : 2) nanocomposite photocatalyst, in which Degussa P25 T i O2 nanoparticles are embedded inthe body of SiO2 fibers and which shows good photocatalytic activity due to its 3-D open structure, as evidenced by photocatalytic reduction of silver ions and decomposition of acetaldehyde.     

Synthesis,structure, electrochemical properties,and antioxidant activities of copper(II) and zinc(II) complexes with N,N-bis(N-ethyl-2-ylmethylbenzimidazol)allylamine ligand

N,N-bis(N-methyl-2-ylmethylbenzimidazole)aniline (EtAIDB) and its transition metal complexes, [Cu(EtAIDB)Br₂]·EtOH {dibromo[N,N-bis(N-methyl-2-ylmethylbenzimidazole)aniline] copper(II) ethanol} (1) and [Zn(EtAIDB)Br₂] {dibromo[N,N-bis(N-methyl-2-ylmethylbenzimidazole)aniline] zinc(II)} (2), have been synthesized and characterized by elemental analysis, molar conductivity, UV–visible, and IR spectroscopy. The X-ray crystallographic studies of 1 and 2 have shown two different arrangements: 1 is distorted square-based pyramidal, while 2 can be treated as distorted tetrahedral. The cyclic voltammogram of 1 represents quasi-reversible Cu²⁺/Cu⁺ pairs. In vitro antioxidant tests showed that 1 had significant antioxidant activity against superoxide and hydroxy radicals.     

Orthogonal Trichromatic Upconversion with High Color Purity in Core-Shell Nanoparticles for a Full-Color Display

Materials with tunable emission colors has attracted increasing interest in both fundamental research and applications. As a key member of light-emitting materials family, lanthanide doped upconversion nanoparticles (UCNPs) have been intensively demonstrated to emit light in any color upon near-infrared excitation. However, realizing the trichromatic emission in UCNPs with a fixed composition remains a great challenge. Here, without excitation pulsed modulation and three different near-infrared pumping, we report an experimental design to fine-control emission in the full color gamut from core–shell-structured UCNPs by manipulating the energy migration through dual-channel pump scheme. We also demonstrate their potential application in full-color display. These findings may benefit the future development of convenient and versatile optical methos for multicolor tuning and open up the possibility of constructing full-color volumetric display systems with high spatiotemporal resolution.     

Regulation of Multiple Resonance Delayed Fluorescence via Through-Space Charge Transfer Excited State towards High-Efficiency and Stable Narrowband Electroluminescence

B- and N-embedded multiple resonance (MR) type thermally activated delayed fluorescence (TADF) emitters usually suffer from slow reverse intersystem crossing (RISC) process and aggregation-caused emission quenching. Here, we report the design of a sandwich structure by placing the B−N MR core between two electron-donating moieties, inducing through-space charge transfer (TSCT) states. The proper adjusting of the energy levels brings about a 10-fold higher RISC rate in comparison with the parent B−N molecule. In the meantime, a high photoluminescence quantum yield of 91 % and a good color purity were maintained. Organic light-emitting diodes based on the new MR emitter achieved a maximum external quantum efficiency of 31.7 % and small roll-offs at high brightness. High device efficiencies were also obtained for a wide range of doping concentrations of up to 20 wt % thanks to the steric shielding of the B−N core. A good operational stability with LT₉₅ of 85.2 h has also been revealed. The dual steric and electronic effects resulting from the introduction of a TSCT state offer an effective molecular design to address the critical challenges of MR-TADF emitters.