Oxygen-17 nuclear magnetic resonance: The effects of remote unsaturation on 17o-chemical shifts in polycyclic ethers

Natural-abundance ¹⁷O-NMR spectra of 7-oxanorbornane exo-3-oxatricyclo [3.2.1.0^2.4]octane and their unsaturated derivatives (endo cyclic and exocyclic double bonds) have been measured. Linear correlation laws were observed for $\text{δ}{}_{\mathrm{o}}\text{δ}{}_{\mathrm{c}}$ of these ethers/corresponding hydrocarbons. The “cyclization shifts” for δ_o in ethers were not correlated by the “cyclization shifts” for δ_c of the corresponding hydrocarbons.     

Simple test system for single molecule recognition force microscopy

We have established an easy-to-use test system for detecting receptor-ligand interactions on the single molecule level using atomic force microscopy (AFM). For this, avidin-biotin, probably the best characterized receptor-ligand pair, was chosen. AFM sensors were prepared containing tethered biotin molecules at sufficiently low surface concentrations appropriate for single molecule studies. A biotin tether, consisting of a 6 nm poly(ethylene glycol) (PEG) chain and a functional succinimide group at the other end, was newly synthesized and covalently coupled to amine-functionalized AFM tips. In particular, PEG₈₀₀ diamine was glutarylated, the mono-adduct NH₂-PEG-COOH was isolated by ion exchange chromatography and reacted with biotin succinimidylester to give biotin-PEG-COOH which was then activated as N-hydroxysuccinimide (NHS) ester to give the biotin-PEG-NHS conjugate which was coupled to the aminofunctionalized AFM tip. The motional freedom provided by PEG allows for free rotation of the biotin molecule on the AFM sensor and for specific binding to avidin which had been adsorbed to mica surfaces via electrostatic interactions. Specific avidin-biotin recognition events were discriminated from nonspecific tip-mica adhesion by their typical unbinding force (∼40 pN at 1.4 nN/s loading rate), unbinding length (<13 nm), the characteristic nonlinear force-distance relation of the PEG linker, and by specific block with excess of free d-biotin. The convenience of the test system allowed to evaluate, and compare, different methods and conditions of tip aminofunctionalization with respect to specific binding and nonspecific adhesion. It is concluded that this system is well suited as calibration or start-up kit for single molecule recognition force microscopy.     

Analysis of F-53B,Gen-X,ADONA, and emerging fluoroalkylether substances in environmental and biomonitoring samples: A review

The persistent, bioaccumulative, and toxic properties of certain per- and polyfluoroalkyl substances (PFAS) raise concerns for environmental and human health. This has led to the gradual phase-out from production and commerce of some legacy PFAS. Fluoroalkylether compounds (ether-PFAS) are among the fluorinated alternative chemicals that are beginning to be reported in impacted and background environments. Extensive monitoring activities were conducted since 2015–2019 to bridge knowledge gaps on the environmental fate and effects of ether-PFAS including F-53B (6:2 chlorinated polyfluoroalkyl ether sulfonate [6:2 Cl-PFAES] and 8:2 Cl-PFAES), Gen-X (hexafluoropropylene oxide dimer acid [HFPO-DA]), and ADONA (dodecafluoro-3H-4,8-dioxanonanoate). In recent years, advances in nontarget screening using high-resolution mass spectrometry have revealed the identities of other infrequently monitored ether-PFAS. In this critical review, we provide an up-to-date inventory of the structures of ether-PFAS discovered in the recent literature. Their environmental occurrence, fate, and effects are discussed on a comparative perspective with some legacy PFAS such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Information on the methods employed for the quantitative and semi-quantitative analysis of ether-PFAS is also provided, including sample preparation and mass spectrometry analysis, analytical performance, and limitations. In particular, the compiled database of MS/MS fragment ions (n = 111) can be useful in spectrum interpretation of novel ether-PFAS. The concluding remarks open on possible research avenues and the challenges that remain to be addressed.     

美军F-35战斗机PHM体系结构分析

为借鉴国外状态预测与健康管理(PHM)技术的发展经验,促进大型平台实现从状态监控向健康管理过渡,本文回顾了美军PHM技术的发展概况,分析了F-35战斗机PHM的体系结构组成以及各模块的主要功能,总结了F-35战斗机PHM的工作流程,介绍了F-35战斗机PHM系统的发展现状及存在的主要问题,提出了对发展PHM技术的认识,为从事PHM技术工作者提供了参考。     

不同浓度比的硫酸根和氯离子溶液中钝化膜的半导体特性转变机制研究

800合金作为核电站蒸汽发生器的一种关键材料,服役环境下其表面钝化膜的特性一直是人们研究的热点.本文用Mott-Schottky方法研究了800合金在不同硫酸根离子和氯离子浓度比的溶液中钝化膜的半导体特性,并结合电化学阻抗谱(EIS)、扫描电镜(SEM)、扫描电化学显微镜(SECM)研究了钝化膜的耐蚀性和表面活性.Mott-Schottky结果表明,800合金表面钝化膜的半导体特性与溶液中硫酸根、氯离子的浓度比有关,随硫酸根与氯离子浓度比的降低,半导体特性发生转变.当硫酸根与氯离子的浓度比较高时,钝化膜为p型半导体;而当硫酸根与氯离子的浓度比较低时,钝化膜为n型半导体.EIS、SECM、SEM结果表明,随浓度比的降低钝化膜由过钝化溶解转为明显的点蚀特征,钝化膜表面活性增加.钝化膜特性的改变与其半导体类型的转变密切相关,而半导体特性的转变由氯离子、硫酸根离子在800合金钝化膜表面的竞争吸附所致,其在表面的竞争吸附直接影响钝化膜表面发生的化学反应,改变电极/溶液界面电势差,使钝化膜中的空位类型改变,最终决定半导体类型.     

Synthesis of [18F]F-γ-T-3, a Redox-Silent γ-Tocotrienol (γ-T-3) Vitamin E Analogue for Image-Based In Vivo Studies of Vitamin E Biodistribution and Dynamics

Vitamin E, a natural antioxidant, is of interest to scientists, health care pundits and faddists; its nutritional and biomedical attributes may be validated, anecdotal or fantasy. Vitamin E is a mixture of tocopherols (TPs) and tocotrienols (T-3s), each class having four substitutional isomers (α-, β-, γ-, δ-). Vitamin E analogues attain only low concentrations in most tissues, necessitating exacting invasive techniques for analytical research. Quantitative positron emission tomography (PET) with an F-18-labeled molecular probe would expedite access to Vitamin E’s biodistributions and pharmacokinetics via non-invasive temporal imaging. (R)-6-(3-[¹⁸F]Fluoropropoxy)-2,7,8-trimethyl-2-(4,8,12-trimethyltrideca-3,7,11-trien-1-yl)-chromane ([¹⁸F]F-γ-T-3) was prepared for this purpose. [¹⁸F]F-γ-T-3 was synthesized from γ-T-3 in two steps: (i) 1,3-di-O-tosylpropane was introduced at C6-O to form TsO-γ-T-3, and (ii) reaction of this tosylate with [¹⁸F]fluoride in DMF/K₂₂₂. Non-radioactive F-γ-T-3 was synthesized by reaction of γ-T-3 with 3-fluoropropyl methanesulfonate. [¹⁸F]F-γ-T-3 biodistribution in a murine tumor model was imaged using a small-animal PET scanner. F-γ-T-3 was prepared in 61% chemical yield. [¹⁸F]F-γ-T-3 was synthesized in acceptable radiochemical yield (RCY 12%) with high radiochemical purity (>99% RCP) in 45 min. Preliminary F-18 PET images in mice showed upper abdominal accumulation with evidence of renal clearance, only low concentrations in the thorax (lung/heart) and head, and rapid clearance from blood. [¹⁸F]F-γ-T-3 shows promise as an F-18 PET tracer for detailed in vivo studies of Vitamin E. The labeling procedure provides acceptable RCY, high RCP and pertinence to all eight Vitamin E analogues.     

高精度半导体激光打标机F-θ镜头设计

为保证半导体激光打标机F-θ镜头的扫描质量,实现系统像高与扫描角的线性变化,需对F-θ镜头给予一定的畸变量,并使其满足等晕条件。分析F-θ镜头工作原理及像差要求,根据1 064 nm半导体激光打标机的光源成像要求选择合适的玻璃材料,合理分配每片透镜的光焦度,以保证等晕成像;根据F-θ镜头线性成像要求,计算系统总畸变量为1.6%,系统总畸变量为系统的实际桶形畸变与相对畸变量之和;在光学系统优化设计时,引入这两项优化参数,优化过程中观察系统成像变化情况。设计结果表明:系统MTF曲线接近衍射极限,F-θ镜头相对畸变小于0.36%,各视场均方根半径均小于艾里斑直径,并且整个系统70%的能量集中在直径为16 μm的圆内,系统总畸变量为1.58%,满足设计指标要求。     

F-θ镜头的光学设计

介绍一种适合于激光打标的聚焦镜头－F-θ镜头的光学设计.通过引入桶形畸变，得到的F-θ镜头的像高与入射角成正比，可实现打标速度的线性控制.优化设计得到的工作面积达500×500 mm2的F-θ镜头，结构简单紧凑、聚焦性能达到衍射极限.     

The ternary system cerium-rhodium-silicon

Phase relations have been established in the ternary system Ce-Rh-Si for the isothermal section at 800 °C based on X-ray powder diffraction and EPMA on about 80 alloys, which were prepared by arc melting under argon or by powder reaction sintering. From the 25 ternary compounds observed at 800 °C 13 phases have been reported earlier. Based on XPD Rietveld refinements the crystal structures for 9 new ternary phases were assigned to known structure types. Structural chemistry of these compounds follows the characteristics already outlined for their prototype structures: τ₇—Ce₃RhSi₃, (Ba₃Al₂Ge₂-type), τ₈—Ce₂Rh_3−xSi_3+x (Ce₂Rh_1.35Ge_4.65-type), τ₁₀—Ce₃Rh_4−xSi_4+x (U₃Ni₄Si₄-type), τ₁₁—CeRh₆Si₄ (LiCo₆P₄-type), τ₁₃—Ce₆Rh₃₀Si_19.3 (U₆Co₃₀Si₁₉-type), τ₁₈—Ce₄Rh₄Si₃ (Sm₄Pd₄Si₃-type), τ₂₁—CeRh₂Si (CeIr₂Si-type), τ₂₂—Ce₂Rh_3+xSi_1−x (Y₂Rh₃Ge-type) and τ₂₄—Ce₈(Rh_1−xSi_x)₂₄Si (Ce₈Pd₂₄Sb-type). For τ₂₅—Ce₄(Rh_1−xSi_x)₁₂Si a novel bcc structure was proposed from Rietveld analysis. Detailed crystal structure data were derived for τ₃—CeRhSi₂ (CeNiSi₂-type) and τ₆—Ce₂Rh₃Si₅ (U₂Co₃Si₅-type) by X-ray single crystal experiments, confirming the structure types. The crystal structures of τ₄—Ce₂₂Rh₂₂Si₅₆, τ₅—Ce₂₀Rh₂₇Si₅₃ and τ₂₃—Ce_33.3Rh_58.2−55.2Si_8.5−11.5 are unknown. High temperature compounds with compositions Ce₁₀Rh₅₁Si₃₃ (U₁₀Co₅₁Si₃₃-type) and CeRhSi (LaIrSi-type) have been observed in as-cast alloys but these phases do not participate in the phase equilibria at 800 °C.     

辛巴蓝F-3GA修饰的啤酒废酵母菌亲和吸附溶菌酶

利用j嗪染料辛巴蓝F-3GA修饰经戊二醛交联的啤酒废酵母菌,得到一种新型染料亲和吸附剂.辛巴蓝F-3GA的固载量为161.1 mg/g.以溶菌酶为研究对象,考察吸附时间、酶初始浓度、pH值、离子强度等因素对吸附率的影响.结果表明:当pH=7.0时,其对溶菌酶有较高的吸附量(229.1 mg/g),吸附性能明显优于未接枝...