Embedding carbon dots in Eu3+-doped metal-organic framework for label-free ratiometric fluorescence detection of Fe3+ ions

Fluorescent detection is a new spectroscopic measurement for ions sensing due to the advantages of real-time determination with high selectivity, accuracy, and low cost. However, chemosensors based on fluorescent detection are usually determined by absolute intensity from a monochromatic emission signal, which is easy to be fluctuated by the external environment, especially for Fe³⁺ detection in complex fluids. Herein, we rationally design a dual-emission Eu³⁺: CDs@ZIF-8 to construct a ratiometric fluorescent sensor with self-calibrating ability for Fe³⁺ determination. High efficient carbon dots (CDs) are embedded in europium ions (Eu³⁺)-doped MOF by simple stirring preparation at room temperature. The label-free ratiometric fluorescent probe (I_CDs@ZIF-8/I_Eu) exhibits simultaneous blue and red emission under the same excitation at 365 nm. Remarkably, Eu³⁺: CDs@ZIF-8 displays the superiority of high selectivity to Fe³⁺, which shows ratiometric fluorescence characteristics (I₀/I) in a range of 0-6 μmol\L with a low limit of detection (LOD) of 0.897 μmol\L. Besides, the CDs-MOF nanocomposite holds good aqueous dispersibility and low cytotoxicity, which shows great potential applications in medical aid including biological detection and clinical diagnosis.     

电容式力感知牙周探针设计建模与实验研究

针对当前牙周探针在探诊力控制方面的不足,提出一种基于悬臂梁挠曲效应的差动电容式力感知牙周探针解决方案,设计了探针验证结构,建立了探诊力作用下具有不规则形状的探针工作尖的挠曲模型,导出了探诊力和差动电容之间的求解方程,并通过仿真和实验对模型与方程进行了验证。结果表明,所建立的探针工作尖挠曲模型与静应力仿真结果的最大相对误差不超过±4.5%,所设计的力感知牙周探针多次重复探诊力检测实验的标准差小于均值的0.1%,所导出的求解方程的计算值与实验数据之间趋向一致,以探诊力为拟合权重进行修正后全量程的平均偏差为2.49%,具备进一步产品开发的可行性。     

Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

基于柠檬酸-铕纳米配位聚合物构建荧光探针快速检测汤煲中5’-肌苷酸含量

基于柠檬酸-铕金属有机纳米配体聚合物（citrate/europium lanthanide coordination polymer nanoparticles，Cit/Eu LCP NPs）构建快速检测肉品汤煲中5’-肌苷酸（inosine-5’-monophosphate，5’-IMP）的荧光探针。研究结果表明，5’-IMP对Cit/Eu?LCP?NPs有良好的荧光猝灭作用。在最佳条件下，该荧光探针在5’-IMP?2.5～200?μg/mL的质量浓度范围内呈现出良好的线性关系，检出限为0.17?μg/mL，且具备良好的抗干扰、稳定性和重复性。为了验证方法可行性，将该方法应用于实际鸡汤样品中的5’-IMP检测，测得加标回收率为97.85%～103.95%，可为快速检测肉品汤煲中5’-IMP提供新的思路和方法。     

TiO2/MXene-Assisted LDI-MS for Urine Metabolic Profiling in Urinary Disease

Cancer remains an intractable medical problem. Rapid diagnosis and identification of cancer are critical to differentiate it from nonmalignant diseases. High-throughput biofluid metabolic analysis has potential for cancer diagnosis. Nevertheless, the present metabolite analysis method does not meet the demand for high-throughput screening of diseases. Herein, a high-throughput, cost-effective, and noninvasive urine metabolic profiling method based on TiO₂/MXene-assisted laser desorption/ionization mass spectrometry (LDI-MS) is presented for the efficient screening of bladder cancer (BC) and nonmalignant urinary disease. Combined with machine learning, TiO₂/MXene-assisted LDI-MS enables high diagnostic accuracy (96.8%) for the classification of patient groups (including 47 BC and 46 ureteral calculus (UC) patients) from healthy controls (113 cases). In addition, BC patients can also be identified from noncancerous UC individuals with an accuracy of 88.3% in the independent test cohort. Furthermore, metabolite variations between BC and UC individuals are investigated based on relative quantification, and related pathways are also discussed. These results suggest that this method, based on urine metabolic patterns, provides a potential tool for rapidly distinguishing urinary diseases and it may pave the way for precision medicine.     

Labeling and Characterization of Phenol-Containing Glycopeptides Using Chemoselective Probes with Isotope Tags

Secondary metabolites are structurally diverse natural products (NPs) and have been widely used for medical applications. Developing new tools to enrich NPs can be a promising solution to isolate novel NPs from the native and complex samples. Here, we developed native and deuterated chemoselective labeling probes to target phenol-containing glycopeptides by the ene-type labeling used in proteomic research. The clickable azido-linker was included for further biotin functionalization to facilitate the enrichment of labeled substrates. Afterward, our chemoselective method, in conjunction with LC-MS and MSn analysis, was demonstrated in bacterial cultures. A vancomycin-related phenol-containing glycopeptide was labeled and characterized by our labeling strategy, showing its potential in glycopeptide discovery in complex environments.     

瞬态闭锁试验在0.13 μm大规模集成电路中引起的潜在损伤

瞬态剂量率辐射试验会引起集成电路发生损伤或失效，其原因至少有两种：闭锁大电流引起的电路内部金属互连熔融；累积电离总剂量引起的氧化层电荷造成阈值电压偏移。本文以一种0.13 μm体硅CMOS处理器为对象，研究了瞬态剂量率和稳态电离总剂量辐射效应规律。结果表明：瞬态剂量率闭锁效应对处理器造成了显著的潜在损伤，导致其总剂量失效阈值从1 030 Gy(Si)降低至600 Gy(Si)。研究结论对于大规模集成电路的可靠性评估和指导辐射加固设计有重要参考意义。     

Enhanced Sensitivity in Nanopore Sensing of Cancer Biomarkers in Human Blood via Click Chemistry

Cancer biomarkers are expected to be indicative of the occurrence of certain cancer diseases before the tumors form and metastasize. However, many biomarkers can only be acquired in extremely low concentrations, which are often beyond the limit of detection (LOD) of current instruments and technologies. A practical strategy for nanopore sensing of cancer biomarkers in raw human blood down to the femtomolar level is developed here. This strategy first converts the detection of cancer biomarkers to the quantification of copper ions by conducting a sandwich assay involving copper oxide nanoparticles. The released Cu²⁺ is then taken to catalyze the “click” reaction which ligates a host–guest modified DNA probe. Finally, this DNA probe is subjected to single‐channel recordings to afford the translocation events that can be used to derive the concentrations of the original biomarkers. Due to the amplification effects of nanoparticle loadings and the “click” reaction, the LOD of this strategy can be as low as the subfemtomolar level. Further, the acid treatment step could effectively eliminate the interferences from plasma proteins in raw human blood and make the strategy highly suitable for the detection of cancer biomarkers in clinical samples.