Real-Time Sniffing Mass Spectrometry Aided by Venturi Self-Pumping Applicable to Gaseous and Solid Surface Analysis

Based on the Venturi self-pumping effect, real-time sniffing with mass spectrometry (R-sniffing MS) is developed as a tool for direct and real-time mass spectrometric analysis of both gaseous and solid samples. It is capable of dual-mode operation in either gaseous or solid phase, with the corresponding techniques termed as Rg-sniffing MS and Rs-sniffing MS, respectively. In its gaseous mode, Rg-sniffing MS is capable of analyzing a gaseous mixture with response time (0.8–2.1 s rise time and 7.3–9.6 s fall time), spatial resolution (<80 μm), three-dimensional diffusion imaging, and aroma distribution imaging of red pepper. In its solid mode, an appropriate solvent droplet desorbs the sample from a solid surface, followed by the aspiration of the mixture using the Venturi self-pumping effect into the mass spectrometer, wherein it is ionized by a standard ion source. Compared with the desorption electrospray ionization (DESI) technique, Rs-sniffing MS demonstrated considerably improved limit of detection (LOD) values for arginine (0.07 μg/cm2 Rs-sniffing vs 1.47 μg/cm2 DESI), thymopentin (0.10 μg/cm2vs 2.67 μg/cm2), and bacitracin (0.16 μg/cm2vs 2.28 μg/cm2). Rs-sniffing is applicable for the detection of C60(OCH3)6Cl–, an intermediate in the methoxylation reaction involving C60Cl6 (solid) and methanol (liquid). The convenient and highly sensitive R-sniffing MS has a characteristic separation of desorption from the ionization process, in which the matrix atmosphere of desorption can be interfaced by a pipe channel and self-pumped by the Venturi effect with consequent integration using a standard ion source. The R-sniffing MS operates in a voltage-, heat-, and vibration-free environment, wherein the analyte is ionized by a standard ion source. Consequently, a wide range of samples can be analyzed simultaneously by the R-sniffing MS technique, regardless of their physical state

Tetraphenylethylene-Functionalized Metal–Organic Frameworks with Strong Aggregation-Induced Electrochemiluminescence for Ultrasensitive Analysis through a Multiple Convertible Resonance Energy Transfer System

Since aggregation-induced electrochemiluminescence (AIECL) combined the merits of aggregation-induced emission (AIE) and electrochemiluminescence (ECL), it has become a research hotspot recently. Herein, novel kinds of functional metal–organic frameworks (MOFs) with strong AIECL were reported through doping tetraphenylethylene (TPE) into UiO-66. Due to the porosity and highly ordered topological structure that caused the confinement effect of MOFs, the molecular motion of TPE was effectively limited within UiO-66, resulting in strong AIE. Meanwhile, the large specific surface area and porous structure of UiO-66 allowed TPE to react with coreactants more effectively, which was beneficial to ECL. Thus, the TPE-functionalized UiO-66 (TPE-UiO-66) showed excellent AIECL performance surprisingly. Inspired by this, a multiple convertible ECL resonance energy transfer (ECL-RET) system was constructed through a DNA Y structure that regulated the distance between the energy donor (TPE-UiO-66) and different energy acceptors (gold nanoparticles and Adriamycin). Furthermore, an ultrasensitive ECL biosensor for the detection of Mucin 1 (MUC1) was developed through the introduction of the novel ECL-RET system. In the presence of MUC1, the DNA Y structure was constructed, keeping the gold nanoparticles (AuNPs) away from TPE-UiO-66. Then, Adriamycin (Dox) could be embedded in the DNA Y structure and act as an energy acceptor to receive the energy of TPE-UiO-66, which made the biosensor produce a strong ECL response. As expected, the developed ECL biosensor exhibited superior detection performance for MUC1. This work provided a novel way to realize AIECL and board the application of AIECL in analytical chemistry

Construction of Highly Efficient Resonance Energy Transfer Platform Inside a Nanosphere for Ultrasensitive Electrochemiluminescence Detection

Electrochemiluminescence (ECL) detection has attracted increasing attention as a promising analytical approach. A considerable number of studies showed that ECL intensity can be definitely improved by resonance energy transfer (RET), while the RET efficiency is strongly dependent on the distance between exited donors and acceptors. Herein we disclose for the first time a highly enhanced RET strategy to promote the energy transfer efficiency by coencapsulating the donor ([Ru­(bpy)₃]²⁺)/acceptor (CdTe quantum dots, CdTe QDs) pairs into a silica nanosphere. Plenty of [Ru­(bpy)₃]²⁺ and CdTe QDs closely packed inside a single nanosphere greatly shortens the electron-transfer path and increases the RET probability, therefore significantly enhancing the luminous efficiency. Further combining with molecularly imprinting technique, we develop a novel ECL sensor for ultrasensitive and highly selective detection of target molecules. Proof of concept experiments showed that extremely low detection limits of subfg/mL (S/N = 3) with broad linear ranges (fg/mL to ng/mL) could be obtained for detection of two kinds of mycotoxins (α-ergocryptine and ochratoxin A) that are recognized as potential health hazards at very low concentrations. This strategy combining enhanced RET system and molecularly imprinting technique, represents a versatile ECL platform toward low-cost, rapid, ultrasensitive, and highly selective detection of target molecules in diverse applications

An Unconventional Hydrofullerene C₆₆H₄ with Symmetric Heptagons Retrieved in Low-Pressure Combustion

The combustion has long been applied for industrial synthesis of carbon materials such as fullerenes as well as carbon particles (known as carbon black), but the components and structures of the carbon soot are far from being clarified. Herein, we retrieve an unprecedented hydrofullerene C66H4 from a soot of a low-pressure combustion of benzene–acetylene–oxygen. Unambiguously characterized by single-crystal X-ray diffraction, the C66H4 renders a nonclassical geometry incorporating two heptagons and two pairs of fused pentagons in a C2v symmetry. The common vertexes of the fused pentagons are bonded with four hydrogen atoms to convert the hydrogen-linking carbon atoms from sp2 to sp3 hybridization, which together with the adjacent heptagons essentially releases the sp2-bond strains on the abutting-pentagon sites of the diheptagonal fused pentagon C66 (dihept-C66). DFT computations suggest the possibility for an in situ hydrogenation process leading to stabilization of the dihept-C66. In addition, the experiments have been carried out to study heptagon-dependent properties of dihept-C66H4, indicating the key responsibility of the heptagon for changing hydrocarbon activity and electronic properties. The present work with the unprecedented double-heptagon-containing hydrofullerene successfully isolated and identified as one of the low-pressure combustion products shows that the heptagon is a new building block for constructing fullerene products in addition to pentagons and hexagons in low-pressure combustion systems

Formation of Curvature Subunit of Carbon in Combustion

Curvature prevalently exists in the world of carbon materials (e.g., fullerenes, buckyl bowls, carbon nanotubes, and onions), but traditional C2-addition mechanisms fail to elucidate the mechanism responsible for the formation of carbon curvature starting from a pentagonal carbon ring in currently available chemical-physical processes such as combustion. Here, we show a complete series of nascent pentagon-incorporating C₅–C₁₈ that are online produced in the flame of acetylene–cyclopentadiene–oxygen and in situ captured by C₆₀ or trapped as polycyclic aromatic hydrocarbons for clarifying the growth of the curved subunit of C₂₀H₁₀. A mechanism regarding C1-substitution and C2-addition has been proposed for understanding the formation of curvature in carbon materials, as exemplified by the typical curved molecule containing a single pentagon completely surrounded by five hexagons. The present mechanism, supported by the intermediates characterized by X-ray crystallography as well as NMR, has been experimentally validated for the rational synthesis of curved molecule in the commercially useful combustion process

Formation of Curvature Subunit of Carbon in Combustion

Curvature prevalently exists in the world of carbon materials (e.g., fullerenes, buckyl bowls, carbon nanotubes, and onions), but traditional C2-addition mechanisms fail to elucidate the mechanism responsible for the formation of carbon curvature starting from a pentagonal carbon ring in currently available chemical-physical processes such as combustion. Here, we show a complete series of nascent pentagon-incorporating C₅–C₁₈ that are online produced in the flame of acetylene–cyclopentadiene–oxygen and in situ captured by C₆₀ or trapped as polycyclic aromatic hydrocarbons for clarifying the growth of the curved subunit of C₂₀H₁₀. A mechanism regarding C1-substitution and C2-addition has been proposed for understanding the formation of curvature in carbon materials, as exemplified by the typical curved molecule containing a single pentagon completely surrounded by five hexagons. The present mechanism, supported by the intermediates characterized by X-ray crystallography as well as NMR, has been experimentally validated for the rational synthesis of curved molecule in the commercially useful combustion process