Vacuum Ultraviolet Free-Electron Laser Photoionization Mass Spectrometry of Alpha-pinene Ozonolysis

\begin{document}$\alpha$\end{document}-pinene is the most abundant monoterpene that represents an important family of volatile organic compounds. Molecular identification of key transient compounds during the \begin{document}$\alpha$\end{document}-pinene ozonolysis has been proven to be a challenging experimental target because of a large number of intermediates and products involved. Here we exploit the recently developed hybrid instruments that integrate aerosol mass spectrometry with a vacuum ultraviolet free-electron laser to study the \begin{document}$\alpha$\end{document}-pinene ozonolysis. The experiments of \begin{document}$\alpha$\end{document}-pinene ozonolysis are performed in an indoor smog chamber, with reactor having a volume of 2 m\begin{document}$^3$\end{document} which is made of fluorinated ethylene propylene film. Distinct mass spectral peaks provide direct experimental signatures of previously unseen compounds produced from the reaction of \begin{document}$\alpha$\end{document}-pinene with O\begin{document}$_3$\end{document}. With the aid of quantum chemical calculations, plausible mechanisms for the formation of these new compounds are proposed. These findings provide crucial information on fundamental understanding of the initial steps of \begin{document}$\alpha$\end{document}-pinene oxidation and the subsequent processes of new particle formation.     

Enhanced photoactivity of CdS nanorods by MXene and ZnSnO3: Application in photoelectrochemical biosensor for the effect of environmental pollutants on DNA hydroxymethylation in wheat tissues

The photoactivity of CdS nanorods was greatly improved by amino functionalized accordion-like MXene and spherical ZnSnO₃. MXene possesses good electron transfer capability and ZnSnO₃ presents matched energy band with CdS, which deeply accelerate the electron transfer and prevent the recombination of photogenerated electron-hole pair, leading to a strong photoelectrochemical (PEC) response. Taking the merit of the improved photoactivity of CdS nanorods, a novel PEC biosensor was constructed for DNA hydromethylation detection based on immune recognition of target molecule, where 5-hydroxymethyl-2′-deoxycytidine triphosphate (5hmdCTP) was employed as detect target, CdS/MXene was used as photoactive material, and ZnSnO₃ was adopted as signal amplification unit. Under enzymatic covalent reaction of –CH₂OH of 5hmdCTP with –NH₂ of MXene, 5hmdCTP was specifically recognized and captured. Then, taking advantages of the covalent reaction between phosphate group of 5hmdCTP and ZnSnO₃, the signal amplification unit was captured. Under the optimum conditions, this PEC biosensor presents wide linear range of 0.008–100 nM and low detection limit of 4.21 pM (3σ). The applicability of the developed method was evaluated by investigating the effect of Cd²⁺ and perfluorohexane compound pollutant on 5-hydroxymethylcytosine content in the genomic DNA of the roots and leaves of wheat seedlings.     

Polydopamine-assisted co-deposition of polyacrylic acid inducing dentin biomimetic mineralization for tooth-like structure repair in vitro

The aging of the global population has caused dentin exposure and root caries to become significant patient-management issues in clinical dentistry. Biomimetic remineralization, as a non-invasive therapeutic method, is of great significance to solve the problem. Herein, a novel biomimetic-mineralizing strategy to induce the self-healing of dentin defects with similar tooth structure was developed through the easy one-step polydopamine (PDA)-assisted co-deposition of polyacrylic acid (PAA) (denoted as PDA@PAA) in vitro. Immersing demineralized dentin into PAA and dopamine (DA) mixed solutions. Hereafter, the modified demineralized dentin was immersed in the supersaturated solution of calcium and phosphate at 37 °C at designated time. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and attenuated total reflection fourier transform infrared (ATR-FTIR) were performed to analyze the interaction and co-deposition between PDA and PAA. The remineralization of demineralized dentin was characterized by field emission scanning electron microscope (FE-SEM), TEM, X-ray diffraction (XRD), friction and wear test, nanoindentation, acid resistance. And the cytocompatibility of PDA@PAA was evaluated by cell counting kit-8 (CCK-8) and cell morphology observation. The results that PAA inhibited further PDA polymerization and aggregation, PDA@PAA were co-deposited onto the surface of demineralized dentin matrix. SEM and TEM showed that the demineralized-dentin modified with PDA@PAA was completely remineralized at 12 h, not only the dentin tubules were occluded, but more importantly, the demineralized dentin collagen matrix was remineralized. Moreover, after mineralization for 24 h, a dense mineral layer similar to enamel structure was regenerated on the surface of dentin and closely combined with dentin. The results of mechanical properties and acid resistance suggested that the mechanical properties of the regenerated enamel-like structure are close to that of enamel, and its acid resistance is better than that of enamel. This study demonstrated that the PDA-assisted co-deposition of PAA can offer an inexpensive, rapid, and efficient strategy for the management of illnesses related to exposed and demineralized dentin.     

Cu2O-Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion

Nitrogen transfer from cyanide anion to an aldehyde is emerging as a promising method for the synthesis of aromatic nitriles. However, this method still suffers from a disadvantage that a use of stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction. As we report herein, we overcame this drawback and developed a catalytic method for nitrogen transfer from cyanide anion to an alcohol via the complete cleavage of the C≡N triple bond using phen/Cu₂O as the catalyst. The present condition allowed a series of benzyl alcohols to be smoothly converted into aromatic nitriles in moderate to high yields. In addition, the present method could be extended to the conversion of cinnamic alcohol to 3-phenylacrylonitrile.     

Adsorption of Volatile Organic Compounds (VOCs) on Oxygen-rich Porous Carbon Materials Obtained from Glucose/Potassium Oxalate

To investigate the effects of oxygen-containing functional groups on the adsorption of volatile organic compounds (VOCs) with different polarity, oxygen-rich porous carbon materials (OPCs) were synthesized by heat treatment of glucose/potassium oxalate material. The carbon material had a large specific surface area (1697 m² g⁻¹) and a high oxygen content (18.95 at.%). OPC exhibited high adsorption capacity of toluene (309 mg g⁻¹) and methanol (447 mg g⁻¹). The specific surface area and total pore volume determined the adsorption capacity of toluene and methanol at the high-pressure range, while the oxygen-containing groups became the main factor affecting the methanol adsorption at the low-pressure range due to the hydrogen bond interaction through the density functional theory (DFT) calculations. This study provides an important hint for developing a novel O-doped adsorbent for the VOCs adsorption applications and analyzing the role of oxygen-containing groups in the VOCs adsorption under the low-pressure range.     

Metal-Free B,N co-Doped Hierarchical Porous Carbon Electrocatalyst with an Excellent O2 Reduction Performance

Fuel cells have attracted increasing attention due to their low cost, high energy density, low environmental pollution, and abundant raw materials. Oxygen reduction reaction (ORR) is a core technology of fuel cells, and the development of new electrocatalysts with high ORR performance is highly desirable. Herein, we synthesize a series of B, N co-doped hierarchical porous carbons using a soft template method with the integration of self-assembly, calcination and etching. The obtained materials exhibit hierarchical porous structures, controllable pore distribution, partial graphite structures, and B, N co-doping. They can function as the cost-effective and metal-free electrocatalysts, facilitating the diffusion of electrolyte ions and the improvement of ORR performance. Especially, the B, N co-doped porous carbon with the B-to-N molar ratio of 5 (BNC-5) displays a high ORR activity with a half-wave potential (E_1/2) of 0.73 V, an onset potential (E_onset) of 0.94 V, and a high limiting current density (J_L) of 5.98 mA cm⁻², superior to the N-doped C (NC) and BNC-1 (the B-to-N molar ratio=1), BNC-3 (the B-to-N molar ratio=3) and BNC-7 (the B-to-N molar ratio=7) under the identical conditions. Moreover, the BNC-5 exhibits good cycling stability after 5000 cyclic voltammetry (CV) cycles and excellent tolerance toward even 3 M methanol. This research provides a new approach for the facile synthesis of dual element-doped carbon electrocatalysts with high ORR performance.     

Chemical Analyses and Antimicrobial Activity of Nine Kinds of Unifloral Chinese Honeys Compared to Manuka Honey (12+ and 20+)

Honey has good antimicrobial properties and can be used for medical treatment. The antimicrobial properties of unifloral honey varieties are different. In this study, we evaluated the antimicrobial and antioxidant activities of nine kinds of Chinese monofloral honeys. In addition, headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS) technology was used to detect their volatile components. The relevant results are as follows: 1. The agar diffusion test showed that the diameter of inhibition zone against Staphylococcus aureus of Fennel honey (21.50 ± 0.41 mm), Agastache honey (20.74 ± 0.37 mm), and Pomegranate honey (18.16 ± 0.11 mm) was larger than that of Manuka 12+ honey (14.27 ± 0.10 mm) and Manuka 20+ honey (16.52 ± 0.12 mm). The antimicrobial activity of Chinese honey depends on hydrogen peroxide. 2. The total antioxidant capacity of Fennel honey, Agastache honey, and Pomegranate honey was higher than that of other Chinese honeys. There was a significant positive correlation between the total antioxidant capacity and the total phenol content of Chinese honey (r = 0.958). The correlation coefficient between the chroma value of Chinese honey and the total antioxidant and the diameter of inhibition zone was 0.940 and 0.746, respectively. The analyzed dark honeys had better antimicrobial and antioxidant activities. 3. There were significant differences in volatile components among Fennel honey, Agastache honey, Pomegranate honey, and Manuka honey. Hexanal-D and Heptanol were the characteristic components of Fennel honey and Pomegranate honey, respectively. Ethyl 2-methylbutyrate and 3-methylpentanoic acids were the unique compounds of Agastache honey. The flavor fingerprints of the honey samples from different plants can be successfully built using HS-GC-IMS and principal component analysis (PCA) based on their volatile compounds. Fennel honey, Agastache honey, and Pomegranate honey are Chinese honey varieties with excellent antimicrobial properties, and have the potential to be developed into medical grade honey.     

The Effects of Hydrophobicity and Textural Properties on Hexamethyldisiloxane Adsorption in Reduced Graphene Oxide Aerogels

To expand the applications of graphene-based materials to biogas purification, a series of reduced graphene oxide aerogels (rGOAs) were prepared from industrial grade graphene oxide using a simple hydrothermal method. The influences of the hydrothermal preparation temperature on the textural properties, hydrophobicity and physisorption behavior of the rGOAs were investigated using a range of physical and spectroscopic techniques. The results showed that the rGOAs had a macro-porous three-dimensional network structure. Raising the hydrothermal treatment temperature reduced the number of oxygen-containing groups, whereas the specific surface area (S_BET), micropore volume (V_micro) and water contact angle values of the rGOAs all increased. The dynamic adsorption properties of the rGOAs towards hexamethyldisiloxane (L2) increased with increasing hydrothermal treatment temperature and the breakthrough adsorption capacity showed a significant linear association with S_BET, V_micro and contact angle. There was a significant negative association between the breakthrough time and inlet concentration of L2, and the relationship could be reliably predicted with a simple empirical formula. L2 adsorption also increased with decreasing bed temperature. Saturated rGOAs were readily regenerated by a brief heat-treatment at 100 °C. This study has demonstrated the potential of novel rGOA for applications using adsorbents to remove siloxanes from biogas.     

Camu-Camu Fruit Extract Inhibits Oxidative Stress and Inflammatory Responses by Regulating NFAT and Nrf2 Signaling Pathways in High Glucose-Induced Human Keratinocytes

Myrciaria dubia (HBK) McVaugh (camu-camu) belongs to the family Myrtaceae. Although camu-camu has received a great deal of attention for its potential pharmacological activities, there is little information on the anti-oxidative stress and anti-inflammatory effects of camu-camu fruit in skin diseases. In the present study, we investigated the preventative effect of 70% ethanol camu-camu fruit extract against high glucose-induced human keratinocytes. High glucose-induced overproduction of reactive oxygen species (ROS) was inhibited by camu-camu fruit treatment. In response to ROS reduction, camu-camu fruit modulated the mitogen-activated protein kinases (MAPK)/activator protein-1 (AP-1), nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB), and nuclear factor of activated T cells (NFAT) signaling pathways related to inflammation by downregulating the expression of proinflammatory cytokines and chemokines. Furthermore, camu-camu fruit treatment activated the expression of nuclear factor E2-related factor 2 (Nrf2) and subsequently increased the NAD(P)H:quinone oxidoreductase1 (NQO1) expression to protect keratinocytes against high-glucose-induced oxidative stress. These results indicate that camu-camu fruit is a promising material for preventing oxidative stress and skin inflammation induced by high glucose level.     

血液接触生物材料的血液相容性评价研究进展

生物材料的血液相容性是决定该材料能否在临床成功应用的重要标准之一。当材料与血液接触后,会引起溶血、凝血和免疫等一系列反应,机制复杂且受多种因素影响。因此,在材料临床应用前需根据ISO 10993-4进行生物相容性评价,血液相容性评价是其中重要部分,但目前尚未形成统一的评价标准与评价体系。本文总结了近年对血液相容性评价的主要方法,为今后生物材料血液相容性评价体系的建立提供参考。