Developing the Low-Temperature Oxidation Mechanism of Cyclopentane: An Experimental and Theoretical Study

At present, the reactivity of cyclic alkanes is estimated by comparison with acyclic hydrocarbons. Due to the difference in the structure of cycloalkanes and acycloalkanes, the thermodynamic data obtained by analogy are not applicable. In this study, a molecular beam sampling vacuum ultraviolet photoionization time-of-flight mass spectrometer (MB-VUV-PI-TOFMS) was applied to study the low-temperature oxidation of cyclopentane (CPT) at a total pressure range from 1–3 atm and low-temperature range between 500 and 800 K. Low-temperature reaction products including cyclic olefins, cyclic ethers, and highly oxygenated intermediates (e. g., ketohydroperoxide KHP, keto-dihydroperoxide KDHP, olefinic hydroperoxides OHP and ketone structure products) were observed. Further investigation of the oxidation of CPT – electronic structure calculations – were carried out at the UCCSD(T)-F12a/aug-cc-pVDZ//B3LYP/6-31+ G(d,p) level to explore the reactivity of O₂ molecules adding sequentially to cyclopentyl radicals. Experimental and theoretical observations showed that the dominant product channel in the reaction of CPT radicals with O₂ is HO₂ elimination yielding cyclopentene. The pathways of second and third O₂ addition – the dissociation of hydroperoxide – were further confirmed. The results of this study will develop the low-temperature oxidation mechanism of CPT, which can be used for future research on accurately simulating the combustion process of CPT.     

Developing Flexible Quinacridone-Derivatives-Based Photothermal Evaporaters for Solar Steam and Thermoelectric Power Generation

Solar-driven interfacial vaporization by localizing solar-thermal energy conversion to the air−water interface has attracted tremendous attention. In the process of converting solar energy into heat energy, photothermal materials play an essential role. Herein, a flexible solar-thermal material di-cyan substituted 5,12-dibutylquinacridone (DCN−4CQA)@Paper was developed by coating photothermal quinacridone derivatives on the cellulose paper. The DCN−4CQA@Paper combines desired chemical and physical properties, broadband light-absorbing, and shape-conforming abilities that render efficient photothermic vaporization. Notably, synergetic coupling of solar-steam and solar-electricity technologies by integrating DCN−4CQA@Paper and the thermoelectric devices is realized without trade-offs, highlighting the practical consideration toward more impactful solar heat exploitation. Such solar distillation and low-grade heat-to-electricity generation functions can provide potential opportunities for fresh water and electricity supply in off-grid or remote areas.     

Enhanced Power Density of Alcohol Biofuel Cell by Polymer-assisted Crosslinks of 3D Graphene on Carbon Paper as the Bioanode

Herein, we successfully construct the 3D biocompatible graphene through crosslinking 2D graphene nanosheet onto carbon fiber paper with poly(diallyldimethylammonium chloride) (PDDA) as anode of the alcohol biofuel cell. Compared with the bioanode without 3D graphene, the current density and output power of PDDA-graphene-ADH bioanode is increased by 23 % and 41 % at a high concentration of ethanol at pH 8.9, suggesting the stabilization role of graphene in enzyme loading. The study provides us a deep analysis on structures and performances of the bioanode incl. electrochemistry, X-ray photoelectron spectra, and atomic force microscopy images, which is significant to develop the new methods to construct 3D porous electrodes in energy conversion device.     

Sensitive CE-MS method for monitoring of riociguat and desmethylriociguat levels in human serum

Riociguat is novel antihypertensive drug for treatment of pulmonary hypertension. As such, it is still being tested in many clinical and pharmacokinetic trials. Existing methods that determine serum riociguat and desmethylriociguat (DMR) are based solely on liquid chromatography with mass spectrometry. Therefore, we present a novel capillary electrophoresis with mass spectrometry method (CE-MS) for their determination in human serum as alternative method for ongoing trials. Complete resolution of both analytes was achieved by means of pH optimization of ammonium formate background electrolytes that are fully compatible with ESI/MS detection. Simple liquid-liquid extraction was used as sample pretreatment. The calibration dependence of the method was linear (in the range of 10–1000 ng/mL), with adequate accuracy (90.1–114.9%) and precision (13.4%). LOD and LOQ were arbitrarily set at 10 ng/mL for both analytes. Clinical applicability was validated using serum samples from patients treated with riociguat in pharmacokinetic study and the results corresponded with reference HPLC-MS/MS values. Capillary electrophoresis proved to be sensitive and selective tool for the analysis of riociguat and DMR.     

Direct visualization of the nanoscopic three‐phase structure and stiffness of NBR/PVC blends by AFM nanomechanical mapping

The PeakForce Quantitative Nanomechanical Mapping based on atomic force microscope (AFM) is employed to first visualize and then quantify the elastic properties of a model nitrile rubber/poly(vinyl chloride) (NBR/PVC) blend at the nanoscale. This method allows us to consistently observe the changes in mechanical properties of each phase in polymer blends. Beyond measuring and discriminating elastic modulus and adhesion forces of each phase, we tune the AFM tips and the peak force parameters in order to reliably image samples. In view of viscoelastic difference in each phase, a three‐phase coexistence of an unmixed NBR phase, the mixed phase, and PVC microcrystallites is directly visualized in NBR/PVC blends. The nanomechanical investigation is also capable of recognizing the crosslinked rubber phase in cured rubber. The contribution of the mixed phase was quantified and it was found that the mechanical properties of blends are mainly determined by the homogeneity and stiffness of the mixed phase. This study furthers our understanding the structure–mechanical property relationship of thermoplastic elastomers, which is important for their potential design and applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 662–669     

Sensitive targeted multiple protein quantification based on elemental detection of Quantum Dots

A generic strategy based on the use of CdSe/ZnS Quantum Dots (QDs) as elemental labels for protein quantification, using immunoassays with elemental mass spectrometry (ICP-MS), detection is presented. In this strategy, streptavidin modified QDs (QDs-SA) are bioconjugated to a biotinylated secondary antibody (b-Ab₂). After a multi-technique characterization of the synthesized generic platform (QDs-SA-b-Ab₂) it was applied to the sequential quantification of five proteins (transferrin, complement C3, apolipoprotein A1, transthyretin and apolipoprotein A4) at different concentration levels in human serum samples. It is shown how this generic strategy does only require the appropriate unlabeled primary antibody for each protein to be detected. Therefore, it introduces a way out to the need for the cumbersome and specific bioconjugation of the QDs to the corresponding specific recognition antibody for every target analyte (protein). Results obtained were validated with those obtained using UV–vis spectrophotometry and commercial ELISA Kits.     

Plasmon Coupling-Induced Hot Electrons for Photocatalytic Hydrogen Generation

We present the fabrication of core-shell-satellite Au@SiO₂-Pt nanostructures and demonstrate that LSPR excitation of the core Au nanoparticle can induce plasmon coupling effect to initiate photocatalytic hydrogen generation from decomposition of formic acid. Further studies suggest that the plasmon coupling effect induces a strong local electric field between the Au core and Pt nanoparticles on the SiO₂ shell, which enables creation of hot electrons on the non-plasmonic-active Pt nanoparticles to participate hydrogen evolution reaction on the Pt surface. In addition, small SiO₂ shell thickness is required in order to obtain a strong plamon coupling effect and achieve efficient photocatalytic activities for hydrogen generation.     

从废水到新能源:光催化燃料电池的优化与应用

随着经济的飞速发展,社会对能源的需求日益扩大,对工业废水的无害化处理也提出了更高的要求。光催化燃料电池 (photocatalytic fuel cell, PFC) 在燃料电池中引入半导体光催化材料作为电极,实现了有机污染物高效降解和同步对外产电的双重功能,在废水无害化与资源化利用方面具有潜在的应用价值。半导体光催化电极是PFC系统高效运行的核心组件,增强其可见光响应和光生载流子分离是提高PFC性能的关键策略。反应器结构设计和运行参数优化也有利于改善PFC性能。本文从PFC基本原理和应用入手,综述了PFC在环境污染物资源化处理中的研究进展,并详细阐述了提高PFC的污染控制性能和产电效率的优化手段,为进一步设计高效稳定的PFC系统并实现其在水污染控制和清洁能源生产中的应用提供理论指导。     

A simple,rapid and sensitive method based on modified multiwalled carbon nanotube for preconcentration and determination of lead ions in aqueous media in natural pHs

In this study, multiwalled carbon nanotube (MWCNT) was modified by the pyridine group using a silane agent and characterized by infrared spectroscopy (IR), thermal analysis (TG/DTA), and elemental analysis (CHN) and scanning electron microscopy (SEM). The application of this sorbent was investigated in determination of lead ions in aqueous samples, using flame atomic absorption spectrometry (FAAS). Through this study, different parameters such as pH and sample flow rate on adsorption process and eluent concentration, volume and flow rate were optimized. The limit of detection (LOD), the relative standard deviation and the recovery of the method were 2 ng mL^?1, 1.3% and 99.7%, respectively. Two standard reference materials (NIST 1571 and NIST 1572) were used to verify accuracy of this method. Finally, the sorbent was successfully applied for extraction and determination of low levels of Pb(II) ions in aqueous samples.