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Electrochemical energy conversion is an important supplement for storage and on-demand use of renewable energy. In this regard, microfluidics offers prospects to raise the efficiency and rate of electrochemical energy conversion through enhanced mass transport, flexible cell design, and ability to eliminate the physical ion-exchange membrane, an essential yet costly element in conventional electrochemical cells. Since the 2002 invention of the microfluidic fuel cell, the research field of microfluidics for electrochemical energy conversion has expanded into a great variety of cell designs, fabrication techniques, and device functions with a wide range of utility and applications. The present review aims to comprehensively synthesize the best practices in this field over the past 20 years. The underlying fundamentals and research methods are first summarized, followed by a complete assessment of all research contributions wherein microfluidics was proactively utilized to facilitate energy conversion in conjunction with electrochemical cells, such as fuel cells, flow batteries, electrolysis cells, hybrid cells, and photoelectrochemical cells. Moreover, emerging technologies and analytical tools enabled by microfluidics are also discussed. Lastly, opportunities for future research directions and technology advances are proposed.Here we demonstrate the feasibility and efficiency of simple iridium-based catalytic systems in the synthesis of multisubstituted alkenyl boronates from internal alkynes with high selectivities. A variety of alkynes were smoothly decorated with HBpin under a mild [Ir(cod)Cl]2/dppm/acetone condition to afford trisubstituted alkenyl boronic esters with up to >991 regioselectivity. The diboration reaction could effectively occur in the presence of [Ir(cod)Cl]2/DCM. Plausible mechanisms were provided to illustrate these two catalytic processes, in which the intrinsic functional group of the alkyne was supposed to be important in facilitating these reactions as well as the regioselectivity.Synthetic molecular probes, chemosensors, and nanosensors used in combination with innovative assay protocols hold great potential for the development of robust, low-cost, and fast-responding sensors that are applicable in biofluids (urine, blood, and saliva). Particularly, the development of sensors for metabolites, neurotransmitters, drugs, and inorganic ions is highly desirable due to a lack of suitable biosensors. In addition, the monitoring and analysis of metabolic and signaling networks in cells and organisms by optical probes and chemosensors is becoming increasingly important in molecular biology and medicine. Thus, new perspectives for personalized diagnostics, theranostics, and biochemical/medical research will be unlocked when standing limitations of artificial binders and receptors are overcome. In this review, we survey synthetic sensing systems that have promising (future) application potential for the detection of small molecules, cations, and anions in aqueous media and biofluids. Special attention was given to sensing systems that provide a readily measurable optical signal through dynamic covalent chemistry, supramolecular host-guest interactions, or nanoparticles featuring plasmonic effects. This review shall also enable the reader to evaluate the current performance of molecular probes, chemosensors, and nanosensors in terms of sensitivity and selectivity with respect to practical requirement, and thereby inspiring new ideas for the development of further advanced systems.The sequestering and complete conversion of SO2 to valuable chemicals in a metal-free pathway is highly demanded. The recent success of SO2 fixation by N-heterocyclic carbenes instigated further studies in this regard. Previous reports were confined within the carbene-SO2 reaction mechanism and the stability of oxathiirane S-oxide derivatives. The complete conversion of captured SO2 to precious chemicals was not studied. The present inquisition has accomplished the scarcity of the earlier studies. It is observed that in the presence of an excess amount of carbene, the registered SO2 is converted to the ketone derivative and thiocarbonyl S-oxide derivative. An electronic level investigation of these reactions is carried out. From the change of the molecular orbitals along the reaction path, it is concluded that the reaction between the oxathiirane S-oxide derivative and carbene follows a frog's hunting mechanism.Smart nanotheranostic systems (SNSs) have attracted extensive attention in antitumor therapy. Nevertheless, constructing SNSs with disease diagnosis ability, improved drug delivery efficiency, inherent imaging performance, and high treatment efficiency remains a scientific challenge. Herein, ultrasmall tin dioxide (SnO2) was assembled with upconversion nanoparticles (UCNPs) to form mesoporous nanocapsules by an in situ hydrothermal deposition method, followed by loading with doxorubicin (DOX) and modification with bovine serum albumin (BSA). pH/near-infrared dual-responsive nanotheranostics was constructed for computed tomography (CT) and magnetic resonance (MR) imaging-induced collaborative cancer treatment. The mesoporous channel of SnO2 was utilized as a reservoir to encapsulate DOX, an antineoplastic drug, for chemotherapy and as a semiconductor photosensitizer for photodynamic therapy (PDT). Furthermore, the DOX-loaded UCNPs@SnO2-BSA nanocapsules combined PDT, Nd3+-doped UCNP-triggered hyperthermia effect, and DOX-triggered chemotherapy simultaneously and demonstrated prominently enhanced treatment efficiency compared to the monotherapy model. Moreover, tin, as one of the trace elements in the human body, has a similar X-ray attenuation coefficient to iodine and therefore can act as a contrast agent for CT imaging to monitor the treatment process. Such an orchestrated synergistic anticancer treatment exhibited apparent inhibition of tumor growth in tumor-bearing mice with negligible side effects. Our study demonstrates nanocapsules with excellent biocompatibility and great potential for cancer treatment.Through regulation of the epigenome, the bromodomain and extra terminal (BET) family of proteins represent important therapeutic targets for the treatment of human disease. Through mimicking the endogenous N-acetyl-lysine group and disrupting the protein-protein interaction between histone tails and the bromodomain, several small molecule pan-BET inhibitors have progressed to oncology clinical trials. This work describes the medicinal chemistry strategy and execution to deliver an orally bioavailable tetrahydroquinoline (THQ) pan-BET candidate. Critical to the success of this endeavor was a potency agnostic analysis of a data set of 1999 THQ BET inhibitors within the GSK collection which enabled identification of appropriate lipophilicity space to deliver compounds with a higher probability of desired oral candidate quality properties. SAR knowledge was leveraged via Free-Wilson analysis within this design space to identify a small group of targets which ultimately delivered I-BET567 (27), a pan-BET candidate inhibitor that demonstrated efficacy in mouse models of oncology and inflammation.The ability of cells to take and change shape is a fundamental feature underlying development, wound repair, and tissue maintenance. Central to this process is physical and signaling interactions between the three cytoskeletal polymeric networks F-actin, microtubules, and intermediate filaments (IFs). Vimentin is an IF protein that is essential to the mechanical resilience of cells and regulates cross-talk among the cytoskeleton, but its role in how cells sense and respond to the surrounding extracellular matrix is largely unclear. To investigate vimentin's role in substrate sensing, we designed polyacrylamide hydrogels that mimic the elastic and viscoelastic nature of in vivo tissues. Using wild-type and vimentin-null mouse embryonic fibroblasts, we show that vimentin enhances cell spreading on viscoelastic substrates, even though it has little effect in the limit of purely elastic substrates. Our results provide compelling evidence that vimentin modulates how cells sense and respond to their environment and thus plays a key role in cell mechanosensing.Investigation of LiOH decomposition in nonaqueous electrolytes not only expands the fundamental understanding of four-electron oxygen evolution reactions in aprotic media but also is crucial to the development of high-performance lithium-air batteries involving the formation/decomposition of LiOH. read more In this work, we have shown that the decomposition of LiOH by ruthenium metal catalysts in a wet DMSO electrolyte occurs at the catalyst-electrolyte interface, initiated via a potential-triggered dissolution/reprecipitation process. The in situ UV-vis methodology devised herein provides direct experimental evidence that the hydroxyl radical is a common reaction intermediate formed in several nonaqueous electrolytes; this method is applicable to study other battery systems. Our results highlight that the reactivity of the hydroxyl radical toward nonaqueous electrolyte represents a major factor limiting O2 evolution during LiOH decomposition. Coupling catalysts restraining hydroxyl reactivity with electrolytes more resistant to hydroxyl radical attack could help improve the reversibility of this reaction.Fluorescence sensors based on small organic molecules are drawing increasing attention. In this contribution, the underlying detection mechanism of a typical fluorescence sensor for 2,4,6-trinitrophenol (TNP) based on fluorescence quenching is comprehensively investigated. The TNP molecule is proved to plant an intermolecular electron transfer state (dark state) below the bright state. Strong π-π interaction is observed between the sensor and TNP, which provides considerable orbital overlaps between the sensor and analyte. Electron transfer from the sensor to analyte is facilitated by such a strong interaction, which quenches the sensor's fluorescence. The design strategy for such TNP sensors is proposed based on the detection mechanism, and a series of new sensors is designed, which is likely to have better sensitivity than the original sensor.A room-temperature self-healing silicone elastomer was prepared based on the synergistic effect of multiple H-bonding and dynamic covalent bond. The multiple bonds constructed by inserting thiourea into the polyurea network can inhibit the crystallization of hard urea H-bonds segments and activate the diffusion movement of polymer chains. Dynamic imine endows materials with a strong connection for the fracture interface by imine metathesis. The effect of thiourea on urea H-bonds was confirmed by the Fourier transform infrared spectrum, which showed obvious changes of H-bond density according to peak revolution of C═O and N-H. Differential scanning calorimetry demonstrated the transition from the crystalline to amorphous state after the introduction of thiourea. Tensile tests and scratch-healing tests showed that this design method can improve the self-healing property without sacrificing the mechanical strength. Finally, the optimized self-healing process was analyzed from the perspectives of the contact process, the interpenetration diffusion of the polymer chain, and rebuilding of crosslinking points between the two interfaces, which would build an avenue for constructing a fast, self-healing, and tough material.
Website: https://www.selleckchem.com/products/px-12.html
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