Mereditharmstrong6852
Although metal nanoclusters (MNCs) have shown great promise for the further development of photochemical techniques to be applied in diverse areas (e.g., photoelectronic devices, photochemical sensors, photocatalysts, and energy storage and conversion systems), the fundamental problem of their electron transfer behavior still remains unsolved. Herein, a driving force-dependent photoinduced electron transfer process of gold nanoclusters (AuNCs) is clarified for the first time from a rational-designed opposite-charged system. It was found that the electron transfer dynamic of carboxylated chitosan and dithiothreitol-commodified AuNCs (CC/DTT-AuNCs) can be satisfactorily described by the Marcus electron transfer theory. This proved model was applied to estimate the ultrafast charge separation process between CC/DTT-AuNCs and mitoxantrone, which was confirmed by fluorescence quenching and femtosecond transient absorption spectroscopy measurements. We envision that this work will open a new door for understanding the electron transfer behavior of MNCs and facilitate the design of advanced optoelectronic devices.Luo Han Guo fruit extract (Siraitia grosvenorii), mainly composed of mogroside V (50%), could be considered a suitable alternative to free sugars; however, its commercial applications are limited by its unpleasant off-notes. In the present work, a central composite design method was employed to optimize the transglycosylation of a mogroside extract using cyclodextrin glucosyltransferases (CGTases) from three different bacteriological sources (Paenibacillus macerans, Geobacillus sp., and Thermoanaerobacter sp.) considering various experimental parameters such as maltodextrin and mogroside concentration, temperature, time of reaction, enzymatic activity, and pH. Product structures were determined by liquid chromatography coupled to a diode-array detector (LC-DAD), liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS), and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). Sensory analysis of glucosylated mogrosides showed an improvement in flavor attributes relevant to licorice flavor and aftereffect. Consequently, an optimum methodology was developed to produce new modified mogrosides more suitable when formulating food products as free sugar substitutes.The precise and effective generation of micron-sized droplets is one of the most common and important issues for droplet-based microfluidics. Active droplet generation makes use of additional energy input in promoting interfacial instabilities for droplet generation. Here, we report a new technique for the active generation of femtoliter droplets in microfluidic systems using confined interfacial vibration (CIV). find more The CIV is formed at the orifice of a traditional inkjet nozzle first by pushing the liquid out and then pulling it back. Droplets are pinched off during the withdrawal process, and this is different from the current active droplet generation techniques, which only monodirectionally push the liquid out. Droplets with radius ranging from ca. 1 to 28 μm can be actively generated by CIV at an orifice with radius 30 μm, distinguishing from conventional active generation techniques in which the droplets are always comparable or slightly bigger than the orifice. Experimental results showed that the droplet volume can be customized by controlling the intensity of the CIV. The inherent digital nature of the inkjet technique enables easy and precise regulating of the droplet volume, making it seamlessly compatible with the digital microfluidic systems.The ability of carboxylate groups to promote the direct functionalization of C-H bonds in organic compounds is unquestionably one of the most important discoveries in modern chemical synthesis. Extensive computational studies have indicated that this process proceeds through the deprotonation of a metal-coordinated C-H bond by the basic carboxylate, yet experimental validation of these predicted mechanistic pathways is limited and fraught with difficulty, mainly as rapid proton transfer is frequently obscured in ensemble measures in multistep reactions (i.e., a catalytic cycle consisting of several steps). In this paper, we describe a strategy to experimentally observe the microscopic reverse of the key C-H bond activation step underpinning functionalization processes (viz. M-C bond protonation). This has been achieved by utilizing photochemical activation of the thermally robust precursor [Mn(ppy)(CO)4] (ppy = metalated 2-phenylpyridine) in neat acetic acid. Time-resolved infrared spectroscopy on the picosecond-millisecond time scale allows direct observation of the states involved in the proton transfer from the acetic acid to the cyclometalated ligand, providing direct experimental evidence for the computationally predicted reaction pathways. The power of this approach to probe the mechanistic pathways in transition-metal-catalyzed reactions is demonstrated through experiments performed in toluene solution in the presence of PhC2H and HOAc. These allowed for the observation of sequential displacement of the metal-bound solvent by the alkyne, C-C bond formation though insertion in the Mn-C bond, and a slower protonation step by HOAc to generate the product of a Mn(I)-catalyzed C-H bond functionalization reaction.Lead in drinking water remains a significant human health risk. At-home lead in water test kits could provide consumers with a convenient and affordable option to evaluate this risk, but their accuracy and reliability is uncertain. This study examined the ability of at-home lead test kits to detect varying concentrations of dissolved and particulate lead in drinking water. Sixteen brands representing four test kit types (binary color, binary strip, colorimetric vial, and color strip) were identified. Most kits (12 of 16 brands) were not suitable for drinking water analysis, with lead detection limits of 5-20 mg/L. Binary strips detected dissolved lead at drinking water-relevant levels but failed to detect particulate lead. Household acids (lemon juice and vinegar) improved the strip's ability to detect lead by dissolving some of the lead particulates to the point soluble lead exceeded 15 μg/L. These results illustrate the applications of at-home testing kits for drinking water analysis, highlight limitations and areas for possible improvement, and put forth a testing protocol by which new at-home lead test kits can be judged.