Here reported is the layer-by-layer-based advanced manufacturing that yields a simple, novel, and cost-effective technique for generating selective nanoparticle deposition and orientation in the form of well-controlled patterns. The surface roughness of the three-dimensionally printed patterns and the solid-liquid-air contact line, as well as the nanoparticle interactions in dipped suspensions, determine the carbon nanofiber (CNF) alignment, while the presence of triangular grooves supports the pinning of the meniscus, resulting in a configuration consisting of alternating CNF and polymer channels. The polymer/nanoparticle composites show 10 times lower resistance along with the particle alignment direction than the randomly distributed CNF networks and 6 orders of magnitude lower than that along the transverse direction. The unidirectional alignment of the CNF also demonstrates linear piezoresistivity behavior under small strain deformation along with high sensitivity and selectivity toward volatile organic compounds. The reported advanced manufacturing shows broad applications in microelectronics, energy transport, light composites, and multifunctional sensors.Diabetic wounds are a worldwide health problem causing extremely heavy public health burden and require effective treatment. Optimal strategies for treating nonhealing diabetic wounds include stem-cell-based therapy and delivery of novel drug substances, such as functional microRNAs (miRNAs); however, miRNA easily degrades in the wound microenvironment. Herein, we developed a human adipose stem-cell-derived exosome (hASC-exos)-based miRNA delivery strategy to enhance its therapeutic efficacy. The miR-21-5p mimics, as novel therapeutic candidates for diabetic wounds, were loaded into hASC-exos by electroporation, taking advantage of natural availability and biocompatibility of exosomes as extracellular miRNA transporting particles. The engineered exosomes (E-exos) exhibited excellent effects on promoting proliferation and migration of keratinocytes via Wnt/β-catenin signaling in vitro and accelerating diabetic wound healing by increasing re-epithelialization, collagen remodeling, angiogenesis, and vessel maturation in vivo. Results from this study would set the fundamentals of applying hASC-exos to deliver future drug substances and to develop cell-free therapy for wound-healing treatments.An unprecedented synthesis of polysubstituted pyrrolidines from anilines and diazo pyruvates by ruthenium catalysis under mild reaction conditions is reported. An enol intermediate derived from the N-H insertion of aniline toward the ruthenium carbene species as well as an imine ester intermediate generated by SET-mediated oxidation of enol were proposed as the key intermediates. This strategy provides various pyrrolidines containing four contiguous stereocenters in good efficiency with high diastereoselectivities.The synthesis of the biologically active alkaloid simulenoline, isolated from the roots of Zanthoxylum simulans, is reported. The natural product was assembled from simple commercial reagents via initial domino Knoevenagel/oxa-6π-electrocyclization followed by a one-pot singlet-oxygen ene-reaction/reduction sequence. New insights of singlet oxygen reactivity with olefinic substrates have been revealed.Nonvalence states of neutral molecules (Rydberg states) play important roles in nonadiabatic dynamics of excited states. In anions, such nonadiabatic transitions between nonvalence and valence states have been much less explored even though they are believed to play important roles in electron capture and excited state dynamics of anions. The aim of this Feature Article is to provide an overview of recent experimental observations, based on time-resolved photoelectron imaging, of valence to nonvalence and nonvalence to valence transitions in anions and to demonstrate that such dynamics may be commonplace in the excited state dynamics of molecular anions and cluster anions.New neutral nickel and palladium ethylene polymerization catalysts have been prepared that incorporate an anionic (N,O) chelating ligand. Extensive axial shielding is provided by two 3,5-dichloroaryl moieties in a "sandwich" orientation. Such shielding results in an exceptionally slow rate of chain transfer relative to migratory insertion in the nickel catalyst, and thus highly controlled polymerization of ethylene is observed, leading to lightly branched ultra-high molecular weight polyethylene with Mn values up to 4.1 × 106 g/mol.  https://www.selleckchem.com/products/ki16198.html  The analogous palladium catalysts provide the means for a detailed mechanistic study of chain propagation in an electronically asymmetric neutral palladium catalyst. Both isomers of the methyl ethylene complex can be generated and observed at low temperatures allowing experimental elucidation of mechanistic details of chain propagation probed in other electronically asymmetric systems only through DFT studies or by examination of model studies. The barrier to migratory insertion in these complexes is ca. 19.2 kcal/mol. Investigation of the equilibration of the methyl ethylene isomers in the presence of excess ethylene showed the isomerization rate is dependent on ethylene concentration. This is the first direct proof that isomerization in these alkyl ethylene intermediates is catalyzed by ethylene. Furthermore, isomer equilibration is much faster than migratory insertion so that the barriers for insertion of individual isomers cannot be determined.Ammonia (NH3) is typically present at higher concentrations in indoor air (∼10-70 ppb) than in outdoor air (∼50 ppt to 5 ppb). It is the dominant neutralizer of acidic species in indoor environments, strongly influencing the partitioning of gaseous acidic and basic species to aerosols, surface films, and bulk water. We have measured NH3 emissions from humans in an environmentally controlled chamber. A series of experiments, each with four volunteers, quantified NH3 emissions as a function of temperature (25.1-32.6 °C), clothing (long-sleeved shirts/pants or T-shirts/shorts), age (teenagers, adults, and seniors), relative humidity (low or high), and ozone ( less then 2 ppb or ∼35 ppb). Higher temperature and more skin exposure (T-shirts/shorts) significantly increased emission rates. For adults and seniors (long clothing), NH3 emissions are estimated to be 0.4 mg h-1 person-1 at 25 °C, 0.8 mg h-1 person-1 at 27 °C, and 1.4 mg h-1 person-1 at 29 °C, based on the temperature relationship observed in this study. Human NH3 emissions are sufficient to neutralize the acidifying impacts of human CO2 emissions.