A multicomponent reaction among dipyrranes, aryl-propargyl aldehydes, and p-chloranil leading to 10-(benzofuran-2-yl)corroles is described. p-Chloranil was identified as a crucial reagent playing a twofold role an oxidant taking part in the formation of the corrole macrocycle and a component undergoing heteroannulation to the incipient 10-arylethynylcorrole. A series of corroles bearing persubstituted benzofuran-2-yl moieties have been synthesized, and their fundamental electronic properties have been studied via UV-vis absorption and fluorescence spectroscopies.Siamenoside I is a rare mogroside in Siraitia grosvenorii Swingle and has become one of the target ingredients in natural sweetener production. However, the complex structure of siamenoside I has hindered its production in various ways. Here, a yeast cell that produces a specific β-glucosidase for siamenoside I conversion from mogroside V was constructed, and the enzymes were coelectrospun with poly(vinyl alcohol) followed by phenylboronic acid cross-linking to provide potential usage in the batch production process of Siamenoside I. A central composite design (CCD)-response surface methodology (RSM) was used to find the optimum coelectrospinning parameters. The pH stability and sodium dodecyl sulfate tolerance increased for the entrapped enzymes, and positive correlations between the fiber diameter and enzymatic activity were confirmed. The batch process showed an average siamenoside I production rate of 118 ± 0.08 mg L-1 h-1 per gram of fiber. This is the first research article showing specific siamenoside I production on enzyme-loaded electrospun fibers.Metal electrodeposition in room-temperature ionic liquids (RTILs) often shows high overpotentials. Although this is often explained by the formation of a negatively charged metal complex due to the coordination of RTIL anions and the hindrance of its close approach onto the negatively charged electrode, we propose an alternative model based upon surface-enhanced infrared absorption spectroscopy measurements under Co electrodeposition. We found that the anionic first layer exists on the negatively charged electrode, and its replacement with a cationic one and Co electrodeposition both begin at an identical onset potential. The correlation between the interfacial structure and the electrodeposition reaction that can be modified by additives indicated that the high overpotential can be mainly attributed to the restructuring of the characteristic interfacial multilayer structure stabilized by its charge order, which is required for the reorganization of solvent ions after the reduction of Co2+.The development of an asymmetric "clip-cycle" synthesis of 2,2- and 3,3-disubstituted pyrrolidines and spiropyrrolidines, which are increasingly important scaffolds in drug discovery programs, is reported. Cbz-protected bis-homoallylic amines were activated by "clipping" them to thioacrylate via an alkene metathesis reaction. Enantioselective intramolecular aza-Michael cyclization onto the activated alkene, catalyzed by a chiral phosphoric acid, formed a pyrrolidine. The reaction accommodated a range of substitutions to form 2,2- and 3,3-disubstituted pyrrolidines and spiropyrrolidines with high enantioselectivities. The importance of the thioester activating group was demonstrated by comparison to ketone and oxoester-containing substrates. DFT studies supported the aza-Michael cyclization as the rate- and stereochemistry-determining step and correctly predicted the formation of the major enantiomer. The catalytic asymmetric syntheses of N-methylpyrrolidine alkaloids (R)-irnidine and (R)-bgugaine, which possess DNA binding and antibacterial properties, were achieved using the "clip-cycle" methodology.The mechanistic resemblance of oil-based molecular gels (oleogels) to solid fats (trans and saturated) makes molecular gelation an ideal alternative in developing fat-based food and cosmetic products. The recent upsurge in the preference for oleogels (structured oils) is due to them being healthier than conventional solid fats. The present study reveals a simple means of modulating the mechanical and aesthetic properties of oleogels by physically mixing two isomeric low-molecular-weight gelators, mannitol dioctanoate (M8) and sorbitol dioctanoate (S8), which have contrasting oil-structuring behaviors; while M8 formed oleogels with a higher gel strength, the S8 gels were more aesthetic, translucent, and appealing. The gelators were synthesized by enzyme catalysis (a generally regarded as safe protocol). The M8/S8 gels were systematically and thoroughly characterized using a suite of analytical techniques, including minimum gelation concentration, gel melting point, rheological storage modulus, oil binding capacity, light transmittance, and optical microscopy. The results showed that the percentage of light transmittance, which is associated with aesthetics, increased from about 40 to 95% with an increasing fraction of S8 from 0 to 1. Parameters associated with mechanical strength, such as rheology, were also quite responsive to varying proportions of the gelators. The storage modulus (G', a rheological property) increased from about 3300 to about 12 500 Pa with an increasing fraction of M8. As the fraction of M8 increased, the solid fat content (SFC) changed from about 3.51 to 2.08%, while the oil binding capacity changed from about 70.2 to 100.0. This work enables the modulation of the aesthetic and organoleptic properties of a gel via a simple formulation of stereoisomeric molecular gelators.To increase the water solubility of zein as a stabilizing agent for oil-in-water (O/W) emulsions, three zein-polyglycerol (Zein-PG) conjugates, Zein-PG-2, Zein-PG-6, and Zein-PG-10, were prepared by dehydration between zein and polyglycerol aldehydes obtained by NaIO4 oxidation of polyglycerol-2, -6, and -10 and characterized by free amine content, grafting degree, Fourier transform infrared spectroscopy, and fluorescence spectra. All conjugates dispersed in water as nanoparticles were verified by transmission electron microscopy. Conjugation with PG changed the isoelectric point of zein from 6.2 to 6.8 and to 4.0. Zein-PG-6 and Zein-PG-10 showed strong stabilization on the O/W emulsions with 18-fold loading of soybean oil on the basis of conjugate mass, displaying high oil loading capacity. Confocal laser scanning microscopy (CLSM) confirmed the O/W structure of emulsions and that the absorption of Zein-PG-10 on the oil droplet surface offered the driving force to be stable. Ipatasertib The present Zein-PG conjugates thus produced an enticing resource for use as nanocarriers or bioemulsifiers in food or pharmaceutical industries.