Copper-Catalyzed Enantioconvergent Radical C(sp3)-N Cross-Coupling of Activated Racemic Alkyl Halides with (Hetero)aromatic Amines under Ambient Conditions.

The enantioconvergent C(sp3)-N cross-coupling of racemic alkyl halides with (hetero)aromatic amines represents an ideal means to afford enantioenriched N-alkyl (hetero)aromatic amines yet has remained unexplored due to the catalyst poisoning specifically for strong-coordinating heteroaromatic amines. Here, we demonstrate a copper-catalyzed enantioconvergent radical C(sp3)-N cross-coupling of activated racemic alkyl halides with (hetero)aromatic amines under ambient conditions. The key to success is the judicious selection of appropriate multidentate anionic ligands through readily fine-tuning both electronic and steric properties for the formation of a stable and rigid chelating Cu complex. Thus, this kind of ligand could not only enhance the reducing capability of a copper catalyst to provide an enantioconvergent radical pathway but also avoid the coordination with other coordinating heteroatoms, thereby overcoming catalyst poisoning and/or chiral ligand displacement. This protocol covers a wide range of coupling partners (89 examples for activated racemic secondary/tertiary alkyl bromides/chlorides and (hetero)aromatic amines) with high functional group compatibility. When allied with follow-up transformations, it provides a highly flexible platform to access synthetically useful enantioenriched amine building blocks.

Cu(I)-Catalyzed Chemo- and Enantioselective Desymmetrizing C-O Bond Coupling of Acyl Radicals.

Transition-metal-catalyzed enantioselective functionalization of acyl radicals has so far not been realized, probably due to their relatively high reactivity, which renders the chemo- and stereocontrol challenging. Herein, we describe Cu(I)-catalyzed enantioselective desymmetrizing C-O bond coupling of acyl radicals. This reaction is compatible with (hetero)aryl and alkyl aldehydes and, more importantly, displays a very broad scope of challenging alcohol substrates, such as 2,2-disubstituted 1,3-diols, 2-substituted-2-chloro-1,3-diols, 2-substituted 1,2,3-triols, 2-substituted serinols, and meso primary 1,4-diols, providing enantioenriched esters characterized by challenging acyclic tetrasubstituted carbon stereocenters. Partnered by one- or two-step follow-up transformations, this reaction provides a convenient and practical strategy for the rapid preparation of chiral C3 building blocks from readily available alcohols, particularly the industrially relevant glycerol. Mechanistic studies supported the proposed C-O bond coupling of acyl radicals.

Cu-catalysed enantioselective radical heteroatomic S-O cross-coupling.

The transition-metal-catalysed cross-coupling reaction has established itself as one of the most reliable and practical synthetic tools for the efficient construction of carbon-carbon/heteroatom (p-block elements other than carbon) bonds in both racemic and enantioselective manners. In contrast, development of the corresponding heteroatom-heteroatom cross-couplings has so far remained elusive, probably due to the under-investigated and often challenging heteroatom-heteroatom reductive elimination. Here we demonstrate the use of single-electron reductive elimination as a strategy for developing enantioselective S-O coupling under Cu catalysis, based on both experimental and theoretical results. The reaction manifests its synthetic potential by the ready preparation of challenging chiral alcohols featuring congested stereocentres, the expedient valorization of the biomass-derived feedstock glycerol, and the remarkable catalytic 4,6-desymmetrization of inositol. These results demonstrate the potential of enantioselective radical heteroatomic cross-coupling as a general chiral heteroatom-heteroatom formation strategy.

Parameter estimation of three-parameter Weibull probability model based on outlier detection.

The Weibull probability model used in statistical analysis has become more popular in the inconsistency evaluation of used Li-ion batteries due to its flexibility in fitting asymmetrically distributed data. However, despite its better fitting of data with a non-zero minimum, the three-parameter Weibull model is less used because of its complicated calculation. Additionally, the Weibull family is likely to overfit and shows inference from outliers. Although conventional estimation methods for Weibull parameters based on dispersion and symmetry of the overall distribution lead to derivation from the actual data features, there is little research into methods to solve the contradiction between estimation accuracy and proper outlier detection. In this study, a Weibull parameter estimation method was proposed that features simplified computation and eliminates the interference from outliers. The outliers were identified based on the obtained Weibull parameters and excluded from the sample data. The method was implemented for fitting the capacity distribution of Li-ion batteries, which was verified by a chi-square test at a confidence of 95% and the Anderson-Darling test. It showed a higher goodness-of-fit and less error than the results of the maximum likelihood estimated Weibull model as well as the normal distribution. The optimal presetting of column number and peak reference point selection were determined by parameter discussion.

Copper-Catalyzed anti-Selective Radical 1,2-Alkylarylation of Terminal Alkynes.

A copper-catalyzed highly anti-selective radical 1,2-alkylarylation of terminal alkynes with aryl boronic acids and alkyl bromides has been established. The reaction exhibits high compatibility with a wide range of terminal alkynes and diverse aryl boronic acids, thus providing facile access to various stereodefined trisubstituted alkenes in high yield under mild reaction conditions. Preliminary mechanistic investigations support the formation of alkyl radicals and their subsequent addition to alkynes in the reaction.

Quality improvement effects of electrolyzed water on rice noodles prepared with semidry-milled rice flours.

To investigate the effects of electrolyzed water treatment on the qualities of rice noodles prepared with semidry- milled rice flour, pasting properties and thermal properties of rice flour, and the cooking and textural properties of rice noodles were determined. Higher peak viscosity and lower melting enthalpy were observed in electrolyzed water (EW) treated rice flour. The hardness, gumminess and chewiness of rice noodle in slightly acidic electrolyzed water treated rice noodles with available chlorine concentration (ACC) 20.32 mg/L were increased significantly (p < 0.05). The cooking loss decreased significantly in strong acidic electrolyzed water treated noodles with ACC 10.09 mg/L treatment (p < 0.05). The results indicated that EW could promote the gelatinization of rice flour, and improve the textural qualities of rice noodles. Therefore EW was appropriate to be used in rice noodle production.

A cycling robust network binder for high performance Si-based negative electrodes for lithium-ion batteries.

Silicon has been a pivotal negative electrode material for the next generation lithium-ion batteries due to its superior theoretical capacity. However, commercial application of Si negative electrodes is seriously restricted by its fast capacity fading as a result of severe volume changes during the process of charge and discharge. A novel functional binder is essential to resolve this conflict. In this work, we have proposed a composite of carboxymethyl cellulose (CMC) and cationic polyacrylamides (CPAM) as an effective network binder to improve the electrochemical performance of Si-based negative electrodes in lithium-ion batteries. The CMC-CPAM composite binder is cross-linked physically through reversible electrostatic interaction. Unlike common covalent cross-linked binders, the network structure of it forms spontaneously at room temperature, which makes it self-healing. Besides, benefits from the use of high molecular CPAM, the CMC-CPAM network binder exhibits excellent mechanical and adhesive strength, which makes it robust enough to tolerate the volume change of Si. As a result, the Si electrode with the self-healing CMC-CPAM composite binder shows an excellent cycling stability than the covalent cross-linked CMC-polyacrylic acid (PAA) and linear CMC binders, with a capacity of 1906.4 mAh·g-1 remaining after 100 cycles. Moreover, the cycling performance of retaining 78% of the initial capacity after 350 cycles is achieved based on the commercial Si@C/graphite negative electrode using the self-healing CMC-CPAM network binder with a very high mass loading (~4 mg·cm-2).

Desymmetrization of unactivated bis-alkenes via chiral Brønsted acid-catalysed hydroamination.

Although great success has been achieved in catalytic asymmetric hydroamination of unactivated alkenes using transition metal catalysis and organocatalysis, the development of catalytic desymmetrising hydroamination of such alkenes remains a tough challenge in terms of attaining a high level of stereocontrol over both remote sites and reaction centers at the same time. To address this problem, here we report a highly efficient and practical desymmetrising hydroamination of unactivated alkenes catalysed by chiral Brønsted acids with both high diastereoselectivity and enantioselectivity. This method features a remarkably broad alkene scope, ranging from mono-substituted and gem-/1,2-disubstituted to the challenging tri- and tetra-substituted alkenes, to provide access to a variety of diversely functionalized chiral pyrrolidines bearing two congested tertiary or quaternary stereocenters with excellent efficiency under mild and user-friendly synthetic conditions. The key to success is indirect activation of unactivated alkenes by chiral Brønsted acids via a concerted hydroamination mechanism.

Recent Advances in First-Row Transition Metal/Chiral Phosphoric Acid Combined Catalysis.

Since the pioneering independent reports of Akiyama and Terada, the use of chiral phosphoric acids (CPAs) and derivatives as a versatile tool for asymmetric synthesis with good reactivity, regioselectivity, diastereoselectivity and enantioselectivity has emerged, forming an important part of the implementation of asymmetric counteranion-directed catalysis reported to date. In these achievements, the combination of metals with CPAs has enabled various catalytic modes beyond the scope of typical acid catalysis, such as relay catalysis, ion-pairing catalysis, and binary acid catalysis. The first-row transition metals (Sc-Zn) are considered to be sustainable transition metals and have received a great deal of attention. These naturally abundant metals display excellent Lewis acidity and function as powerful redox catalysts in synthesis involving both one and two-electron transfers. Hence, in this chapter, we summarize recent advances in the development of asymmetric reactions using a combination of first-row transition metals and CPAs. Furthermore, we provide a detailed discussion of the mechanisms involved in order to understand the interaction of the metal/phosphate and the origins of the asymmetric control of the transformations.

Effect of electrolyzed water on enzyme activities of triticale malt during germination.

Triticale malt can be used as a source of enzymes or as a raw material for the production of functional foods. In this study, triticale malt was produced by soaking triticale seeds either in tap water (TW) or slightly acidic electrolyzed water (SAEW) and then rinsing with TW, SAEW, or alkaline electrolyzed water (AEW). We determined the length of the hypocotyl of triticale malt and the activities of α-amylase, phytase, proteases, and lipase during 4 days of germination. The electrolyzed water (EW) treatments promoted the growth of triticale malt. On the 4th day of germination, the hypocotyl length of triticale malt soaked in TW and watered with SAEW was 24.57% longer than that of triticale malt soaked and watered with TW. The α-amylase, phytase, acidic protease, and lipase activities of triticale malt soaked in SAEW and watered with AEW were high on the 4th germination day (0.11, 1.24 × 10-4, 0.62, and 0.51 units/mg protein, respectively). The main finding of this study is that the use of EW, especially during the soaking procedure, may be a promising way to obtain triticale malt with high enzyme activity for use in the production of functional foods.

Achiral Pyridine Ligand-Enabled Enantioselective Radical Oxytrifluoromethylation of Alkenes with Alcohols.

A conceptually novel strategy with achiral pyridine as the ancillary ligand to stabilize high-valent copper species for the first asymmetric radical oxytrifluoromethylation of alkenes with alcohols under CuI /phosphoric acid dual-catalysis has been developed. The transformation features mild reaction conditions, a remarkably broad substrate scope and excellent functional group tolerance, offering an efficient approach to a wide range of trifluoromethyl-substituted tetrahydrofurans bearing an α-tertiary stereocenter with excellent enantioselectivity. Mechanistic studies support the presumed role of the achiral pyridine as a coordinative ligand on copper metal to stabilize the key transient reaction species involved in the asymmetric induction process.

Application of electrolyzed water on reducing the microbial populations on commercial mung bean sprouts.

The efficacy of acidic electrolyzed water (AEW) for reducing total bacteria, coliforms, yeast and mold counts on commercial mung bean sprouts was investigated. The impact of pH, available chlorine concentration (ACC) and the cleaning method on antimicrobial efficacy of AEW was studied. AEW with a pH of 4.47 reduced the total bacterial, coliform, and yeast and mold counts on mung bean sprouts by 1.23, 1.42 and 1.25 log CFU/g, respectively. The efficacy of AEW increased with increasing ACC, and further studies showed that its antimicrobial ability was based on a combination of pH and ACC values. Cleaning using ultrasonic waves enhanced the antimicrobial activity of electrolyzed water, achieving reduction of 2.46, 2.13 and 2.92 log CFU/g for total bacterial, yeast and mold, and coliform counts, respectively. These results have indicated that using ultrasonic waves as a cleaning method, combined with AEW, could be a promising way to reduce the microbial populations on mung bean sprouts.

Intracellular interferons in fish: a unique means to combat viral infection.

We demonstrate for the first time in vertebrates, that alternative splicing of interferon (IFN) genes can lead to a functional intracellular IFN (iIFN). Fish IFN genes possess introns and in rainbow trout three alternatively spliced transcripts of the IFN1 gene exist. Two of the encoded IFNs are predicted to lack a signal peptide. When overexpressed these iIFNs induce antiviral responses. Variants of the two IFNR receptor chains (IFNAR1 and IFNAR2) lacking a signal peptide are also present in trout. Transfection of HEK 293T cells with the iIFN and iIFNR molecules results in STAT phosphorylation and induction of antiviral genes. These results show that fish possess a functioning iIFN system that may act as a novel defence to combat viral infection.

Low-background, highly sensitive DNA biosensor by using an electrically neutral cobalt(II) complex as the redox hybridization indicator.

An electrically neutral cobalt complex, [Co(GA)2(phen)] (GA = glycollic acid, phen = 1,10-phenathroline), was synthesized and its interactions with double-stranded DNA (dsDNA) were studied by using electrochemical methods on a glassy carbon electrode (GCE). We found that [Co(GA)2(phen)] could intercalate into the DNA duplex through the planar phen ligand with a high binding constant of 6.2(±0.2)×10(5) M(-1). Surface studies showed that the cobalt complex could electrochemically accumulate within the modified dsDNA layer, rather than within the single-stranded DNA (ssDNA) layer. Based on this feature, the complex was applied as a redox-active hybridization indicator to detect 18-base oligonucleotides from the CaMV35S promoter gene. This biosensor presented a very low background signal during hybridization detection and could realize the detection over a wide kinetic range from 1.0×10(-14) M to 1.0×10(-8) M, with a low detection limit of 2.0 fM towards the target sequences. The hybridization selectivity experiments further revealed that the complementary sequence, the one-base-mismatched sequence, and the non-complementary sequence could be well-distinguished by the cobalt-complex-based biosensor.