Improved Mobility-Stretchability Properties of Diketopyrrolopyrrole-Based Conjugated Polymers with Diastereomeric Conjugation Break Spacers.

Stretchable conjugated polymers with conjugation break spacers (CBSs) synthesized via random terpolymerization have gained considerable attention because of their efficacy in modulating mobility and stretchability. This study incorporates a series of dianhydrohexitol diastereomers of isosorbide (ISB) and isomannide (IMN) units into the diketopyrrolopyrrole-based backbone as CBSs. It is found that the distorted CBS (IMN) improves the mobility-stretchability properties of the polymer with a highly coplanar backbone, whereas the extended CBS (ISB) enhances those of the polymer with a noncoplanar backbone. Additionally, the different configurations of ISB and IMN sufficiently affect the solid-state packing, aggregation capabilities, crystallographic parameters, and mobility-stretchability properties of the polymer. The IMN-based polymers exhibit the highest mobility of 1.69 cm2 V-1 s-1 and crystallinity retentions of (85.7, 78.6)% under 20% and 60% strains, outperforming their ISB-based or unmodified counterparts. The improvement is correlated with a robust aggregation capability. Furthermore, the CBS content affects aggregation behavior, notably affecting mobility. This result indicates that incorporating CBSs into the polymer can enhance backbone flexibility via movement and rotation of the CBS without affecting the crystalline regions.

Asymmetric 1,n-Remote Aminoacetoxylation of Unactivated Internal Alkenes Enabled by Palladium Catalysis.

A palladium-catalyzed asymmetric 1,n-remote aminoacetoxylation of cis-alkenes has been developed using PhI(OAc)2 as an oxidant, providing the acetoxylated lactams with excellent enantioselectivities under mild reaction conditions. The sterically hindered pyridine-oxazoline (Pyox) L3 with a tert-butyl group in oxazoline ring and propyl group in C6 position of pyridinyl is vital for the reaction, where the former is good for asymmetric aminopalladation step and the latter for the chain walking process. The enantioenriched lactam products were proven to be good building blocks for the synthesis of azabicycles.

Palladium-Catalyzed Remote Hydrosulfonamidation of Alkenes: Access to Primary N-Alkyl Sulfamides by the SuFEx Reaction.

Herein, we establish a remote hydrosulfonamidation (HSA) of alkenes using palladium catalysis, where N-fluoro-N-(fluoro-sulfonyl)-carbamate with a sulfur(VI) fluoride moiety is demonstrated as a good amidation reagent. The anti-Markovnikov HSA reaction of terminal alkenes and the remote HSA of internal alkenes are achieved to efficiently yield primary N-alkyl-N-(fluorosulfonyl)-carbamates. In addition, this protocol enables the high-value utilization of alkane by combining the dehydrogenation process. The generated N-alkyl products exhibit a unique reactivity of sulfur(VI) fluorides, which can be directly transferred to N-alkyl sulfamides or amines via the sulfur(VI) fluoride exchange reaction, thereby streamlining their synthesis. Moreover, a (pyridyl) benzazole-type ligand proved to be vital for the excellent chemo- and regioselectivities.

Site-Selective sp2 C-H Cyanation of Allenes via Copper-Catalyzed Radical Relay.

Compared with the extensively reported hydrogen atom transfer (HAT) at sp3 C-H, abstraction of hydrogen atoms at the sp2 carbon is extremely rare. Here, we communicate the site-selective cyanation of the sp2 C-H bond of allenes using the strategy of copper-catalyzed radical relay. The reactions afford various allenyl nitriles directly from simple allenes with a broad substrate scope and a remarkable functional group compatibility under mild conditions. These reactions exhibit excellent site-selectivity toward sp2 C-H, which can be attributed to the unique pocket created by the Cu-bound nitrogen-centered radical. The favorable HAT on sp2 C-H is due to crucial hydrogen bonding between the fluoride bonded to the Cu(II) center and the hydrogen atom at the allylic position. These features enable the late-stage functionalization of druglike bioactive molecules containing an allene motif.

Effects of acute stress on risky decision-making are related to neuroticism: An fMRI study of the Balloon Analogue Risk Task.

BACKGROUND: Decision making under acute stress is frequent in daily life. While evidence suggests for a modulatory role of neuroticism on risky decision-making behaviors, the neural correlates underlying the association between neuroticism and risky decision-making under acute stress remain to be elucidated. METHODS: Based on a modified Balloon Analogue Risk Task (BART) with concurrent functional magnetic resonance imaging, we evaluated the effect of acute stress on risk-taking behavior in 27 healthy male adults, and further assessed stress-induced changes in brain activation according to the individual differences in neuroticism. RESULTS: Higher trait neuroticism levels positively correlated with increased stress-modulated activation of the right dorsal anterior cingulate cortex during risk-taking, and negatively correlated with decreased stress-modulated activation of the right dorsolateral prefrontal cortex during cash-outs. LIMITATIONS: Only male participants were recruited. CONCLUSIONS: We found a positive correlation between neuroticism and greater risk-taking behavior under acute stress. These results extend our understanding of the increased risk-taking propensity in high neurotic individuals under acute stress.

Copper-Catalyzed Asymmetric Functionalization of Vinyl Radicals for the Access to Vinylarene Atropisomers.

A novel asymmetric radical strategy for the straightforward synthesis of atropisomerically chiral vinyl arenes has been established herein, proceeding through copper-catalyzed atroposelective cyanation/azidation of aryl-substituted vinyl radicals. Critical to the success of the radical relay process is the atroposelective capture of the highly reactive vinyl radicals with chiral L*Cu(II) cyanide or azide species. Moreover, these axially chiral vinylarene products can be easily transformed into atropisomerically enriched amides and amines, enantiomerically enriched benzyl nitriles via an axis-to-center chirality transfer process, and an atropisomerically pure organocatalyst for the chemo-, diastereo-, and enantioselective (4 + 2) cyclization reaction.

Asymmetric Palladium-Catalyzed Aminochlorination of Unactivated Alkenes.

A novel Pd-catalyzed enantioselective aminochlorination of alkenes via a 6-endo cyclization is reported herein, which provides easy access to a wide array of structurally diverse 3-chloropiperidines in good yields with excellent enantioselectivities. Notably, both an electrophilic chlorination reagent (NCS) and the sterically bulky chiral pyridinyl-oxazoline (Pyox) ligand are crucial to the successful reaction.

Regio- and enantioselective remote dioxygenation of internal alkenes.

Methods for the enantioselective direct oxygenation of internal alkenes have provided chemists with versatile and powerful toolboxes for the synthesis of optically pure alcohols, one of the most privileged structural motifs. Regioselectivity, however, remains a formidable challenge in the functionalization of internal alkenes. Here we report a palladium-catalysed highly regio- and enantioselective remote 1,n-dioxygenation (n ≥ 4) of internal alkenes with engineered pyridine-oxazoline (Pyox) ligands. The reactions proceed efficiently and exhibit a broad substrate scope with excellent regio- and enantioselectivity, affording optically pure 1,n-diol acetates as the key synthons for important bioactive molecules. Experimental studies and density functional theory calculations provide evidence that the regioselectivity is governed by the reactivity disparity of two allylic C-H bonds, where the oxypalladation is reversible and the first palladium migration step proves to be the regioselectivity-determining step, enabled by the modified phenyl-substituted Pyox ligands.

Enantioselective cyanation of propargylic C-H bonds via cooperative photoredox and copper catalysis.

Herein, we report an enantioselective cyanation of propargylic C-H bonds by combining photoredox catalysis with a copper-catalyzed radical relay in which the propargylic radical was generated by an intramolecular 1,5-HAT process. This reaction provides easy access to optically pure propargyl nitrile compounds under mild conditions.

Dissociable brainstem functional connectivity changes correlate with objective and subjective vigilance decline after total sleep deprivation in healthy male subjects.

The maintenance of vigilance relies on the activation of the cerebral cortex by the arousal system centered on the brainstem. Previous studies have suggested that both objective and subjective vigilance are susceptible to sleep deprivation. This study aims to explore the alterations in brainstem arousal system functional connectivity (FC) and its involvement in these two types of vigilance decline following total sleep deprivation (TSD). Thirty-seven healthy male subjects underwent two counterbalanced resting-state fMRI scans, once in rested wakefulness (RW) and once after 36 h of TSD. The pontine tegmental area and caudal midbrain (PTA-cMidbrain), the core regions of the brainstem arousal system, were chosen as the seeds for FC analysis. The difference in PTA-cMidbrain FC between RW and TSD conditions was then investigated, as well as its associations with objective vigilance measured by psychomotor vigilance task (PVT) and subjective vigilance measured by Stanford Sleepiness Scale. The sleep-deprived subjects showed increased PTA-cMidbrain FC with the thalamus and cerebellum and decreased PTA-cMidbrain FC with the occipital, parietal, and sensorimotor regions. TSD-induced increases in PVT reaction time were negatively correlated with altered PTA-cMidbrain FC in the dorsolateral prefrontal cortex, extrastriate visual cortex, and precuneus. TSD-induced increases in subjective sleepiness were positively correlated with altered PTA-cMidbrain FC in default mode regions including the medial prefrontal cortex and precuneus. Our results suggest that different brainstem FC patterns underlie the objective and subjective vigilance declines induced by TSD.

Palladium-Catalyzed Remote Hydro-Oxygenation of Internal Alkenes: An Efficient Access to Primary Alcohols.

As a general method for the synthesis of alcohols, the direct oxygenation of alkenes is difficult to afford linear alcohols. Herein, we communicate the remote hydro-oxygenation of alkenes under palladium catalysis, in which both terminal and internal alkenes are suitable to yield the corresponding linear alcohols efficiently. A compatible SelectFluor/silane redox system plays an essential role for the excellent chemo- and regioselectivities. The reaction features a broad substrate scope and excellent functional group compatibility.

Electrophotocatalytic Decoupled Radical Relay Enables Highly Efficient and Enantioselective Benzylic C-H Functionalization.

Asymmetric sp3 C-H functionalization has been demonstrated to substantially expedite target molecule synthesis, spanning from feedstocks upgradation to late-stage modification of complex molecules. Herein, we report a highly efficient and sustainable method for enantioselective benzylic C-H cyanation by merging electrophoto- and copper catalysis. A novel catalytic system allows one to independently regulate the hydrogen atom transfer step for benzylic radical formation and speciation of Cu(II)/Cu(I) to effectively capture the transient radical intermediate, through tuning the electronic property of anthraquinone-type photocatalyst and simply modulating the applied current, respectively. Such decoupled radical relay catalysis enables a unified approach for enantioselective benzylic C-H cyanation of diverse alkylarenes, many of which are much less reactive or even unreactive using the existing method relying on coupled radical relay. Moreover, the current protocol is also amenable to late-stage functionalization of bioactive molecules, including natural products and drugs.

Association of Transferrin Gene Polymorphism with Cognitive Deficits and Psychiatric Symptoms in Patients with Chronic Schizophrenia.

A large amount of recent literature has focused on impaired iron homeostasis in the pathophysiology of schizophrenia. Specifically, microarray analysis has illustrated associations between the transferrin locus and schizophrenia. To elaborate on the effects of transferrin on schizophrenia and its psychiatric phenotypes, our study aimed to investigate whether transferrin gene polymorphism was correlated with cognitive deficits and clinical symptoms in schizophrenia. We recruited 564 patients with chronic schizophrenia and 422 healthy controls (HCs) in a Han Chinese population, collected phenotypic data, and genotyped the rs3811655 polymorphism of the transferrin gene. Our results showed that the rs3811655 polymorphism was related to cognitive performance in both patients and HCs, as well as negative symptoms in patients (all p < 0.05), and patients carrying at least one G-allele showed worsened cognition/severe negative symptoms (all p < 0.05). Further analyses also found that the rs3811655 polymorphism in combination with cognition may exert small but significant contributions to the negative (ß = −0.10, t = −2.48, p < 0.05) or total psychiatric symptoms (ß = −0.08, t = −1.92, p < 0.05) in patients. Our findings indicated that the rs3811655 polymorphism may be implicated in the cognitive deficits of schizophrenia and HCs as well as psychiatric symptoms in patients, which suggested the possible iron regulatory mechanism in the pathology of schizophrenia.

Enantioselective Radical Trifluoromethylation of Benzylic C-H Bonds via Cooperative Photoredox and Copper Catalysis.

The first enantioselective radical trifluoromethylation of benzylic C-H bonds has been established by a cooperative photoredox and copper catalysis system, providing straightforward access to structurally diverse benzylic trifluoromethylation products in good yields with excellent enantioselectivities under mild conditions. Our method features a broad substrate scope and excellent functional group compatibility. Merging the cooperative photoredox catalysis with copper catalysis is essential for the reaction, where the photoredox catalysis is used for the generation of benzylic radicals from alkyl arenes through a hydrogen atom transfer process and the copper catalysis is used for the enantioselective trifluoromethylation of the benzylic radicals.

Electrospun nanofibrous membrane with antibacterial and antiviral properties decorated with Myoporum bontioides extract and silver-doped carbon nitride nanoparticles for medical masks application.

Public health safety issues have been plaguing the world since the pandemic outbreak of coronavirus disease (COVID-19). However, most personal protective equipments (PPE) do not have antibacterial and anti- toxicity effects. In this work, we designed and prepared a reusable, antibacterial and anti-toxicity Polyacrylonitrile (PAN) based nanofibrous membrane cooperated with Ag/g-C3N4 (Ag-CN), Myoporum.bontioides (M. bontioides) plant extracts and Ag nanoparticles (NPs) by an electrospinning-process. The SEM and TEM characterization revealed the formation of raised, creased or wrinkled areas on the fiber surface caused by the Ag nanoparticles, the rough surface prevented the aerosol particles on the fiber surface from sliding and stagnating, thus providing excellent filtration performance. The PAN/M. bontioides/Ag-CN/Ag nanofibrous membrane could be employed as a photocatalytic bactericidal material, which not only degraded 96.37% of methylene blue within 150 min, but also exhibited the superior bactericidal effect of 98.65 ± 1.49% and 97.8 ± 1.27% against E. coli and S. aureus, respectively, under 3 hs of light exposure. After 3 cycles of sterilization experiments, the PAN/M. bontioides/Ag-CN/Ag nanofibrous membrane maintained an efficient sterilization effect. Molecular docking revealed that the compounds in M. bontioides extracts interacted with neo-coronavirus targets mainly on Mpro and RdRp proteins, and these compounds had the strongest docking energy with Mpro protein, the shortest docking radius, and more binding sites for key amino acids around the viral protein targets, which influenced the replication and transcription process of neo-coronavirus. The PAN/M.bontioides/Ag-CN/Ag nanofibrous membrane also performed significant inhibition of influenza A virus H3N2. The novel nanofiber membrane is expected to be applied to medical masks, which will improve human isolation and protection against viruses.

Palladium(II)-Catalyzed Enantioselective Hydrooxygenation of Unactivated Terminal Alkenes.

A novel Pd(II)-catalyzed enantioselective Markovnikov hydrooxygenation of unactivated terminal alkenes using a substituted pyridinyl oxazoline (Pyox) ligand has been developed. Herein it was discovered that the (EtO)2MeSiH/BQ redox system is vital for the highly selective and efficient hydrooxygenation, where the alkylpalladium(II) species generated from enantioselective oxypalladation step is reduced by silane. This method provides efficient access to optically pure alcohol esters from easily available alkenes with excellent enantioselectivities and features a broad substrate scope.

Copper-catalyzed radical relay in C(sp3)-H functionalization.

Radical-involved transition metal (TM) catalysis has greatly enabled new reactivities in recent decades. Copper-catalyzed radical relay offers enormous potential in C(sp3)-H functionalization which combines the unique regioselectivity of hydrogen atom transfer (HAT) and the versatility of copper-catalyzed cross-coupling. More importantly, significant progress has been achieved in asymmetric C-H functionalization through judicious ligand design. This tutorial review will highlight the recent advances in this rapidly growing area, and we hope this survey will inspire future strategic developments for selective C(sp3)-H functionalization.

Catalytic remote hydrohalogenation of internal alkenes.

Primary alkyl halides have broad utility as fine chemicals in organic synthesis. The direct halogenation of alkenes is one of the most efficient approaches for the synthesis of these halides. Internal alkenes, in particular mixtures of isomers from refineries, constitute readily available and inexpensive feedstock and are the most attractive starting materials for this synthesis. However, the hydrohalogenation of alkenes generally affords branched alkyl halides; there are no catalytic methods to prepare linear alkyl halides directly from internal alkenes, let alone from a mixture of alkene isomers. Here we report the remote oxidative halogenation of alkenes under palladium catalysis via which both terminal and internal alkenes yield primary alkyl halides efficiently. Engineering pyridine-oxazoline ligands by introducing a hydroxyl group is essential for achieving excellent chemo- and regioselectivity. The catalytic system is also good for the mixture of alkene isomers generated from dehydrogenation of alkanes, providing a window to investigate the high-value utilization of inexpensive alkanes.

Polymorphism of Transferrin Gene Impacts the Mediating Effects of Psychotic Symptoms on the Relationship between Oxidative Stress and Cognition in Patients with Chronic Schizophrenia.

A series of studies indicated that iron distribution that partly derives from transferrin-bound iron in the peripheral nervous system in the brain may act in processes such as myelination and brain development. However, the relationship between schizophrenia, its psychotic symptoms, and the transferrin (TF) gene has not been systematically explored. Our study aimed to investigate how a particular polymorphism of the transferrin gene, rs3811655, affects the superoxide dismutase (SOD), malondialdehyde (MDA), psychotic symptoms, cognition, or the mediation model between antioxidant enzymes and cognition via symptoms. A total of 564 patients with chronic schizophrenia and 468 healthy control subjects were recruited. The psychotic symptoms and cognition were assessed by the Positive and Negative Syndrome Scale (PANSS) and the Repeatable Battery for the Assessment of Neuropsychological Status (RBANS), respectively. Furthermore, the serum SOD, MDA activity, and transferrin gene polymorphism were measured in patients. Our results demonstrated that patients with the G allele possessed more severe negative symptoms, worse cognitive performance with respect to attention, and higher serum Mn-SOD activity. Additionally, the rs3811655 polymorphism may act as a moderator in the association between Cu/Zn-SOD activity and cognition, as well as psychotic symptoms in patients suffering from schizophrenia. According to this study, the single nucleotide polymorphism (SNP) rs3811655 polymorphism may fail to contribute to the susceptibility of schizophrenia in an individual but is involved in the iron-induced oxidative stress disturbance and cognitive impairment in schizophrenia. This deepens our understanding of the critical role of iron-induced oxidative stress that might underlie the pathophysiology of schizophrenia.

Palladium-catalyzed intermolecular alkynylcarbonylation of unactivated alkenes: easy access to ß-alkynylcarboxylic esters.

A palladium-catalyzed intermolecular alkynylcarbonylation of unactivated alkenes has been established with ethynyl benziodoxolones (EBXs) as alkynylation reagents, providing ß-alkynylcarboxylic esters efficiently from simple alkenes. The reaction features moderate to excellent regioselectivity and excellent functional group compatibility under mild reaction conditions.