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Targeting receptor‐interacting protein kinase 1 (RIPK1) has emerged as a promising therapeutic stratagem for neurodegenerative disorders, particularly Alzheimer's disease (AD). A positron emission tomography (PET) probe enabling brain RIPK1 imaging can provide a powerful tool to unveil the neuropathology associated with RIPK1. Herein, the development of a new PET radioligand, [11C]CNY‐10 is reported, which may enable brain RIPK1 imaging. [11C]CNY‐10 is radiosynthesized with a high radiochemical yield (41.8%) and molar activity (305 GBq/µmol). [11C]CNY‐10 is characterized by PET imaging in rodents and a non‐human primate, demonstrating good brain penetration, binding specificity, and a suitable clearance kinetic profile. It is performed autoradiography of [11C]CNY‐10 in human AD and healthy control postmortem brain tissues, which shows strong radiosignal in AD brains higher than healthy controls. Subsequently, it is conducted further characterization of RIPK1 in AD using [11C]CNY‐10‐based PET studies in combination with immunohistochemistry leveraging the 5xFAD mouse model. It is found that AD mice revealed RIPK1 brain signal significantly higher than WT control mice and that RIPK1 is closely related to amyloid plaques in the brain. The studies enable further translational studies of [11C]CNY‐10 for AD and potentially other RIPK1‐related human studies. [ABSTRACT FROM AUTHOR]

An efficient and broadly applicable rhodium‐catalyzed direct ortho‐arylation of anilines with aryl iodides relying on readily available aminophosphines as traceless directing groups is reported. Its scope and functional group compatibility were both found to be quite broad as a large variety of both aminophosphines and (hetero)aryl iodides, including complex ones, could be utilized. The ortho‐arylated anilines could be obtained in high average yields, without any competing diarylation and with full regioselectivity, which constitutes a major step forward compared to other processes. The reaction is moreover not limited to aryl iodides, as an aryl bromide and a triflate could be successfully used, and could be extended to diarylation. Mechanistic studies revealed the key and unique role of the aminophosphine, acting not only as a substrate but also as a ligand for the rhodium catalyst. [ABSTRACT FROM AUTHOR]

The characteristics of soil phosphorus (P) fixation and release have a critical impact on the availability of P and the risk of environmental loss. Investigation of the effects of corn stalk and corn stalk biochar on the P adsorption–desorption characteristics of brown earth can provide a theoretical basis for the rational return of crop stalk to the field and improving the availability of soil P. The Langmuir adsorption isotherm equation provided a better fit than the Freundlich equation for the curve of soil P adsorption and equilibrium solution P concentration. Biochar application increased the maximum adsorption capacity (MAC) and maximum buffer capacity (MBC) of the soil for P by 8.5% and 17.2%, respectively. Corn stalk and its biochar reduced the P adsorption saturation (DPS) by 41.8% and 31.9%, respectively, but increased the amount of readily desorbable P (RDP) by 39.7% and 154.4%, respectively. The application of corn stalk and its biochar improved the soil P desorption rate at substrate P concentrations of less than 5 mg L−1, whereas significant reductions in the soil P desorption rate were observed between 5 mg L−1 and 30 mg L−1, and no significant effects were observed at P concentrations over 40 mg L−1. In addition, the total P and Olsen‐P contents of the soil were significantly associated with the P adsorption–desorption process (p <.05). Therefore, corn stalk and corn stalk biochar can enhance the capacity of soil for P adsorption, with a stronger effect observed for biochar than for corn stalk, and the rate of P desorption from treated soil is dependent on P concentration in the soil solution. [ABSTRACT FROM AUTHOR]

Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles in the previous reports, however, has restrained their synthetic potential. Herein we disclose the ambiphilic reactivity of α‐halogenated geminal bis(boronates), of which the first catalytic utilization was accomplished by merging a formal Heck cross‐coupling with a highly diastereoselective allylboration of aldehydes or imines, providing a new avenue for rapid assembly of polyfunctionalized boron‐containing compounds. We demonstrated that this cascade reaction is highly efficient and compatible with various functional groups, and a wide range of heterocycles. In contrast to a classical Pd(0/II) scenario, mechanistic experiments and DFT calculations have provided strong evidence for a catalytic cycle involving Pd(I)/diboryl carbon radical intermediates. [ABSTRACT FROM AUTHOR]

Summary: Black wolfberry (Lycium ruthenicum Murr.) contains various bioactive metabolites represented by flavonoids, which are quite different among production regions. However, the underlying regulation mechanism of flavonoid biosynthesis governing the bioactivity of black wolfberry remains unclear.Presently, we compared the bioactivity of black wolfberry from five production regions. Multi‐omics were performed to construct the regulation network associated with the fruit bioactivity. The detailed regulation mechanisms were identified using genetic and molecular methods.Typically, Qinghai (QH) fruit exhibited higher antioxidant and anti‐inflammatory activities. The higher medicinal activity of QH fruit was closely associated with the accumulation of eight flavonoids, especially Kaempferol‐3‐O‐rutinoside (K3R) and Quercetin‐3‐O‐rutinoside (rutin). Flavonoid biosynthesis was found to be more active in QH fruit, and the upregulation of LrFLS, LrCHS, LrF3H and LrCYP75B1 caused the accumulation of K3R and rutin, leading to high medicinal bioactivities of black wolfberry. Importantly, transcription factor LrMYB94 was found to regulate LrFLS, LrCHS and LrF3H, while LrWRKY32 directly triggered LrCYP75B1 expression. Moreover, LrMYB94 interacted with LrWRKY32 to promote LrWRKY32‐regulated LrCYP75B1 expression and rutin synthesis in black wolfberry. Transgenic black wolfberry overexpressing LrMYB94/LrWRKY32 contained higher levels of K3R and rutin, and exhibited high medicinal bioactivities. Importantly, the LrMYB94/LrWRKY32‐regulated flavonoid biosynthesis was light‐responsive, showing the importance of light intensity for the medicinal quality of black wolfberry.Overall, our results elucidated the regulation mechanisms of K3R and rutin synthesis, providing the basis for the genetic breeding of high‐quality black wolfberry. [ABSTRACT FROM AUTHOR]

Background: Wrinkle formation is the most visible characteristic of facial aging. Radiofrequency (RF) technology is currently utilized to reduce facial wrinkles and contribute to skin rejuvenation. Objective: To analyze the efficacy and safety of a noninvasive, home‐based RF device applied for facial rejuvenation in Chinese people. Methods: A single‐center, open‐label, intraindividual controlled trial was performed on subjects who received an 8‐week treatment of the RF device. A total of 22 female individuals aged 25–60 years with Fitzpatrick skin type III–IV were enrolled. Efficacy of treatment was subjectively evaluated using the Fitzpatrick Wrinkle Classification Scale (FWCS) assessed by physician or overall satisfaction of subject with a 10‐point VAS, and objectively using the skin ultrasound examination as well as the 3D skin analysis system. Adverse event was recorded at each visit. Results: In comparison with the baseline, evaluator‐assessed FWCS scores showed significant improvement at 4 weeks (p < 0.005) and 8 weeks (p < 0.005) after treatment. All subjects reported different degrees of improvement in facial wrinkles after 8 weeks of treatment. The results of skin ultrasound examination revealed significant increase of the dermal thickness at week 8 (p < 0.05) as compared to the baseline. In addition, a significant decrease in the proportion and density of perioral wrinkles evaluated by the 3D skin analysis system was observed from baseline to week 4. The treatment was well‐tolerated, and no serious adverse event was observed. Conclusion: This noninvasive, home‐based RF device was effective in improving skin texture and elasticity with a safe and well‐tolerated treating procedure. [ABSTRACT FROM AUTHOR]

Ginseng (Panax ginseng Meyer) has long been consumed as a medicinal or functional food in East Asia. It is available as dried white ginseng (WG) and steamed red ginseng (RG), which might differ in ginsenoside profiles. We compared ginsenoside types of RG and WG using UPLC‐MS/MS and evaluated how they biologically affected heart of healthy rats by recording electrocardiography, measuring biochemical indicators, analyzing cardiac tissue slides, and Ca2+ signaling pathways. About 25 and 29 ginsenosides were detected in WG and RG, respectively, and the total ginsenoside content of RG contained was nearly 1.8 times higher than that of WG. Among them, ginsenoside Rg4, ginsenoside Rg6, ginsenoside Rh4, ginsenoside Rk1, ginsenoside Rg5, and protopanaxadiol were detected only in RG, while 20(R)‐ginsenoside Rg2 was detected only in WG. Male SD rats treated by intraperitoneal injection of WG or RG extracts were similar to the control in terms of electrocardiography and heart histology, indicating that both may not significantly affect the rats' myocardial function. However, WG and RG may induce mild cardiac injury resulting in increased cardiac collagen and creatine kinase levels. In addition, upregulated p‐CaMKII and PPARδ and downregulated SERCA2a for WG and RG treatments were further associated with increased cardiac contractility. In general, RG had less effect on the heart of healthy rats than WG, which may be due to RG having a high proportion of low‐polar ginsenosides. [ABSTRACT FROM AUTHOR]

Generalized pustular psoriasis (GPP) is considered to be a distinct clinical entity from psoriasis vulgaris (PV), with different clinical and histological manifestations. The pathogenesis of GPP has not been thoroughly elucidated, especially in those patients lacking interleukin (IL)36RN. In present study, we performed RNA sequence analysis on skin lesions from 10 GPP patients (4 with and 6 without IL36RN mutation) and 10 PV patients without IL36RN mutation. Compared with PV, significantly overexpressed genes in GPP patients were enriched in IL‐17 signalling pathway (MMP1, MMP3, DEFB4A and DEFB4B, etc.) and associated with neutrophil infiltration (MMP1, MMP3, ANXA and SERPINB, etc.). GPP with IL36RN mutations evidenced WNT11 upregulation and IL36RN downregulation in comparison to those GPP without IL36RN mutations. The expression of IL‐17A/IL‐36 in skin or serum and the origin of IL‐17A in skin were also investigated. IL‐17A expression in skin was significantly higher in GPP than PV patients, whereas, there were no differences in skin IL‐36α/IL‐36γ/IL‐36RA or serum IL‐17A/IL‐36α/IL‐36γ between GPP than PV. Besides, double immunofluorescence staining of MPO/IL‐17A or CD3/IL‐17A further confirmed that the majority of IL‐17A in GPP skin was derived from neutrophils, but not T cells. These data emphasized the role of neutrophil‐derived IL‐17A in the pathogenesis of GPP with or without IL36RN mutations. Targeting neutrophil‐derived IL‐17A might be a promising treatment for GPP. [ABSTRACT FROM AUTHOR]

Boronate rearrangements, such as the Matteson and Petasis reactions, are valuable metal‐free reactions for the transfer of the carbo group on boron to intramolecular electrophilic sites. However, only highly reactive electrophiles are suitable, and ketones are too inactive for those boronate rearrangements due to the high energy barriers. We disclose here the 1,3‐boronate rearrangement to ketones, for which a high energy barrier (44.9 kcal/mol) is prohibitory for thermal reactions in the ground state. The reaction is enabled by the key keto‐enol‐boronate bidentate complex formation in situ, which absorbs visible light to reach the excited state for the chemoselective 1,3‐boronate rearrangement to ketones. Experimental and computational investigations exclude free radical intermediates from organoboronates. The aryl, alkenyl, and alkyl boronic acids react with various 1,3‐diketones driven by visible light irradiation to construct structurally diverse β‐keto tertiary alcohols under metal‐free conditions. The reaction demonstrates substrate diversity with 58 examples, yields up to 98 %, and it is suitable for gram‐scale synthesis. [ABSTRACT FROM AUTHOR]

Dianhong Black Tea, a fermented tea containing various bioactive ingredients, has been found to have a significant role in alleviating alcoholic liver injury (ALI). One of its main unique components, Dianhong Black Tea volatile substances (DBTVS), may have potential anti‐ALI effects. However, its effects and underlying molecular mechanisms are still unknown. In this study, we aimed to investigate the potential of DBTVS as an anti‐ALI agent using alcohol‐fed rats. We assessed the effect of DBTVS on ALI by analyzing serum transaminase and lipid levels, as well as conducting hematoxylin–eosin and oil red O staining. Additionally, GC‐MS was used to detect the components of DBTVS, while transcriptome, proteomics analysis, Western blot, and molecular docking were employed to uncover the underlying mechanisms. Our results demonstrated that DBTVS significantly reduced serum ALT and AST levels and improved lipid metabolism disorders. Moreover, we identified 14 components in DBTVS, with five of them exhibiting strong binding affinity with key proteins. These findings suggested that DBTVS could be a promising agent for the prevention and treatment of ALI. Its potential therapeutic effects may be attributed to its ability to regulate lipid metabolism through the PPAR signaling pathway. [ABSTRACT FROM AUTHOR]

Cancer of the central nervous system (CNS) can crosstalk systemically and locally in the tumor microenvironment and has become a topic of attention for tumor initiation and advancement. Recently studied neuronal and cancer interaction fundamentally altered the knowledge about glioma and metastases, indicating how cancers invade complex neuronal networks. This review systematically discussed the interactions between neurons and cancers and elucidates new therapeutic avenues. We have overviewed the current understanding of direct or indirect communications of neuronal cells with cancer and the mechanisms associated with cancer invasion. Besides, tumor‐associated neuronal dysfunction and the influence of cancer therapies on the CNS are highlighted. Furthermore, interactions between peripheral nervous system and various cancers have also been discussed separately. Intriguingly and importantly, it cannot be ignored that exosomes could mediate the "wireless communications" between nervous system and cancer. Finally, promising future strategies targeting neuronal–brain tumor interactions were reviewed. A great deal of work remains to be done to elucidate the neuroscience of cancer, and future more research should be directed toward clarifying the precise mechanisms of cancer neuroscience, which hold enormous promise to improve outcomes for a wide range of malignancies. [ABSTRACT FROM AUTHOR]

Objective structured clinical examinations (OSCEs) have been widely used in health care education to simultaneously assess knowledge, skill and attitude. Due to the high cost of running an OSCE, its application in professional psychology is still limited. To solve this problem, virtual standardised patient (VSP) implementations in creating psychology OSCEs can be a cost‐effective method for administering a psychology OSCE regularly. This study aimed to develop and examine the psychometric properties of the VSP version of the Intake OSCE (VSP‐Intake OSCE) in measuring psychologists' psychological assessment competencies (PACs) from entry to early practice. The initial development of the VSP‐Intake OSCE contains a VSP station and a follow‐up written station to measure PACs when conducting an intake assessment. To administer the VSP station, we built a new VSP system that allows psychologists to interact with a VSP verbally. A sample of 36 participants, including 27 graduate students and nine psychologists, were recruited to examine the psychometric properties of the VSP‐Intake OSCE. As a newly developed instrument, the VSP‐Intake OSCE revealed good inter‐rater reliability and construct validity. We believe using VSP implementations to develop psychology OSCEs will be essential in promoting OSCE applications in professional psychology. [ABSTRACT FROM AUTHOR]

Carboxylation of easily available alkenes with CO2 is highly important to afford value‐added carboxylic acids. Although dicarboxylation of activated alkenes, especially 1,3‐dienes, has been widely investigated, the challenging dicarboxylation of unactivated 1,n‐dienes (n>3) with CO2 remains unexplored. Herein, we report the first dicarboxylation of unactivated skipped dienes with CO2 via electrochemistry, affording valuable dicarboxylic acids. Control experiments and DFT calculations support the single electron transfer (SET) reduction of CO2 to its radical anion, which is followed by sluggish radical addition to unactivated alkenes, SET reduction of unstabilized alkyl radicals to carbanions and nucleophilic attack on CO2 to give desired products. This reaction features mild reaction conditions, broad substrate scope, facile derivations of products and promising application in polymer chemistry. [ABSTRACT FROM AUTHOR]

Carboxylation of easily available alkenes with CO2 is highly important to afford value‐added carboxylic acids. Although dicarboxylation of activated alkenes, especially 1,3‐dienes, has been widely investigated, the challenging dicarboxylation of unactivated 1,n‐dienes (n>3) with CO2 remains unexplored. Herein, we report the first dicarboxylation of unactivated skipped dienes with CO2 via electrochemistry, affording valuable dicarboxylic acids. Control experiments and DFT calculations support the single electron transfer (SET) reduction of CO2 to its radical anion, which is followed by sluggish radical addition to unactivated alkenes, SET reduction of unstabilized alkyl radicals to carbanions and nucleophilic attack on CO2 to give desired products. This reaction features mild reaction conditions, broad substrate scope, facile derivations of products and promising application in polymer chemistry. [ABSTRACT FROM AUTHOR]

Bronchial specimens from patients with well-controlled asthma who had more intact airway epithelium were used for comparison with specimens from patients with severe asthma. Severe asthma: PP4 expression in the denuded epithelium of patients with severe asthma was very low. Loss of PP4 contributes to diesel exhaust particles-induced epithelial barrier integrity disruption and alarmins release. [Extracted from the article]

A large number of studies suggested that biochar can affect the adsorption of phosphorus (P) in soil and the distribution of P in soil aggregates, but it is still unclear whether biochar can indirectly affect the distribution of P in soil profiles through the influence of these two factors. Therefore, the ability of maize straw biochar to mitigate the risk of loss of P and improve the distribution of P in soil profile was evaluated by studying the capacity of soil to adsorb P from the soil and distribution fractions of it in diverse grain‐sized aggregates of soil. A 5‐year field trial site had received NPK fertilizer inputs at the same rate and one‐time biochar inputs at different rates (0, 15.75, 31.5 and 47.25 t ha−1) at the beginning of the experiment. Langmuir and Freundlich equations were fitted to the sorption data of the soil and suggested that the applicataion of biochar can promote P absorption capacity of soil, particularly when the rates of biochar applied were 31.5 and 47.25 t ha−1. Biochar can improve the stability of soil aggregates, and aggregates with particle sizes of 0.25–2 mm have the highest relative rate of contribution to various fractions of P in the soil. Biochar can promote the accumulation of most of the P fractions in soil aggregates, particularly when the rates of biochar applied were 31.5 and 47.25 t ha−1. The TP, Ca2‐P, Al‐P, Ca8‐P, moderately labile organic phosphorus (MLOP) and moderately resistant organic phosphorus (MROP) were primarily distributed in the 0–20 cm soil layer. Biochar increased the contents of MLOP and highly resistant organic phosphorus in the soil layer of 0–20 cm while reducing the contents of Al‐P, Fe‐P and occluded phosphorus (O‐P) in the soil layer of 0–20 cm and decreased the contents of TP, Ca8‐P, O‐P and MROP under the 20 cm soil layers. Biochar can change the distribution of P fractions along the soil profile by improving the adsorption of soil P and its distribution in the soil aggregates (0–20 cm). [ABSTRACT FROM AUTHOR]

In the aorta of mid‐gestational mouse embryos, a specialized endothelial subpopulation termed hemogenic endothelial cells (HECs) develops into hematopoietic stem and progenitor cells (HSPCs), through a conserved process of endothelial‐to‐hematopoietic transition (EHT). EHT is tightly controlled by multiple intrinsic and extrinsic mechanisms. Nevertheless, the molecular regulators restraining this process remain poorly understood. Here, it is uncovered that, one of the previously identified HEC signature genes, Nupr1, negatively regulates the EHT process. Nupr1 deletion in endothelial cells results in increased HSPC generation in the aorta‐gonad‐mesonephros region. Furthermore, single‐cell transcriptomics combined with serial functional assays reveals that loss of Nupr1 promotes the EHT process by promoting the specification of hematopoiesis‐primed functional HECs and strengthening their subsequent hematopoietic differentiation potential toward HSPCs. This study further finds that the proinflammatory cytokine, tumor necrosis factor α (TNF‐α), is significantly upregulated in Nupr1‐deficient HECs, and the use of a specific TNF‐α neutralizing antibody partially reduces excessive HSPC generation in the explant cultures from Nupr1‐deficient embryos. This study identifies a novel negative regulator of EHT and the findings indicate that Nupr1 is a new potential target for future hematopoietic stem cell regeneration research. [ABSTRACT FROM AUTHOR]

The draining of brain interstitial fluid (ISF) to cerebrospinal fluid (CSF) and the subsequent draining of CSF to meningeal lymphatics is well‐known. Nonetheless, its role in the development of glioma is a remarkable finding that has to be extensively understood. The glymphatic system (GS) collects CSF from the subarachnoid space and brain ISF through aquaporin‐4 (AQP4) water channels. The glial limiting membrane and the perivascular astrocyte‐end‐feet membrane both have elevated levels of AQP4. CSF is thought to drain through the nerve sheaths of the olfactory and other cranial nerves as well as spinal meningeal lymphatics via dorsal or basal lymphatic vessels. Meningeal lymphatic vessels (MLVs) exist below the skull in the dorsal and basal regions. In this view, MLVs offer a pathway to drain macromolecules and traffic immunological cells from the CNS into cervical lymph nodes (CLNs), and thus can be used as a candidate curing strategy against glioma and other associated complications, such as neuro‐inflammation. Taken together, the lymphatic drainage system could provide a route or approach for drug targeting of glioma and other neurological conditions. Nevertheless, its pathophysiological role in glioma remains elusive, which needs extensive research. The current review aims to explore the lymphatic drainage system, its role in glioma progression, and possible therapeutic techniques that target MLVs in the CNS. [ABSTRACT FROM AUTHOR]

The aldehydes installation by radical formylation constitutes an attractive synthetic strategy. However, the generation of formyl radicals for organic synthesis applications remains unknown. Herein we report the first formyl radical generation from α‐chloro N‐methoxyphthalimides, which selectively synthesize aldehydes by alkene hydroformylation under mild photoredox conditions. The aldehydes can be installed on acrylates, acrylamides, vinyl sulfones, vinyl ketones, and complex steroids by radical hydroformylation in excellent chemoselectivity and regioselectivity. The concerted hydrochloride elimination for the formyl radical generation from α‐chloro methoxy radicals is established by experimental and computational approaches. [ABSTRACT FROM AUTHOR]

Silanes are important in chemistry and material science. The self‐redistribution of HSiCl3 is an industrial process to prepare SiH4, which is widely used in electronics and automobile industries. However, selective silane cross‐redistribution to prepare advanced silanes is challenging. We now report an enthalpy‐driven silane cross‐redistribution to access bis‐silanes that contain two different types of Si−H bonds in the same molecule. Compared with entropy‐driven reactions, the enthalpy‐driven reaction shows high regioselectivity, broad substrate scope (62 examples) and high atom economy. Our combined experimental and computational study indicates that the reaction proceeds through a Ni0‐NiII‐NiIV catalytic cycle. [ABSTRACT FROM AUTHOR]

Silaspiranes have attracted particular attention due to their chiral spiro‐silicon center, which serves as an ideal carbon isostere and can endow spiro‐analogs with distinct properties. Distinct from previously reported cyclization or cycloaddition strategies to form 5/5‐silaspiranes, we report herein the asymmetric dual ring expansion of spirosilabicyclobutanes with alkynes to synthesize axially chiral spirosilabicyclohexenes bearing a novel 6/6‐silaspirane framework. DFT (density functional theory) calculations provide the deep insight into the origin of the high enantioselectivity controlled by the sterically demanding binaphthyl phosphoramidite ligand. Preliminary studies of chiroptical properties indicate that one of the spirosilabicyclohexene analogs exhibit fluorescence emission, Cotton effects and CPL (circularly polarized luminescence) activity. [ABSTRACT FROM AUTHOR]

Both aryne 1,4‐disubstitution and 1,2,4‐trifunctionalization were accomplished from tertiary amines bearing a penta‐2,4‐dien‐1‐yl moiety. These transformations could directly incorporate a C−N and a C−C bond para to each other on an aryne intermediate via a sequential nucleophilic addition and [5,5]‐sigmatropic rearrangement. When arynes bearing 3‐tethered electrophiles were employed, a cascade regioselective nucleophilic addition, intramolecular cyclization, and remote diastereoselective [5,5]‐sigmatropic rearrangement process was observed. Our density functional theory (DFT) calculations revealed that hydrogen‐bonding interactions between two C−H hydrogens on the penta‐2,4‐dien‐1‐yl chain and the oxygen anion generated upon N‐nucleophilic annulation reaction in the [5,5]‐sigmatropic rearrangement step is responsible for the remote diastereoselective control in this reaction system. [ABSTRACT FROM AUTHOR]

C‐Acyl glycosides are versatile intermediates to natural products and medicinally relevant entities. Conventional cross‐coupling strategies to secure these molecules often relied on two‐component manifolds in which a glycosyl precursor is coupled with an acyl donor (pre‐synthesized or generated in situ) under transition metal or dual catalysis to forge a C−C bond. Here, we disclose a three‐component Ni‐catalyzed reductive regime that facilitates the chemoselective union of glycosyl halides, organoiodides and commercially available isobutyl chloroformate as a CO surrogate. The method tolerates multiple functionalities and the resulting products are obtained in high diastereoselectivities. Theoretical calculations provide a mechanistic rationale for the unexpectedly high chemoselectivity of sequential cross‐electrophile couplings. This approach enables the expeditious assembly of difficult‐to‐synthesize C‐acyl glycosides, as well as late‐stage keto‐glycosylation of oligopeptides. [ABSTRACT FROM AUTHOR]

Objective: High‐risk papillary thyroid carcinoma (PTC) patients with BRAF mutation have lymph node and distant metastases and poor prognosis. Therefore, this study aims to develop a targeted ultrasound contrast agent for the BRAFV600E mutation to screen high‐risk PTC at early stage. Methods: The targeted lipid nanobubbles carrying BRAFV600E antibody were prepared using thin film hydration‐sonication and avidin‐biotin binding methods. The physicochemical properties and stability of the targeted nanobubbles were detected by transmission electron microscopy, atomic force microscopy, and confocal laser scanning microscopy. The target binding abilities of the targeted nanobubbles in the PTC cells (B‐CPAP) overexpressed mutant BRAFV600E were evaluated by immunofluorescence staining, quantitative real‐time polymerase chain reaction, western blot, and fluorescence microscopy. After PTC tumor models overexpressed mutant BRAFV600E were established, the enhanced images of targeted lipid nanobubbles and untargeted lipid nanobubbles on PTC tumors in nude mice were observed using contrast‐enhanced ultrasound imaging. Results: The targeted lipid nanobubbles revealed uniform, round morphology, and good stability with a nanoscale size. Besides, BRAFV600E monoclonal antibody was observed to be combined on the surface of lipid nanobubbles. Furthermore, the targeted nanobubbles had a good targeting diagnosis ability in PTC cells with BRAFV600E overexpression. Moreover, the targeted nanobubbles had better ultrasound enhancement and peak intensity of the time‐intensity curve (P <.001) in PTC tumors with BRAFV600E overexpression as compared to the untargeted lipid nanobubbles. Conclusion: The targeted lipid nanobubbles carrying BRAFV600E antibody could be regarded as a potential targeted ultrasound contrast agent for the diagnosis of high‐risk PTC. Access the CME test here and search by article title. [ABSTRACT FROM AUTHOR]

A catalytic 1,2‐oxyhalogenation method that converts non‐conjugated internal alkynes into tetrasubstituted alkenes with high regio‐ and stereoselectivity is described. Mechanistically, the reaction involves a PdII/PdIV catalytic cycle that begins with a directed oxypalladation step. The origin of regioselectivity is the preference for formation of a six‐membered palladacycle intermediate, which is facilitated by an N,N‐bidentate 2‐(pyridin‐2‐yl)isopropyl (PIP) amide directing group. Selectivity for C(alkenyl)−X versus −N (X=halide) reductive elimination from the PdIV center depends on the identity of the halide anion; bromide and iodide engage in C(alkenyl)−X formation, while intramolecular C(alkenyl)−N reductive elimination occurs with chloride to furnish a lactam product. DFT calculations shed light on the origins of this phenomenon. [ABSTRACT FROM AUTHOR]

With deep sequencing of virus genomes within the hosts, intrahost single nucleotide variations (iSNVs) have been used for analyses of virus genome variation and evolution, which is indicated to correlate with viral pathogenesis and disease severity. Little is known about the features of iSNVs among DNA viruses. We performed the epidemiological and laboratory investigation of one outbreak of adenovirus. The whole genomes of viruses in both original oral swabs and cell‐cultured virus isolates were deeply sequenced. We identified 737 iSNVs in the viral genomes sequenced from original samples and 46 viral iSNVs in cell‐cultured isolates, with 33 iSNVs shared by original samples and cultured isolates. Meanwhile, we found these 33 iSNVs were shared by different patients, among which, three hot spot areas 6367−6401, 9213−9247, and 10 584−10 606 within the functional genes of the adenovirus genome were found. Notably, the substitution rates of iSNVs were closely correlated with the clinical and immune indicators of the patients. Especially a positive correlation to neutrophils was found, indicating a predictable biomarker of iSNV dynamics. Our findings demonstrated the neutrophil‐correlated dynamic evolution features of the iSNVs within adenoviruses, which indicates a virus−host interaction during human infection of a DNA virus. [ABSTRACT FROM AUTHOR]

We herein demonstrated an efficient method for the atroposelective construction of nine‐membered carbonate‐bridged biaryls through vinylidene ortho‐quinone methide (VQM) intermediates. Diverse products with desirable pharmacological features were synthesized in satisfying yields and good to excellent enantioselectivities. In subsequent bioassays, several agents showed considerable antiproliferative activity via the mitochondrial‐related apoptosis mechanism. Further transformations produced more structural diversity and may inspire new ideas for developing functional molecules. [ABSTRACT FROM AUTHOR]

Catalytic asymmetric synthesis of chiral endocyclic allenes remains a challenge in allene chemistry owing to unfavored tension and complex chirality. Here, we present a new relay strategy merging Pd‐catalyzed asymmetric [3+2] annulation with enyne‐Cope rearrangement, providing a facile route to chiral 9‐membered endocyclic allenes with high efficiency and enantioselectivity. Moreover, theoretical calculations and experimental studies were performed to illustrate the critical, but unusual Cope rearrangement that allows for the complete central‐to‐axial chirality transfer. [ABSTRACT FROM AUTHOR]

We report herein a highly efficient palladium‐catalyzed carbene insertion into strained Si−C bonds of benzosilacyclobutanes, which provides an efficient method to access α‐chiral silanes. With a sterically hindered ligand, carbene insertion into the C(sp3)−Si bond of benzosilacyclobutanes occurred in excellent site‐ and enantioselectivity, while C(sp2)−Si bond insertion occurred selectively with less sterically hindered ligands. Reaction mechanism, in particular the roles of the chiral ligands in controlling the site‐selectivity of the insertion reactions, are elucidated by using hybrid density functional theory. [ABSTRACT FROM AUTHOR]

The stannum–ene reactions of both benzyne and cyclohexyne were realized, which is particularly suitable for cyclohexyne with a broad substrate scope and excellent chemoselectivity. Our DFT calculations via distortion/interaction analysis revealed that both stannum– and hydrogen–ene reactions with cyclohexyne have later transition states due to their higher distortion energies in the transition states than those in benzyne reactions, which lead to enhanced Pauli repulsion as the decisive factor in the interaction energy accompanied with enlarged energy gap between two types of ene reactions. Therefore, excellent chemoselectivity was disclosed in the cyclohexyne–ene reaction. [ABSTRACT FROM AUTHOR]

Considering the ubiquitous nature and ready synthesis of amides, and the great significance of organofluorine‐containing species, the cross‐coupling of amides and polyfluoroarenes, leading to new carbon–carbon bond‐forming methodologies, would find useful applications in synthesis, late‐stage functionalization, and rapid generation of molecular diversity. Herein, we present a novel synthesis of α‐polyfluoroaryl amines via Sm/SmI2‐mediated deoxygenative cross‐coupling of aromatic amides with polyfluoroarenes through direct C−H functionalization. The structural and functional diversity of these readily available precursors provides a versatile and flexible strategy for the streamlined synthesis of α‐polyfluoroaryl amines. Combining experimental and theoretical studies, a novel plausible mechanism of the α‐aminocarbene‐mediated C−H insertion has been revealed, which may stimulate future work for the development of novel methods in amine synthesis. [ABSTRACT FROM AUTHOR]

We present herein our experimental and DFT computational studies on the directing ability of chalcogenoether motifs in Pd‐catalyzed atroposelective C−H functionalization. The thioether motif was found to be a superior directing group compared to the corresponding ether and selenoether in terms of reactivity and enantiocontrol. Remarkably, DFT calculation provided a predictive model for the optimization of reaction conditions and the interpretation of the origin of enantioselectivity. Both Pd‐catalyzed enantioselective C−H olefination and allylation reactions were successfully developed using chiral phosphoric acids as efficient ligands, providing a broad range of axially chiral biaryls in good yields with excellent enantioselectivities. The highly enantio‐ and diastereoselective construction of polyaryls bearing multiple stereogenic axes, gram‐scale reaction and various chemical transformations make this protocol more attractive and significant. [ABSTRACT FROM AUTHOR]

Computations and experiments leading to new chiral phosphoric acids (CPAs) for epoxide thionations are reported. Density functional theory calculations reveal the mechanism and origin of the enantioselectivity of such CPA‐catalyzed epoxide thionations. The calculated mechanistic information was used to design new efficient CPAs that were tested experimentally and found to be highly effective. Bulky ortho‐substituents on the 3,3′‐aryl groups of the CPA are important to restrict the position of the epoxide in the key transition states for the enantioselectivity‐determining step. Larger para‐substituents significantly improve the enantioselectivity of the reaction. [ABSTRACT FROM AUTHOR]

Acute kidney injury (AKI) induced by renal ischemia reperfusion (RIR) is typically observed in renal surgeries and is a leading cause of renal failure. However, there is still an unmet medical need currently in terms of clinical treatments. Herein, we report the effect of Urolithin A (UA) in a mouse RIR model, wherein we demonstrated its underlying mechanism both in vitro and in vivo. The expression levels of p62 and Keap1 significantly decreased, while that of nuclear Nrf2 increased in vitro in a hypoxia cell model after UA treatment. Furthermore, the apoptosis of tubular cells was attenuated and the reactive oxygen species (ROS) levels were reduced in the kidneys in a mouse RIR model after UA administration. In this study, we demonstrated that UA can alleviate oxidative stress and promote autophagy by activating the p62-Keap1-Nrf2 signaling pathway, which could protect the kidneys from ischemia reperfusion injury. [ABSTRACT FROM AUTHOR]

Axially chiral open‐chain olefins represent an underexplored class of chiral platform. In this report, two classes of tetrasubstituted axially chiral acyclic olefins have been accessed in excellent enantioselectivity and regioselectivity via C−H activation of (hetero)arenes assisted by a migratable directing group en route to coupling with sterically hindered alkynes. The coupling of indoles bearing an N‐aminocarbonyl directing group afforded C–N axially chiral acrylamides with the assistance of a racemic zinc carboxylate additive. DFT studies suggest a β‐nitrogen elimination–reinsertion pathway for the directing group migration. Meanwhile, the employment of N‐phenoxycarboxamide delivered C−C axially chiral enamides via migration of the oxidizing directing group. Experiments suggest that in both cases the (hetero)arene substrate adopts a well‐defined orientation during the C−H activation, which in turn determines the disposition of the alkyne in migratory insertion. Synthetic applications of representative chiral olefins are demonstrated. [ABSTRACT FROM AUTHOR]

Characterization of functional T cell clusters is key to developing strategies for immunotherapy and predicting clinical responses in leukemia. Here, single‐cell RNA sequencing is performed with T cells sorted from the peripheral blood of healthy individuals and patients with B cell‐acute lymphoblastic leukemia (B‐ALL). Unbiased bioinformatics analysis enabled the authors to identify 13 T cell clusters in the patients based on their molecular properties. All 11 major T cell subsets in healthy individuals are found in the patients with B‐ALL, with the counterparts in the patients universally showing more activated characteristics. Two exhausted T cell populations, characterized by up‐regulation of TIGIT, PDCD1, HLADRA, LAG3, and CTLA4 are specifically discovered in B‐ALL patients. Of note, these exhausted T cells possess remarkable heterogeneity, and ten sub‐clusters are further identified, which are characterized by different cell cycle phases, naïve states, and GNLY (coding granulysin) expression. Coupled with single‐cell T cell receptor repertoire profiling, diverse originations of the exhausted T cells in B‐ALL are suggested, and clonally expanded exhausted T cells are likely to originate from CD8+ effector memory/terminal effector cells. Together, these data provide for the first‐time valuable insights for understanding exhausted T cell populations in leukemia. [ABSTRACT FROM AUTHOR]

An abnormal urine composition is a key reason for kidney stone formation, but little is known about the roles of small metabolites in the urine during kidney stone formation. Here, we found urine glycine in patients with kidney calcium oxalate (CaOx) stone was significantly lower than that in healthy people via 1H NMR spectra detection, and investigated the role and underlying mechanism of glycine in the regulation of CaOx stone formation. Our results showed that glycine could significantly attenuate ethylene glycol‐induced CaOx crystal depositions in rat kidney via decreasing urine oxalate and increasing urine citrate. Mechanism studies revealed that glycine could decrease urine oxalate through downregulating Slc26a6 expression, whereas increase urine citrate via inhibiting Nadc1 expression. Moreover, glycine decreased the protein expression of both Slc26a6 and Nadc1 via increasing the expression of miRNA‐411‐3p, which directly bound to the 3′‐untranslated regions of Slc26a6 and Nadc1 messenger RNAs, in vitro and in vivo. Together, our results revealed a novel role of glycine in the regulation of kidney CaOx crystal formation and provided a potential target for the treatment of kidney CaOx stone. [ABSTRACT FROM AUTHOR]

Return of crop straw and its biochar to the agricultural field decreases pressure on phosphorus (P) resources and reduces leaching and P runoff. We conducted a 5‐year field trial from 2013 to 2017 to study the capability of maize straw and its biochar to retain soil P, which was quantified by investigating the distribution of P fractions in the soil profile (0–100 cm) and soil aggregates of different grain sizes. The impact of soil treatments with nitrogen‐phosphorus‐potassium (NPK) fertiliser alone or combined with biochar or maize straw were examined. We found that maize straw and its biochar increased soil aggregate stability, which showed an increase in mean weight diameter, geometric mean diameter, and aggregates with diameter > 250 μm. Maize straw and its biochar promoted both inorganic (dicalcium phosphate dehydrate [Ca2‐P], octocalcium phosphate [Ca8‐P], aluminium phosphate [Al‐P], iron phosphate [Fe‐P], hydroxyapatite [Ca10‐P], and occluded phosphate [O‐P]) and organic (labile organic phosphorus, LOP, and moderately labile organic phosphorus, MLOP) P accumulation and stabilization in soil aggregates, especially in small macroaggregates of 250–2000 μm. Total phosphorus (TP), Ca8‐P, Fe‐P, LOP, MLOP, moderately resistant organic phosphorus (MROP) and highly resistant organic phosphorus (HROP) were enhanced by maize straw and its biochar, whereas Ca2‐P and O‐P were decreased in the 0–20‐cm topsoil. We measured decreased TP, Fe‐P, O‐P and Ca10‐P in the 40–100‐cm soil layer following maize straw and biochar deposition, whereas higher Ca2‐P, Al‐P, MROP and HROP were obtained in maize straw‐supplemented soil relative to NPK fertiliser treatment in the 20–100‐cm soil layer. Thus, maize straw and its biochar can be used to effectively improve soil structure to support P retention and biochar has the potential to reduce P leaching from the soil profile. Highlights: Maize straw and its biochar effectively improved soil structure to support P retentionInorganic and organic P fractions mainly accumulated in the small macroaggregate fractionBiochar has the potential to reduce P leaching in the soil profile [ABSTRACT FROM AUTHOR]

The cover image is based on the Original Article Ginseng in white and red processed forms: Ginsenosides and cardiac side effects by Jiexin Zhou et al., https://doi.org/10.1002/fsn3.3879.By Jiexin Zhou; Jiarui Zhang; Pu Jing; Yu Lan; Xiaonian Cao; Huafang Feng; Xiaogang Liu and Qingqing LiuReported by Author; Author; Author; Author; Author; Author; Author; Author [Extracted from the article]

Reported herein is the rhodium(III)‐catalyzed C−H activation of anilines bearing an N‐isoquinolyl directing group for oxidative [3+2] annulation with four classes of internal alkynes, leading to atroposelective indole synthesis via dynamic kinetic annulation with C‐N reductive elimination constituting the stereo‐determining step. This reaction proceeds under mild conditions with high regio‐ and enantioselectivity and functional group compatibility. [ABSTRACT FROM AUTHOR]

Background: Previous studies showed that mice lacking Fgf18 function had cleft palate defects and that the FGF18 locus was associated with cleft lip and palate in humans, but what specific roles Fgf18 plays during palatogenesis are unclear. Results: We show that Fgf18 exhibits regionally restricted expression in developing palatal shelves, mandible, and tongue, during palatal outgrowth and fusion in mouse embryos. Tissue‐specific inactivation of Fgf18 throughout neural crest‐derived craniofacial mesenchyme caused shortened mandible and reduction in ossification of the frontal, nasal, and anterior cranial base skeletal elements in Fgf18c/c;Wnt1‐Cre mutant mice. About 64% of Fgf18c/c;Wnt1‐Cre mice exhibited cleft palate. Whereas palatal shelf elevation was impaired in many Fgf18c/c;Wnt1‐Cre embryos, no significant difference in palatal cell proliferation was detected between Fgf18c/c;Wnt1‐Cre embryos and their control littermates. Embryonic maxillary explants from Fgf18c/c;Wnt1‐Cre embryos showed successful palatal shelf elevation and fusion in organ culture similar to the maxillary explants from control embryos. Furthermore, tissue‐specific inactivation of Fgf18 in the early palatal mesenchyme did not cause cleft palate. Conclusion: These results demonstrate a critical role for Fgf18 expression in the neural crest‐derived mesenchyme for the development of the mandible and multiple craniofacial bones but Fgf18 expression in the palatal mesenchyme is dispensable for palatogenesis. Key Findings: The Fgf18 gene exhibits tissue‐ and domain‐specific expression during development of the mandible, tongue, and palate. Mice with neural crestspecific inactivation of Fgf18 exhibited complete penetrance of micrognathia but only 64% showed cleft palate. Maxillary explant culture assays suggested that the cleft palate defect in the neural crest‐specific Fgf18 mutant mice was secondary to other craniofacial defects. Furthermore, tissue‐specific inactivation of Fgf18 in the early developing palatal mesenchyme did not cause cleft palate. Results from this study identify multiple roles of Fgf18 in regulating craniofacial development and demonstrate that Fgf18 expression in the palatal mesenchyme is dispensable for palatogenesis. [ABSTRACT FROM AUTHOR]

Objective: Ultrasonography‐guided radiofrequency ablation (RFA) has been used to treat low‐risk small papillary thyroid carcinoma (PTC) and yielded promising results. However, little research has been conducted on the application of RFA for the management of T1bN0M0 PTC. Therefore, this study was to compare the midterm outcome of RFA with that of surgery for the treatment of clinical solitary T1bN0M0 PTC. Design: This is a retrospective study. Patients: In total, 182 patients with solitary T1bN0M0 PTC between April 2014 and May 2019 were treated with RFA or surgery (n = 91/group). Measurements: The primary end points were local tumour progression and complication rates. Local tumour progression were defined as: (a) new or persistent PTC confirmed by core needle biopsy; (b) cervical lymph node metastasis (LNM) confirmed by core needle biopsy or surgery; (c) ablation zone increased in the RFA group. Results: In the RFA group, local tumour progression was seen in four patients (4.4%, three persistent PTC and one LNM). In the surgery group, two patients (2.2%) developed LNM; no new or persistent PTC was confirmed. There was no significant difference between the two groups in local tumour progression. Permanent hypoparathyroidism was observed in four patients (4.4%) in the surgery group, while no major or minor complications were observed in the RFA group. Conclusions: Ultrasonography‐guided RFA is feasible and safe for treating solitary T1bN0M0 PTC, so it may be considered an alternative to surgery in select patients, especially those who are ineligible for or refusal of surgery. [ABSTRACT FROM AUTHOR]

Objective: Papillary thyroid microcarcinoma (PTMC) has a good prognosis and a long survival time, surgery is the common treatment including total thyroidectomy (TT) and unilateral lobectomy (LT), but recent studies showed that TT does not show an advantage over LT for PTMC in preventing cancer recurrence and reducing mortality. Given this, the health‐related quality of life (HRQoL) has become one of the important factors that physicians must consider when making treatment decisions. The aim of this study was to compare the HRQoL of patients between undergoing TT and LT. Methods: From October 2019 to December 2019, 69 PTMC patients were enrolled in our study, including 34 in the LT group and 35 in the TT group, respectively. We used three questionnaires which included the 36‐item short‐form health survey (SF‐36), thyroid cancer‐specific quality of life (THYCA‐QOL), and Fear of Progression Questionnaire‐Short Form (FoP‐Q‐SF) for each patient to evaluate their scores of HRQoL. Results: According to the SF‐36, the scores of the domain for the role limitation due to physical problems, emotional problems, and social function (RP, RE, and SF) as well as Physical Component Summary (PCS) and Mental Component Summary (MCS) showed a significant negative linear association between the LT group and TT group: RP (coefficient [coef]: −33.953 [confidence interval (CI) −51.187 to −16.720], p < 0.001, RE (coef: −21.633 [CI −39.500 to −3.766], p = 0.018), SF (coef: −10.169 [CI −19.586 to −0.752], p = 0.035)and PCS (coef: −10.571 [CI −17.768 to −3.373], p = 0.005), MCS (coef: −10.694 [CI −19.465 to −1.923], p = 0.018). The THYCA‐QOL showed that the scores of the TT group were higher than that of the LT group in the problem of scar (coef: 16.245 [CI 1.697 to 30.794], p = 0.029 according to the multivariate analysis), suggesting a higher level of complaint in the TT group. There was no statistically significant difference in the scores of FoP‐Q‐SF between the two groups. Conclusions: In patients with PTMC, LT offers an advantage over TT in terms of HRQoL, which supports the role of LT as an alternative strategy to TT. [ABSTRACT FROM AUTHOR]

The density functional theory (DFT) calculations were performed to gain insights into possible reaction mechanisms and origin of selectivities on phosphine catalyzed [2+3] and [2+4] annulations of saturated amine with allenoate for the first time. The computed results reveal that allenoate prefers to serve as a C3 synthon rather than C4 synthon under phosphine catalysis, and the whole catalytic cycle generally undergoes through eight processes, i. e. (1) adsorption of catalyst, (2) dissociation of AcO− group, (3) deprotonation of saturated amine, (4) nucleophilic attack by the deprotonated amine anion to the electrophilic phosphonium diene intermediate, (5) [1,6]‐proton shift, (6) ring closure of five‐membered heterocycle, (7) [1,2]‐proton shift, and (8) desorption of catalyst and the formation of 3‐pyrroline. The fourth step was identified as both chemo‐ and stereo‐selectivities determining step, and the pathway associated with R‐isomer is energetically favorable pathway. Further non‐covalent interaction (NCI) and Bader's atoms‐in‐molecules (AIM) analysis reveal that the C−H⋅⋅⋅O interaction has a significant contribution to the stability of R‐configured transition state. The obtained insights should be valuable for understanding the general principle for the detailed mechanism and predicting the origin of the chemo‐ and stereo‐selectivities on the phosphine catalyzed [2+3] and [2+4] annulations of saturated amine with allenoate. [ABSTRACT FROM AUTHOR]

The non‐noble metal‐catalyzed asymmetric hydrogenation of N‐heteroaromatics, quinolines, is reported. A new chiral pincer manganese catalyst showed outstanding catalytic activity in the asymmetric hydrogenation of quinolines, affording high yields and enantioselectivities (up to 97 % ee). A turnover number of 3840 was reached at a low catalyst loading (S/C=4000), which is competitive with the activity of most effective noble metal catalysts for this reaction. The precise regulation of the enantioselectivity were ensured by a π–π interaction. [ABSTRACT FROM AUTHOR]

Versatile wood cellulose, the most prototypical abundant polymer on earth, is considered a promising natural material for the fabrication of biodegradable electronics. The development of biodegradable electronics may help alleviate the adverse environmental impact caused by the fast‐growing electronic waste (e‐waste). The focus of this review is to discuss recent major advances in biodegradable electronics with versatile wood cellulose in terms of supporting substrates and functional components. First, the biological biodegradation and structural hierarchy of versatile wood cellulose is briefly introduced, followed by highlighting three types of cellulose substrates (opaque and hazy cellulose paper, transparent and clear cellulose film, and transparent and hazy cellulose film) for biodegradable electronics. Then, recent progress and research achievements in the use of versatile wood cellulose with multiscale dimensions in biodegradable electronics as a functional component (e.g., advanced light management layer, high capacitance dielectric, and ionic conductor) or even smart materials (e.g., mechanochromic layer, humidity sensing layer, adaptable adhesive layer, and piezoelectric component) are summarized in detail. Finally, an overview of challenges and perspectives for biodegradable electronics with versatile cellulose is provided. [ABSTRACT FROM AUTHOR]

Divergent synthesis for precise constructions of cyclic unsymmetrical diaryl disulfides or diselenides and polythiophenes from CF3‐containing 1,3‐enynes and S8 was developed when the ortho group is F, Cl, Br, and NO2 on aromatic rings. Meanwhile, disulfides (diselenides) were also quickly constructed when the ortho group is H. These transformations undergo cascade thiophene construction/selective C3‐position thiolation process, featuring simple operations, divergent synthesis, broad substrate scope, readily available starting materials, and valuable products. A novel plausible radical annulation process was proposed and validated by DFT calculations for the first time. A series of derivatizations about the thiophene (TBT) and disulfides were also well‐represented. [ABSTRACT FROM AUTHOR]