查看更多>>摘要：Next-generation electronics that are fused into the human body can play a key role in future intelligent communication,smart healthcare,and human en-hancement applications.As a promising energy sup-ply component for smart biointegrated electronics,environment-adaptive electrochemical energy stor-age(EES)devices with complementary adaptability and functions have garnered huge interest in the past decade.Owing to the advancements in autonomous chemistry,which regulate the constitutional dynamic networks in materials,EES devices have witnessed higher freedom of autonomous adaptability in terms of mechano-adaptable,biocompatibility,and stimuli-response properties for biointegrated and smart applications.In this mini-review,we summarize the recent progress in emerging environment-adaptive EES devices enabled by the constitutional dynamic network of mechanical adaptable materials,biocompatible materials,and stimuli-responsive supramolecular polymer materials.Finally,the chal-lenges and perspectives of autonomous chemistry on the environment-adaptive EES devices are dis-cussed.
查看更多>>摘要：Mild and direct conversion of methane into high value-added products is a desired goal for chemistry,energy,and environment.The active species gener-ated in the photocatalytic reaction system under mild conditions activate the inert C-H bond in meth-ane and promote methane conversion.This review focuses on the developed mechanisms for C(sp3)-H bond activation in photocatalytic methane conver-sion,including radical and active site mechanisms.Particular emphasis is placed on the detailed sum-mary of mechanism,characterization method,and corresponding application in photocatalytic meth-ane conversion.We also discuss the challenges and prospects for future direction on C(sp3)-H bond activation mechanism in photocatalytic methane conversion.This review aims to promote the devel-opment of photocatalytic methane conversion and provides guidance for the design of high-efficiency photocatalysts.
查看更多>>摘要：Chemistry on solid surfaces is central to many re-search areas of practical interest,such as synthesis,catalysis,electrochemistry,photochemistry,and materials science.A comprehensive understanding of the nanoscale on-surface chemistry involved in these areas is important for establishing composi-tion-structure-performance relationships.With the rapid development of tip-enhanced Raman spectros-copy(TERS),it has become possible to investigate physical and chemical processes on suitable surfaces at the nanoscale level and in real space.In this review,after a brief introduction of the background of on-surface chemistry and TERS,we systematically dis-cuss the progress in the application of TERS in this field.Our focus is the applications of TERS to nano-scale coordination processes,decomposition reac-tions,polymerization processes,electrochemical reactions,catalytic chemistry,and functionalization chemistry on solid surfaces.We conclude by discuss-ing the future challenges and development of TERS techniques and related applications in on-surface chemistry.
查看更多>>摘要：After years of development,graphdiyne(GDY)has demonstrated the characteristics of transformative materials in many fields and has promoted great progress in fundamental and applied research.In practice,some important new concepts have been proposed,such as natural surface charge distribution inhomogeneity,multicavity space limiting effect,in-complete charge transfer effect on the atomic level,alkyne-alkene conversion of a chemical bond,in situ induction of constrained growth,reversible transition from high to low valence state,and so on.These characteristics originating from the special electron-ic structure and chemical structure of GDY have rapidly promoted the development of GDY science in recent years and produced many exciting results in fundamental and applied science.Therefore,we sys-tematically introduce the recent theoretical and ex-perimental progress of GDY in terms of its new structural,electronic,mechanical,thermal,and opti-cal properties and its promising applications in the energy fields of membrane sciences,catalysis,ener-gy storage,and conversion.Specifically,the great breakthrough of GDY zero-valence atomic catalysts,quantum dots catalysts,and heterostructure cata-lysts for catalytic applications are discussed in detail.We believe this review will provide some significant guidelines for the design and development of GDY-based high-performance materials and devices in energy fields.
查看更多>>摘要：Hard materials typically lack the mechanism of ener-gy dissipation and cannot self-heal.Nature addresses this challenge by creating multiscale interfaces be-tween high-contrast materials,namely minerals and biopolymers.Inspired by the enamel-dentin junction in nature,an enamel-like crown consisting of β-FeOOH nanocolumns is interdigitated with a flexible self-healing layer.The iron oxide top layer has excep-tionally high modulus and hardness,which is more resistant to cyclic deformation than the bottom layer.The latter however provides an additional pathway for viscous and plastic energy dissipation and enables self-healing by allowing upward polymer diffusion to seal the damage.Picture-frame crack patterns were observed under large loading condi-tions using microindentation,which localizes the damage at the indentation site.The bending proper-ties can be optimized by varying the thickness of the bottom layer,and the crack induced by bending can be effectively captured at the interface without any delamination.The biomimetic tooth replicate is high-ly adhesive to a ceramic surface and shows an obvi-ous inhibition effect against Streptococcus mutans,a significant contributor to tooth decay.Combined with ultralow thermal diffusivity,this has great po-tential as dental material.Learning from nature,our work thus provides a powerful pathway to broaden-ing the scope of synthetic materials for dental repli-cates.
查看更多>>摘要：C-Glycosides are important carbohydrate mimetics found in natural products,bioactive compounds,and marketed drugs.However,stereoselective preparation of this class of glycomimetics remains a significant challenge in organic synthesis.Herein,we report an excited-state palladium-catalyzed α-selective C-ketonylation synthetic strategy using readily avail-able 1-bromosugars to access a range of C-glycosides.The reaction featured excellent α-selectivity and mild conditions that tolerated a wide range of functional groups and complex molecular architectures.The resulting α-ketonylsugars could serve as versatile pre-cursors for their β-isomers and other C-glycosides.Preliminary experimental and computational studies of the mechanism suggested a radical pathway involv-ing the formation of palladoradical and glycosyl radi-cal that undergoes polarity-mismatched coupling with silyl enol ether,affording the desired α-ketonylsugars.Insight into the reactivity and mechanism will inspire a new reaction development and provide straightfor-ward access to both α-and β-C-glycosides,thereby greatly expanding the chemical and patent spaces of glycomimetics.
查看更多>>摘要：Recent years have witnessed breakthroughs in the study of zigzag hydrocarbon belts.However,the syn-thesis of heterocycle-containing zigzag molecular belts remains very rare and challenging despite their interesting structures and potential applications in chemistry and materials science.Here,we report the expeditious construction of a highly strained belt[4]arene[4](1,4-dihydropyridine)structure using the fjords-stitching strategy.The synthesis comprised four-fold abnormal m-bromination of four N-pivaloylaniline units and Pd2(dba)3/4-Me2NC6H4 PtBu2-catalyzed intramolecular C-N bond-forming reactions.Subsequent functionalization through N-arylations produced a variety of tetraza-embedded octahydrobelt[8]arenes.Further oxidation ofp-meth-oxy phenyl-substituted belt[4]arene[4](1,4-dihydro-pyridine)with Ag[AI(OtBuF)4]yielded a singlet diradical dication N-doped zigzag belt.
查看更多>>摘要：Myrtoidine and malagashanine,highly complex in-dole alkaloids,are effective adjuvants in developing cures for plasmodium malaria and potent multi-drug resistant agents.Despite nearly 30 years of prog-ress,myrtoidine and the related family of Malagasy alkaloids still present formidable challenges for syn-thetic chemists.Here,we developed a diastereose-lective[2+2+2]tandem cyclization reaction with alkyl-substituted methylene malonate,enabling highly efficient collective total synthesis of four Mal-agasy alkaloids from commercially available trypta-mines within 10-13 steps.The synthetic strategy included rapid and highly stereoselective assembly of the tetracyclic indoline core containing 5-7 con-tiguous stereogenic carbon centers,rarely seen in indole alkaloids.Among the four natural products,(±)-myrtoidine,(±)-11-demethoxymyrtoidine,and(±)-12-hydroxymalagashanine were synthesized for the first time,and the work on(±)-malagashanine represented the shortest synthetic route so far.Our current study should enable further explorations of chemical and biological spaces based on myrtoidine,malagashanine,and related natural products.
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