Hyperbranched Hybridization Chain Reaction for Triggered Signal Amplification and Concatenated Logic Circuits

A hyper‐branched hybridization chain reaction (HB‐HCR) is presented herein, which consists of only six species that can metastably coexist until the introduction of an initiator DNA to trigger a cascade of hybridization events, leading to the self‐sustained assembly of hyper‐branched and nicked double‐stranded DNA structures. The system can readily achieve ultrasensitive detection of target DNA. Moreover, the HB‐HCR principle is successfully applied to construct three‐input concatenated logic circuits with excellent specificity and extended to design a security‐mimicking keypad lock system. Significantly, the HB‐HCR‐based keypad lock can alarm immediately if the “password” is incorrect. Overall, the proposed HB‐HCR with high amplification efficiency is simple, homogeneous, fast, robust, and low‐cost, and holds great promise in the development of biosensing, in the programmable assembly of DNA architectures, and in molecular logic operations.     

Aryne‐Induced Novel Tandem 1,2‐Addition/(3+2) Cycloaddition to Generate Imidazolidines and Pyrrolidines

A new “single‐flask” method was developed for the synthesis of imidazolidines and pyrrolidines with high stereoselectivity. First, a Schiff base was arylated with an aryne. Second, an intramolecular proton transfer took place from the methylene position to the anionic aryne ring. Third, the resultant ylide reacted with a second equivalent of the same Schiff base in situ or an electron‐deficient alkene through a (3+2) cycloaddition. These sequential tandem 1,2‐addition/(3+2) cycloaddition reactions led to the desired heterocycles in 63–88 % yields.     

Clicked Isoreticular Metal–Organic Frameworks and Their High Performance in the Selective Capture and Separation of Large Organic Molecules

Three highly porous metal–organic frameworks (MOFs) with a uniform rht‐type topological network but hierarchical pores were successfully constructed by the assembly of triazole‐containing dendritic hexacarboxylate ligands with Zn^II ions. These transparent MOF crystals present gradually increasing pore sizes upon extension of the length of the organic backbone, as clearly identified by structural analysis and gas‐adsorption experiments. The inherent accessibility of the pores to large molecules endows these materials with unique properties for the uptake of large guest molecules. The visible selective adsorption of dye molecules makes these MOFs highly promising porous materials for pore‐size‐dependent large‐molecule capture and separation.     

Photocatalytically Renewable Micro‐electrochemical Sensor for Real‐Time Monitoring of Cells

Electrode fouling and passivation is a substantial and inevitable limitation in electrochemical biosensing, and it is a great challenge to efficiently remove the contaminant without changing the surface structure and electrochemical performance. Herein, we propose a versatile and efficient strategy based on photocatalytic cleaning to construct renewable electrochemical sensors for cell analysis. This kind of sensor was fabricated by controllable assembly of reduced graphene oxide (RGO) and TiO₂ to form a sandwiching RGO@TiO₂ structure, followed by deposition of Au nanoparticles (NPs) onto the RGO shell. The Au NPs‐RGO composite shell provides high electrochemical performance. Meanwhile, the encapsulated TiO₂ ensures an excellent photocatalytic cleaning property. Application of this renewable microsensor for detection of nitric oxide (NO) release from cells demonstrates the great potential of this strategy in electrode regeneration and biosensing.     

Theoretical Studies of the Reactions CFxH3−xCOOR+Cl and CF3COOCH3+OH

The mechanism and kinetics of the reactions of CF₃COOCH₂CH₃, CF₂HCOOCH₃, and CF₃COOCH₃ with Cl and OH radicals are studied using the B3LYP, MP2, BHandHLYP, and M06‐2X methods with the 6‐311G(d,p) basis set. The study is further refined by using the CCSD(T) and QCISD(T)/6‐311++G(d,p) methods. Seven hydrogen‐abstraction channels are found. All the rate constants, computed by a dual‐level direct method with a small‐curvature tunneling correction, are in good agreement with the experimental data. The tunneling effect is found to be important for the calculated rate constants in the low‐temperature range. For the reaction of CF₃COOCH₂CH₃+Cl, H‐abstraction from the CH₂ group is found to be the dominant reaction channel. The standard enthalpies of formation for the species are also calculated. The Arrhenius expressions are fitted within 200–1000 K as k_T(1)=8.4×10^?20T ^2.63exp(381.28/T), k_T(2)=2.95×10^?21T ^3.13exp(?103.21/T), k_T(3)=1.25×10^?23T ^3.37exp(791.98/T), and k_T(4)=4.53×10^?22T ^3.07exp(465.00/T).     

Direct Determination of Trace Dopamine in an Ascorbic Acid Solution at a Bare Glassy Carbon Electrode Using Differential Pulse Voltammetry

It is difficult to monitor dopamine (DA) accurately with a bare glassy carbon electrode because of the interference of ascorbic acid (AA). In this paper, a method for the determination of DA in an AA solution using differential pulse voltammetry was established. Because AA loses its electrochemical activity after being oxidized, hydrogen peroxide was used to oxidize AA, and the interference of AA was completely eliminated. As a result, trace DA could be directly determined in the AA solution with a bare glassy carbon electrode. When trace DA was determined in a 1.0 mmol L^?1 AA solution, there was a wide linear range from 3.0×10^?8 mol L^?1 to 1.0×10^?5 mol L^?1. The application of this method was demonstrated by the selective measurement of DA in an injection without pretreatment.     

Reversing the Stereoselectivity of a Palladium‐Catalyzed O‐Glycosylation through an Inner‐Sphere or Outer‐Sphere Pathway

An efficient and concise method for the construction of various O‐glycosidic bonds by a palladium‐catalyzed reaction with a 3‐O‐picoloyl glucal has been developed. The stereochemistry of the anomeric center derives from either an inner‐sphere or outer‐sphere pathway. Harder nucleophiles, such as aliphatic alcohols and sodium phenoxides give β‐products, and α products result from using softer nucleophiles, such as phenol.     

Hypervalent Iodine Reagents Enable Chemoselective Deboronative/Decarboxylative Alkenylation by Photoredox Catalysis

Chemoselective C(sp³)? C(sp²) coupling reactions under mild reaction conditions are useful for synthesizing alkyl‐substituted alkenes having sensitive functional groups. Reported here is a visible‐light‐induced chemoselective alkenylation through a deboronation/decarboxylation sequence under neutral aqueous reaction conditions at room temperature. This reaction represents the first hypervalent‐iodine‐enabled radical decarboxylative alkenylation reaction, and a novel benziodoxole‐vinyl carboxylic acid reaction intermediate was isolated. This C(sp³)? C(sp²) coupling reaction leads to aryl‐and acyl‐substituted alkenes containing various sensitive functional groups. The excellent chemoselectivity, stable reactants, and neutral aqueous reaction conditions of the reaction suggest future biomolecule applications.     

Redox‐Neutral α‐Allylation of Amines by Combining Palladium Catalysis and Visible‐Light Photoredox Catalysis

An unprecedented α‐allylation of amines was achieved by combining palladium catalysis and visible‐light photoredox catalysis. In this dual catalysis process, the catalytic generation of allyl radical from the corresponding π‐allylpalladium intermediate was achieved without additional metal reducing reagents (redox‐neutral). Various allylation products of amines were obtained in high yields through radical cross‐coupling under mild reaction conditions. Moreover, the transformation was applied to the formal synthesis of 8‐oxoprotoberberine derivatives which show potential anticancer properties.