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A highly flexible, free ‐ standing and antibacterial inorganic paper made from silver nanoparticle ‐ decorated ultralong hydroxyapatite nanowires has beEN developed. The as ‐ prepared paper exhibits advantages, such as high biocompatibility, high flexibility, long ‐ term sustained silver ‐ ion release, and high antibacterial activity. It is expected that this antibacterial paper can be applied in various fields such as in prevENting bacterial infections in daily life and medical use. More information can be found in the Full Paper by Y. J. Zhu et al. on page 11224. [ABSTRACT FROM AUTHOR]

This document is a guest editorial introducing a special collection titled "Frontiers in Chemical Bonding and Aromaticity" in honor of Professor Miquel Solà's 60th birthday. The collection features over 30 papers contributed by Solà's former students, colleagues, and friends, showcasing his diverse passions in chemistry. The editorial provides a brief biography of Solà, highlighting his achievements and contributions to the field of theoretical and computational chemistry. The guest editors express their gratitude to the contributing authors and the editorial team for their support in bringing this collection to fruition. [Extracted from the article]

Increasing bone formation on the surfaces of implants such as screws, plates, or shims holds great significance for clinical medicine. However, osteogenesis implant coatings that mimic natural bone in terms of both their components and structural features are still lacking. Here we report the biomimetic interface of calcium phosphate (CaP) in a collagen matrix fabricated by controlled mineralization that presents biomimetic porous features. The porous CaP/collagen interface, with a thickness of about 1 μm, significantly enhances osteogenesis, as verified at both the gene and protein levels as well as by in vivo experiments. Taking advantage of the generality of the method, the biomimetic interface was prepared on a variety of substrates, including conductive substrates, 3D metal meshes, plastic or elastic substrates, and even on filter papers. The adjustability and generality of the method have enabled new characterization tests to be developed during experiments on cells and thus should greatly facilitate clinical medicine and tissue engineering. [ABSTRACT FROM AUTHOR]

Abstract: Invited for the cover of this issue is the group of Lan Sheng and Sean Xiao‐An Zhang at the Jilin University. The image depicts a multicolor rewritable printer in action. Read the full text of the article at 10.1002/chem.201801692. [ABSTRACT FROM AUTHOR]

The photoluminescent properties of lanthanide complexes have been thoroughly investigated; however, there have been much fewer studies showcasing their potential use in ionizing radiation detection. In this work, we delve into the photo‐ and radio‐induced luminescence of a series of lanthanide‐bearing organic‐inorganic hybrids and their potential as a platform for X‐ray scintillation and imaging. The judicious synergy between lanthanide cations and 2,6‐di(1H‐pyrazol‐1‐yl)isonicotinate (bppCOO−) ligands affords six new materials with three distinct structures. Notably, Eu‐bppCOO‐1 and Tb‐bppCOO‐2 display sharp fingerprint X‐ray‐excited luminescence (XEL), the intensities of which can be linearly correlated with the X‐ray dose rates over a broad dynamic range (0.007–4.55 mGy s−1). Moreover, the X‐ray sensing efficacies of Eu‐bppCOO‐1 and Tb‐bppCOO‐2 were evaluated, showing that Tb‐bppCOO‐2 features a lower detection limit of 4.06 μGy s−1 compared to 14.55 μGy s−1 of Eu‐bppCOO‐1. Given the higher X‐ray sensitivity and excellent radiation stability of Tb‐bppCOO‐2, we fabricated a flexible scintillator film for X‐ray imaging by embedding finely ground Tb‐bppCOO‐2 in the polydimethylsiloxane (PDMS) polymer. The resulting scintillator film can be utilized for high‐resolution X‐ray imaging with a spatial resolution of approximately 7 lp mm−1. [ABSTRACT FROM AUTHOR]

This correspondence addresses a misassignment of an EPR spectrum in a recent publication by Dr. Jana and co-workers. The authors of the original paper reported the one-electron oxidation of a cyclic(alkyl)(amino)carbene (CAAC) to produce an intermediate iminium radical cation. However, the authors of this correspondence point out that the EPR parameters of the reported spectrum do not align with the proposed structure of the radical cation. Computational analysis suggests that the observed spectrum may actually correspond to an oxyaminyl-type radical, but a definitive structural assignment could not be achieved. Despite this misassignment, the overall conclusions of the original paper regarding the formation of the radical cation as a transient intermediate are unaffected. [Extracted from the article]

This paper provides the first report of the intramolecular [2+2] cycloaddition of vinylsilane. The [2+2] cycloaddition of allenes is a useful reaction that can synthesize cyclobutanes. However, no previous works have attempted to control the regioselectivity between the two double bonds of allenes only by changing the reaction conditions, although there have been some reports of the regioselective [2+2] cycloaddition of allenes by changing the substrate. In this study, we have succeeded in controlling intramolecular [2+2] cycloaddition reactions at the proximal and distal positions of allenes simply by changing the reaction conditions. We found that the atomic radius of silicon is very important for perfect control of the reaction's sites. The structures of all key compounds were determined by the crystal sponge method which could identify the structures of liquid compounds. [ABSTRACT FROM AUTHOR]

Sodium manganese‐based oxides (NMO) are attracting huge attention as safe and cost‐effective cathode materials for sodium‐ion batteries (SIBs). To date, one of the most important challenges of NMO‐based cathodes is the relatively low capacity. Therefore, it is of great significance to develop high‐capacity NMO‐based cathodes. Great efforts have been made to enhance the reversible capacity of NMO‐based cathodes, achieving considerable progress not only on electrochemical performance, but also the mechanism of massive sodium ion storage. In this paper, the structure and sodium storage mechanism for typical phases of NMO are reviewed, including P2, P3, O3, tunnel‐type, and spinel‐type NMO‐based cathodes. Strategies for high‐capacity NMO‐based cathodes, such as cationic substitution, anion redox activation, etc are introduced in detail. Last but not least, the future opportunities and challenges for high‐capacity NMO‐based cathode are prospected. [ABSTRACT FROM AUTHOR]

Radical‐type mechanophores (RMs) can undergo homolytic cleavage of their central C−C bonds upon exposure to mechanical forces, which affords radical species. Understanding the characteristics of these radical species allows bespoke mechanoresponsive materials to be designed and developed. The thermal stability of the central C−C bonds and the oxygen tolerance of the generated radical species are crucial characteristics that determine the functions and applicability of such RM‐containing mechanoresponsive materials. In this paper, we report the synthesis and characterization of two series of arylfluorene‐based RM derivatives, that is, 9,9'‐bis(5‐methyl‐2‐pyridyl)‐9,9'‐bifluorene (BPyF) and 9,9'‐bis(4,6‐diphenyl‐2‐triazyl)‐9,9'‐bifluorene (BTAF). BPyF and BTAF derivatives were synthesized without generating any peroxides initially, albeit that BPyF slowly converted to the corresponding peroxide in solution. DFT calculations revealed the importance of the thermodynamic stability and the values of the α‐SOMO levels of the corresponding radical species for their thermal stability and oxygen tolerance. Furthermore, the mechanochromism of BTAF was demonstrated by ball‐milling a BTAF‐centered polymer, which was synthesized by atom‐transfer radical polymerization (ATRP). [ABSTRACT FROM AUTHOR]

A foldable battery with high flexibility provides great potential in various wearable electronic devices for health and fitness tracking, chronic disease management, performance monitoring, navigation tracking, and portable gears for soldiers. We report a highly flexible, self‐healing Zn‐ion battery with a free‐standing cathode that is composed of a 3D gear‐like NH4V4O10@C composite on carbon paper. The battery retained a capacity of up to 102.4 mAh g−1 even after being folded 60 times with a high angle of 180°. An aqueous hydrogel consisting polyvinyl alcohol, glycerin and Zn(CF3SO3)2 was used as electrolyte, which showed as high as 580 % tensile strain under a loading weight of 78 N. The battery exhibited a better capacity retention of over 100 mAh g−1 and Coulombic efficiency of over 99.8 % after cutting and twisting to 90°, thereby indicating a great self‐healing performance. The gear‐like geometry greatly improved the volume accommodation due to the increased interval space between the blades and the outward configuration. Meanwhile the Zn2+ ionic conductivity was improved by rapid re‐binding of many existing hydroxy groups from the electrolyte and the enhanced contact surface area and diffusion route from the cathode material. The highly flexible, safe aqueous Zn‐ion battery opens a practical way to power various carry‐on electronics under mechanical agitation. [ABSTRACT FROM AUTHOR]

The regioselective deiodinations of L‐thyroxine (T4) play key roles in the thyroid hormone homeostasis. These reactions are catalyzed by three isoforms of the selenoenzymes, iodothyronine deiodinases (Dio1, Dio2 and Dio3), which are highly homologous in nature. Dio1 mediates 5′‐ or 5‐deiodinations of T4 to produce T3 and rT3, respectively. In contrast, Dio2 and Dio3 are selective to 5′‐ or 5‐deiodination to produce T3 and rT3, respectively. Understanding of the regioselectivity of deiodination at the molecular level is important as abnormal levels of thyroid hormone have been implicated in various clinical conditions, such as hypoxia, myocardial infarction, neuronal ischemia and cancer. In this paper, we report that the electronic properties of the iodine atoms in thyroxine (T4) can be modulated through a simple substitution in the 4′‐phenolic moiety. This leads to the change in the regioselectivity of deiodination by different small molecule mimics of Dio enzymes. By using this chemical approach, we also show that the substitution of a strong electron withdrawing group facilitates the removal of all four iodine atoms in the T4 derivative. Theoretical investigations on the hydrogen bonded adducts of T4 with imidazole indicate that the charge on the iodine atoms depend on the nature of hydrogen bond between the −OH group of T4 and the imidazole moiety. While the imidazole can act as either hydrogen bond acceptor (HBA) or hydrogen bond donor (HBD), the protonated imidazole acts exclusively as HBD in T4‐imidazole complex. These studies support the earlier observations that the histidine residue at the active sites of the deiodinases play an important role not only in the substrate binding, but also in altering the regioselectivity of the deiodination reactions. [ABSTRACT FROM AUTHOR]

Nitrogenase is the enzyme that converts N2 to NH3 under ambient conditions. The chemical mechanism of this catalysis at the active site FeMo‐co [Fe7S9CMo(homocitrate)] is unknown. An obligatory co‐product is H2, while exogenous H2 is a competitive inhibitor. Isotopic substitution using exogenous D2 revealed the N2‐dependent reaction D2+2H++2e−→2HD (the 'HD reaction'), together with a collection of additional experimental characteristics and requirements. This paper describes a detailed mechanism for the HD reaction, developed and elaborated using density functional simulations with a 486‐atom model of the active site and surrounding protein. First D2 binds at one Fe atom (endo‐Fe6 coordination position), where it is flanked by H−Fe6 (exo position) and H−Fe2 (endo position). Then there is synchronous transfer of these two H atoms to bound D2, forming one HD bound to Fe2 and a second HD bound to Fe6. These two HD dissociate sequentially. The final phase is recovery of the two flanking H atoms. These H atoms are generated, sequentially, by translocation of a proton from the protein surface to S3B of FeMo‐co and combination with introduced electrons. The first H atom migrates from S3B to exo‐Fe6 and the second from S3B to endo‐Fe2. Reaction energies and kinetic barriers are reported for all steps. This mechanism accounts for the experimental data: (a) stoichiometry; (b) the N2‐dependence results from promotional N2 bound at exo‐Fe2; (c) different N2 binding Km for the HD reaction and the NH3 formation reaction results from involvement of two different sites; (d) inhibition by CO; (e) the non‐occurrence of 2HD→H2+D2 results from the synchronicity of the two transfers of H to D2; (f) inhibition of HD production at high pN2 is by competitive binding of N2 at endo‐Fe6; (g) the non‐leakage of D to solvent follows from the hydrophobic environment and irreversibility of proton introduction. [ABSTRACT FROM AUTHOR]

The templated synthesis of ultralong hydroxyapatite nanowires@metal–organic framework core/shell (HAP@MIL‐100(Fe)) nanofibers has been demonstrated herein. The HAP@MIL‐100(Fe) nanofibers exhibited peroxidase‐like activity towards the oxidation of different peroxidase substrates in the presence of H2O2 accompanying with the clear color change of the solution. A new kind of flexible test paper was prepared by using HAP@MIL‐100(Fe) nanofibers as building blocks, which can be used for the detection of H2O2 and glucose, and it can be easily recovered, exhibiting excellent recyclability and promising applications in various fields. More information can be found in the Full Paper by Y.‐J. Zhu and Z.‐C. Xiong et al. on page 3328 ff. [ABSTRACT FROM AUTHOR]

In this paper, the photophysical behavior of four panchromatically absorbing, homoleptic bis(4H‐imidazolato)CuI complexes, with a systematic variation in the electron‐withdrawing properties of the imidazolate ligand, were studied by wavelength‐dependent time‐resolved femtosecond transient absorption spectroscopy. Excitation at 400, 480, and 630 nm populates metal‐to‐ligand charge transfer, intraligand charge transfer, and mixed‐character singlet states. The pump wavelength‐dependent transient absorption data were analyzed by a recently established 2D correlation approach. Data analysis revealed that all excitation conditions yield similar excited‐state dynamics. Key to the excited‐state relaxation is fast, sub‐picosecond pseudo‐Jahn‐Teller distortion, which is accompanied by the relocalization of electron density onto a single ligand from the initially delocalized state at Franck‐Condon geometry. Subsequent intersystem crossing to the triplet manifold is followed by a sub‐100 ps decay to the ground state. The fast, nonradiative decay is rationalized by the low triplet‐state energy as found by DFT calculations, which suggest perspective treatment at the strong coupling limit of the energy gap law. [ABSTRACT FROM AUTHOR]

Photosensitizers that gather high photo‐oxidizing power and strong visible‐light absorption are of great interest in the development of new photo‐chemotherapeutics. Indeed, such compounds constitute attractive candidates for the design of type I photosensitizers that are not dependent on the presence of oxygen. In this paper, we report on the synthesis and studies of new ruthenium(II) complexes that display strong visible‐light absorption and can oxidize guanine residues under visible‐light irradiation, as evidenced by nanosecond transient absorption spectroscopy. The reported compounds also tightly bind to G‐quadruplex DNA structures from the human telomeric sequence (TTAGGG repeat). The kinetic and thermodynamic parameters of the interaction of these Ru(II) complexes with G‐quadruplex and duplex DNA were studied thanks to luminescence titrations and bio‐layer interferometry measurements, which revealed higher affinities towards the non‐canonical G‐quadruplex architecture. Docking experiments and non‐covalent ionic analysis allowed us to gain information on the mode and the strength of the interaction of the compounds towards G‐quadruplex and duplex DNA. The different studies emphasize the substantial influence of the position and the number of non‐chelating nitrogen atoms on the interaction with both types of DNA secondary structures. [ABSTRACT FROM AUTHOR]

Methane (CH4) is a potent greenhouse gas and the second highest contributor to global warming. CH4 emissions are still growing at an alarmingly high pace. To limit global warming to 1.5 °C, one of the most effective strategies is to reduce rapidly the CH4 emissions by developing large‐scale methane removal methods. The purpose of this perspective paper is threefold. (1) To highlight the technology gap dealing with low concentration CH4 (at many emission sources and in the atmosphere). (2) To analyze the challenges and prospects of solar‐driven gas phase advanced oxidation processes for CH4 removal. And (3) to propose some ideas, which may help to develop solar‐driven gas phase advanced oxidation processes and make them deployable at a climate significant scale. [ABSTRACT FROM AUTHOR]

Controlling radical localization/delocalization is important for functional materials. The present paper describes synthesis and results of electrochemical, spectroscopic, and theoretical studies of diruthenium (p‐diethynylacene)diyl complexes, Me3Si‐(C≡C)2‐Ru(dppe)2‐C≡C−Ar‐C≡C−Ru(dppe)2‐(C≡C)2‐SiMe3 (1–6) (dppe: 1,2‐bis(diphenylphosphino)ethane), and their monocationic radical species ([1]+–[6]+). The HOMO‐LUMO energy gaps can be finely tuned by the acene rings in the bridging ligands installed, as indicated by the absorption maxima of the electronic spectra of 1–6 ranging from the UV region even to the NIR region. The cationic species [1]+–[6]+ show two characteristic NIR bands, which are ascribed to the charge resonance (CR) and π‐π* transition bands, as revealed by spectroelectrochemistry. Expansion of the acene rings in [1]+–[6]+ causes (1) blue shifts of the CR bands and red shifts of the π‐π* transition bands and (2) charge localization on the acene parts as evidenced by the ESR, DFT and TD‐DFT analyses. Notably, the monocationic complexes of the larger acene derivatives are characterized as the non‐classical acene‐localized radicals. [ABSTRACT FROM AUTHOR]

Invited for the cover of this issue is the group of Ying-Jie Zhu at the Chinese Academy of Sciences. The image depicts a highly flexible and free-standing paper with high antibacterial activity made from silver nanoparticle-decorated ultralong hydroxyapatite nanowires. Read the full text of the article at . [ABSTRACT FROM AUTHOR]

We report a method to detect proteins via suppression of rolling circle amplification (RCA) by using an appropriate aptamer as the linear primer (denoted as an aptaprimer) to initiate RCA. In the absence of a protein target, the aptaprimer is free to initiate RCA, which can produce long DNA products that are detected via binding of a fluorescent intercalating dye. Introduction of a target causes the primer region within the aptamer to become unavailable for binding to the circular template, inhibiting RCA. Using SYBR Gold or QuantiFluor dyes as fluorescent probes to bind to the RCA reaction product, it is possible to produce a generic protein‐modulated RCA assay system that does not require fluorophore‐ or biotin‐modified DNA species, substantially reducing complexity and cost of reagents. Based on this modulation of RCA, we demonstrate the ability to produce both solution and paper‐based assays for rapid and quantitative detection of proteins including platelet derived growth factor and thrombin. [ABSTRACT FROM AUTHOR]

Covalency in actinides has emerged as a resounding research topic on account of the technological importance in separating minor actinides from lanthanides for spent nuclear fuel processing, and utilization of their distinct bonding properties has been realized as a route towards overcoming this challenge. Because of the limited radial extent of the 4f orbitals, there is almost no 4f electron participation in bonding in lanthanides; this is not the case for the actinides, which have extended 5f orbitals that are capable of overlapping with ligand orbitals, although not to the degree of overlap as in the d orbitals of transition metals. In this concept paper, a general description of covalency in actinide compounds is provided. After introducing two main approaches to enhance covalency, either by exploiting increased orbital overlap or decreasing energy differences between the orbitals causing orbital energy degeneracy, the current state of the field is illustrated by using several examples from the recent literature. This paper is concluded by proposing the use of actinide chalcogenides as a convenient auxiliary tool to study covalency in actinide compounds. [ABSTRACT FROM AUTHOR]

Ring‐opening metathesis polymerization (ROMP) of strained macrocycles is a key method to prepare diverse polymers. However, lack of ring strain in most macrocycles is an impediment to polymerization. In this paper, the polymerization/oligomerization of unstrained macrocycles was achieved using a supramolecular approach, leading selectively to cyclic products. Diphenyl thiourea and other guest molecules were used as additives to the ROMP reaction of unstrained macrocycles. An intermediate host‐guest complex leads to the stabilization of the open form of the macrocycle after treatment with Grubbs catalysts, thereby favoring polymerization by inhibiting the ring‐closing reaction back to the monomer. This proof‐of‐concept enables ring‐expansion polymerization of unstrained macrocycles leading to cyclic polymers with molecular weights up to 6700 Da. [ABSTRACT FROM AUTHOR]

Chemical‐ and photostability of unnatural base pairs (UBPs) are important to maintain the genetic code integrity, and critical for developing healthy semisynthetic organisms. As reported, dTPT3 was less stable upon irradiation, and thus might act as a pervasive photosensitizer to induce oxidative damage within DNA, causing harm to living semi‐synthetic organisms when exposed to UVA radiation. However, there was no knowledge about molecular‐level understanding of this damage process. In this paper, we not only identified four photoproducts of dTPT3, including desulfur‐dTPT3 (dTPT3H), TPT3 sulphinate (TPT3SO2), TPT3 sulphonate (TPT3SO3) and TPT3‐thioTPT3 (TPT3STPT3), but also established a Type II photosensitized oxidation mechanism. In addition, the antioxidant (sodium ascorbate) was able to effectively inhibit the photoproducts formation of dTPT3 and dTPT3 in DNA, suggesting that a reductive environment might protect DNA bearing dTPT3 against UVA oxidation and ameliorate its adverse biological effects. The comprehensive understanding of TPT3' photochemical stability will give researchers helpful guidance to design more photostable UBPs and construct healthier semisynthetic organisms. [ABSTRACT FROM AUTHOR]

The chemical modification of proteins is an effective technique for manipulating the properties and functions of proteins, and for creating protein‐based materials. The N‐terminus is a promising target for single‐site modification that provides modified proteins with uniform structures and properties. In this paper, a copper(II)‐mediated aldol reaction with 2‐pyridinecarboxaldehyde (2‐PC) derivatives is proposed as an operationally simple method to selectively modify the N‐terminus of peptides and proteins at room temperature and physiological pH. The copper(II) ion activates the N‐terminal amino acids by complexation with an imine of the N‐terminal amino acid and 2‐PCs, realizing the selective formation of the nucleophilic intermediate at the N‐terminus. This results in a stable carbon‐carbon bond between the 2‐PCs and the α‐carbon of various N‐terminal amino acids. The reaction is applied to four different proteins, including biopharmaceuticals such as filgrastim and trastuzumab. The modified trastuzumab retains the human epidermal growth factor receptor 2 recognition activity. [ABSTRACT FROM AUTHOR]

In this paper, we present an unprecedented and general umpolung protocol that allows the functionalization of silyl enol ethers and of 1,3‐dicarbonyl compounds with a large range of heteroatom nucleophiles, including carboxylic acids, alcohols, primary and secondary amines, azide, thiols, and also anionic carbamates derived from CO2. The scope of the reaction also extends to carbon‐based nucleophiles. The reaction relies on the use of 1‐bromo‐3,3‐dimethyl‐1,3‐dihydro‐1λ3[d][1,2]iodaoxole, which provides a key α‐brominated carbonyl intermediate. The reaction mechanism has been studied experimentally and by DFT, and we propose formation of an unusual enolonium intermediate with a halogen‐bonded bromide. [ABSTRACT FROM AUTHOR]

Carbamoyl fluoride is a fluorinated group that, to this date, remains underexplored, probably due to the lack of data concerning its properties. In this paper, a study of carbamoyl fluoride is presented. Stability studies, in particular under physiological conditions, and lipophilicity measurement were performed. A new easy, safe, inexpensive, and metal‐free synthesis method is also described. Finally, a potential use in radiochemistry through a 18F/19F isotopic exchange is demonstrated. [ABSTRACT FROM AUTHOR]

Azobenzene photoswitches are valuable tools for controlling properties of molecular systems with light. We have been investigating azobenzene glycoconjugates to probe carbohydrate‐protein interactions and to design glycoazobenzene macrocycles with chiroptical and physicochemical properties modulated by light irradiation. To date, direct conjugation of glycosides to azobenzenes was performed by reactions providing target compounds in limited yields. We therefore sought a more effective and reliable coupling method. In this paper, we report on a straightforward thioarylation of azobenzene derivatives with glycosyl thiols as well as other thiols, thereby increasing the scope of azobenzene conjugation. Even challenging unsymmetrical conjugates can be achieved in good yields via sequential or one‐pot procedures. Importantly, red‐shifted azoswitches, which are addressed with visible light, were easily functionalized. Additionally, by oxidation of the sulfide bridge to the respective sulfones, both the photochromic and the thermal relaxation properties of the core azobenzene can be tuned. Utilizing this option, we realized orthogonal three‐state photoswitching in mixtures containing two distinct azobenzene thioglycosides. [ABSTRACT FROM AUTHOR]

Since the global peptide drug market demand has been predicted to increase, highly efficient and inexpensive mass scale peptides are required. However, the production process raises questions about the cost of energy input, scale‐up production, raw materials, and solvents treatment. This paper introduces 2 methods for the 2–4 mer oligopeptides bond formation for batch reaction utilizing 50–100 mol% of a mild Brønsted acid under the mild condition. One of the methods has been capably adapted to flow synthesis at room temperature using organic solvents with boiling points below 100 °C. The method applies the tert‐butoxycarbonyl amino methoxy group, forming the desired dipeptide without solvent at mild temperatures. Furthermore, the conversion of the carboxylic acid leaving the group to phenyl ester promotes peptide bond formation, and the reaction were applied to di, tri, and tetrapeptide bond formation in excellent yield without notable racemization at ambient temperature (up to >99 % yield and 99 : 1 dr). Finally, this study proposes this new production method to overcome the limited scale‐up production by reaction device scale: liquid phase biomimetic catalytic peptide flow synthesis utilizing a mild Brønsted acid. [ABSTRACT FROM AUTHOR]

Optically active cyclopropanes have been widely investigated especially from the views of pharmaceutical and agrochemical industries, and substituting one of the methylenes with the difluoromethylene unit should be promising for developing novel biologically relevant compounds and functional materials. In this paper, the copper‐catalyzed enantioselective hydrosilylation of gem‐difluorocyclopropenes to provide the corresponding chiral gem‐difluorocyclopropanes is presented. The use of copper(I) chloride, chiral ligands including bidentate BINAPs and monodentate phosphoramidites, and silylborane Me2PhSi‐Bpin accompanying sodium tert‐butoxide in methanol was appropriate for the enantioselective hydrosilylation of the strained C=C double bond, and the resultant chiral difluorinated three‐membered ring was unambiguously characterized. Subsequent activation of the silyl groups in enantio‐enriched gem‐difluorocyclopropanes showed substantial reduction of the enantiopurity, indicating cleavage of the distal C−C bond leading to the transient acyclic intermediates. [ABSTRACT FROM AUTHOR]

Inclusion of polymethine cyanine dyes in the cavity of macrocyclic receptors is an effective strategy to alter their absorption and emission behavior in aqueous solution. In this paper, the effect of the host‐guest interaction between cucurbit[8]uril (CB[8]) and a model trimethine indocyanine (Cy3) on dye spectral properties and aggregation in water is investigated. Solution studies, performed by a combination of spectroscopic and calorimetric techniques, indicate that the addition of CB[8] disrupts Cy3 aggregates, leading to the formation of a 1 : 1 host‐guest complex with an association constant of 1.5×106 M−1. At concentrations suitable for NMR experiments, the slow formation of a supramolecular polymer was observed, followed by precipitation. Single crystals X‐ray structure elucidation confirmed the formation of a polymer with 1 : 1 stoichiometry in the solid state. [ABSTRACT FROM AUTHOR]

Solar‐driven interfacial vaporization by localizing solar‐thermal energy conversion to the air−water interface has attracted tremendous attention. In the process of converting solar energy into heat energy, photothermal materials play an essential role. Herein, a flexible solar‐thermal material di‐cyan substituted 5,12‐dibutylquinacridone (DCN−4CQA)@Paper was developed by coating photothermal quinacridone derivatives on the cellulose paper. The DCN−4CQA@Paper combines desired chemical and physical properties, broadband light‐absorbing, and shape‐conforming abilities that render efficient photothermic vaporization. Notably, synergetic coupling of solar‐steam and solar‐electricity technologies by integrating DCN−4CQA@Paper and the thermoelectric devices is realized without trade‐offs, highlighting the practical consideration toward more impactful solar heat exploitation. Such solar distillation and low‐grade heat‐to‐electricity generation functions can provide potential opportunities for fresh water and electricity supply in off‐grid or remote areas. [ABSTRACT FROM AUTHOR]

A paper ‐ based self ‐ powered DNA sensor capable of generating signal output without external power sources was developed by using a biofuel cell. Enzymes catalyzed the oxidation of glucose at the anode, and PtNPs grown on cellulose fibers reduced O2 at the cathode. The all ‐ solid ‐ state paper supercapacitor was also integrated for signal amplification. For more information, see the Full Paper by J. Yu et al. on page 12453 ff. [ABSTRACT FROM AUTHOR]

EPR spectroscopic evidence for intramolecular electron transfer in anionic N‐substituted naphthalimides to yield persistent diradical anions and intermolecular electron transfer from a variety of carbanions to 6‐bromo‐N‐phenyl‐naphthalimide to yield persistent radical–radical anion pairs was recently claimed in two papers by Zhang et al. In this comment, it is shown that the EPR spectra published in both papers do not agree with the proposed triplet‐state species. Rather, the spectra are due to various doublet‐state radicals, deriving from minor side reactions. The misinterpretations invalidate the general conclusions of the papers. [ABSTRACT FROM AUTHOR]

To fulfil the potential of Li–S batteries (LSBs) with high energy density and low cost, multiple challenges need to be addressed simultaneously. Most research in LSBs has been focused on the sulfur cathode design, although the performance is also known to be sensitive to other parameters such as binder, current collector, separator, lithium anode, and electrolyte. Here, an integrated LSB system based on the understanding of the different roles of binder, current collector, and separator is developed. By using the cross‐linked carboxymethyl cellulose–citric acid (CMC‐CA) binder, Toray carbon paper current collector, and reduced graphene oxide (rGO) coated separator, LSBs achieve a high capacity of 960 mAh g−1 after 200 cycles (2.5 mg cm−2) and 930 mAh g−1 after 50 cycles (5 mg cm−2) at 0.1 C. Moreover, the failure mechanism at a high sulfur loading with characteristics of fast capacity decay and infinite charging is discussed. This work highlights the synergistic effect of different components and the challenges towards more reliable LSBs with high sulfur loading. Lithium–sulfur batteries: The practical application of lithium–sulfur batteries depends on systematic optimization of the complicated system. A facile integrated approach based on the synergy between the current collector, binder, and separator is developed to improve the performance of batteries. The synergistic effect of different components and the failure mechanism of batteries with high sulfur loading are discussed (see scheme). [ABSTRACT FROM AUTHOR]

(K0.5Na0.5)NbO3 (KNN) is a promising lead‐free alternative for ferroelectric thin films such as Pb(Zr,Ti)O3. One main drawback is its high leakage current density at high electric fields, which has been previously linked to alkali non‐stoichiometry. This paper compares three acetate‐based chemical solution synthesis and deposition methods for 0.5 mol % Mn‐doped KNN film fabrication, using lower crystallization temperature processes in comparison to the sintering temperatures necessary for fabrication of KNN ceramics. This paper shows the crucial role of the A site homogenization step during solution synthesis in preserving alkali chemical homogeneity of Mn doped KNN films. Chemically homogeneous films show a uniform grain size of 80 nm and a leakage current density under 2.8×10−8 A cm−2 up to electric fields as high as 600 kV cm−1, which is the highest breakdown strength reported for KNN thin films. Solution synthesis involving two‐step pyrolysis resulted in films with dense, columnar microstructures, which are interesting for orientation control and enhancement of piezoelectric properties. This study reports detailed solution synthesis and deposition processes with good dielectric, ferroelectric and breakdown field properties. An optimized fabrication method that should couple low leakage current density with dense and oriented microstructures is proposed. [ABSTRACT FROM AUTHOR]

In the present paper, density functional theory (DFT) has been applied to the study of the activation mechanism of a new selenium azo‐rhodamine (azoSeRho) in presence of the tripeptide thiol, glutathione (GSH), as potent activatable photosensitizer to be employed in photodynamic therapy. The introduction of the azo group into the conjugated system of the seleno‐rhodamine dye and its reaction with GSH allow the selective formation of the active photosensitizer, SeRho. Furthermore, DFT calculations have allowed to shed light on the activation mechanism of the azoSeRho photosensitizer when molecular oxygen is present and hydrogen peroxide is formed. This study is the first theoretical investigation revealing how the reductive cleavage of the azo moiety by GSH occurs. Time‐dependent DFT approach has been used to evaluate the chalcogen‐substitution effect on the structures and photophysical properties of the azo derivatives and, then, on the activated photosensitizers. [ABSTRACT FROM AUTHOR]

This paper describes a method that combines a microfluidic device and self‐assembled monolayers for matrix‐assisted laser desorption/ionization mass spectrometry (SAMDI) mass spectrometry to calculate the cooperativity in binding of calcium ions to peptidylarginine deiminase type 2 (PAD2). This example uses only 120 μL of enzyme solution and three fluidic inputs. This microfluidic device incorporates a self‐assembled monolayer that is functionalized with a peptide substrate for PAD2. The enzyme and different concentrations of calcium ions are flowed through each of eight channels, where the position along the channel corresponds to reaction time and position across the channel corresponds to the concentration of Ca2+. Imaging SAMDI (iSAMDI) is then used to determine the yield for the enzyme reaction at each 200 μm pixel on the monolayer, providing a time course for the reactions. Analysis of the peptide conversion as a function of position and time gives the degree of cooperativity (n) and the concentration of ligand required for half maximal activity (K0.5) for the Ca2+ – dependent activation of PAD2. This work establishes a high‐throughput and label‐free method for studying enzyme‐ligand binding interactions and widens the applicability of microfluidics and matrix‐assisted laser desorption/ionization mass spectrometry (MALDI) imaging mass spectrometry. [ABSTRACT FROM AUTHOR]

The onset of COVID‐19, coupled with the finer lens placed on systemic racial disparities within our society, has resulted in increased discussions around mental health. Despite this, mental health struggles in research are still often viewed as individual weaknesses and not the result of a larger dysfunctional research culture. Mental health interventions in the science, technology, engineering, and mathematics (STEM) academic community often focus on what individuals can do to improve their mental health instead of focusing on improving the research environment. In this paper, we present four aspects of research that may heavily impact mental health based on our experiences as research scientists: bullying and harassment; precarity of contracts; diversity, inclusion, and accessibility; and the competitive research landscape. Based on these aspects, we propose systemic changes that institutions must adopt to ensure their research culture is supportive and allows everyone to thrive. [ABSTRACT FROM AUTHOR]

Among all possible NMR crystallography approaches for crystal‐structure determination, crystal structure prediction – NMR crystallography (CSP‐NMRX) has recently turned out to be a powerful method. In the latter, the original procedure exploited solid‐state NMR (SSNMR) information during the final steps of the prediction. In particular, it used the comparison of computed and experimental chemical shifts for the selection of the correct crystal packing. Still, the prediction procedure, generally carried out with DFT methods, may require important computational resources and be quite time‐consuming, especially if there are no available constraints to use at the initial stage. Herein, the successful application of this combined prediction method, which exploits NMR information also in the input step to reduce the search space of the predictive algorithm, is presented. Herein, this method was applied on mebendazole, which is characterized by desmotropism. The use of SSNMR data as constraints for the selection of the right tautomer and the determination of the number of independent molecules in the unit cell led to a considerably faster process, reducing the number of calculations to be performed. In this way, the crystal packing was successfully predicted for the three known phases of mebendazole. To evaluate the quality of the predicted structures, these were compared to the experimental ones. The crystal structure of phase B of mebendazole, in particular, was determined de novo by powder diffraction and is presented for the first time in this paper. [ABSTRACT FROM AUTHOR]

Recently, we presented a strategy for packaging peptides as side‐chains in high‐density brush polymers. For this globular protein‐like polymer (PLP) formulation, therapeutic peptides were shown to resist proteolytic degradation, enter cells efficiently and maintain biological function. In this paper, we establish the role charge plays in dictating the cellular uptake of these peptide formulations, finding that peptides with a net positive charge will enter cells when polymerized, while those formed from anionic or neutral peptides remain outside of cells. Given these findings, we explored whether cellular uptake could be selectively induced by a stimulus. In our design, a cationic peptide is appended to a sequence of charge‐neutralizing anionic amino acids through stimuli‐responsive cleavable linkers. As a proof‐of‐concept study, we tested this strategy with two different classes of stimuli, exogenous UV light and an enzyme (a matrix metalloproteinase) associated with the inflammatory response. The key finding is that these materials enter cells only when acted upon by the stimulus. This approach makes it possible to achieve delivery of the polymers, therapeutic peptides or an appended cargo into cells in response to an appropriate stimulus. [ABSTRACT FROM AUTHOR]

With the development of green chemistry, it is still a challenge to maintain the unstable valence state of the metal in heterogeneous catalysts and realize new catalytic synthesis methods. In this paper, it is reported that an univalent copper nanocomposite (Cu@Al/SBA‐15) can efficiently catalyze the formation of novel amino‐containing benzotriazoles with great fluorescence properties in a new synthetic strategy. Subsequently, its application is further verified by an acylation reaction to produce a series of novel benzotriazoles derivatives with high yield. It is worth noting that the Cu@Al/SBA‐15 nanocomposites not only enable the reaction completed with high yield in a short time, but can also be recycled many times without a significant reduction in activity, and the leaching of copper and aluminum species in reaction system is negligible. Finally, the detailed and feasible reaction mechanism is also provided. [ABSTRACT FROM AUTHOR]

In this work, by using two kinds of viologen ligands three POM‐based Compounds were obtained under hydrothermal conditions, namely [AgI(bmypd)0.5(β‐Mo8O26)0.5] (1) (bmypd ⋅ 2Cl=1,1′‐[Biphenyl‐4,4′‐bis(methylene)]bis(4,4′‐bipyridyinium)dichloride), [AgI2(bypy)4(HSiW12O40)2] ⋅ 14H2O (2) and [AgI(bypy)(γ‐Mo8O26)0.5] (3) (bypy⋅Cl=1‐Benzyl‐4,4′‐bipyridyinium chloride). The structures were characterized by Fourier transform infrared spectroscopy (FT–IR), Powder X‐ray diffraction (PXRD), X‐ray photoelectron spectroscopy (XPS) and single crystal X‐ray diffraction. Compounds 1–3 show excellent photochromic ability with fast photoresponse under the irradiation of ultraviolet light with different degrees of color changes. So compounds 1–3 can be used as visible ultraviolet detectors. Compounds 1–3 also possess photoluminescence properties with fast and excellent fluorescence quenching effect. Compounds 1–3 also can be used as inkless and erasable printing materials with suspensions of 1–3 applied to filter paper. Compounds 1–3 can also produce color changes in amine vapor environment, especially in an NH3 atmosphere. Compounds 1–3 can be used as organic amine detectors. [ABSTRACT FROM AUTHOR]

This article in Chemistry - A European Journal discusses various methods of substitution recombination in protein engineering. The paper explains how these methods can enhance the properties of enzymes through both experimental and computer-assisted techniques. The cover feature of the journal visually represents the concept of substitution recombination using a tree-like structure, with branches representing protein sequences and orbs symbolizing beneficial substitutions. For more detailed information, readers are directed to the review by X. Li, H. Cui, and their colleagues. [Extracted from the article]

This paper presents an enzyme building block for the assembly of megamolecules. The system is based on the inhibition of the human‐derived cellular retinoic acid binding protein II (CRABP2) domain. We synthesized a synthetic retinoid bearing an arylfluorosulfate group, which uses sulfur fluoride exchange click chemistry to covalently inhibit CRABP2. We conjugated both the inhibitor and a fluorescein tag to an oligo(ethylene glycol) backbone and measured a second‐order rate constant for the protein inhibition reaction of approximately 3,600 M−1s−1. We used this new enzyme‐inhibitor pair to assemble multi‐protein structures in one‐pot reactions using three orthogonal assembly chemistries to demonstrate exact control over the placement of protein domains within a single, homogeneous molecule. This work enables a new dimension of control over specificity, orientation, and stoichiometry of protein domains within atomically precise nanostructures. [ABSTRACT FROM AUTHOR]

This paper reports the synthesis and study of new pH‐sensitive DB24C8‐based [2]rotaxane molecular shuttles that contain within their axle four potential sites of interaction for the DB24C8: ammonium, amine, Weinreb amide, and ketone. In the protonated state, the DB24C8 lay around the best ammonium site. After either deprotonation or deprotonation‐then‐carbamoylation of the ammonium, different localizations of the DB24C8 were seen, depending on both the number and nature of the secondary stations and steric restriction. Unexpectedly, the results indicated that the Weinreb amide was not a proper secondary molecular station for the DB24C8. Nevertheless, through its methoxy side chain, it slowed down the shuttling of the macrocycle along the threaded axle, thereby partitioning the [2]rotaxane into two translational isomers on the NMR timescale. The ketone was successfully used as a secondary molecular station, and its weak affinity for the DB24C8 was similar to that of a secondary amine. [ABSTRACT FROM AUTHOR]

This paper reports the first example of C−H arylation of benzene under mild conditions, using H2 as an electron source {turnover numbers (TONs)=0.7–2.0 for 24 h}. The reaction depends on a Rh‐based electron storage catalyst, and proceeds at room temperature and in aqueous solution. Furthermore, the H2 is inactive during the radical transfer step, greatly reducing unwanted side reactions. [ABSTRACT FROM AUTHOR]

Melanin‐like nanomaterials have found application in a large variety of high economic and social impact fields as medicine, energy conversion and storage, photothermal catalysis and environmental remediation. These materials have been used mostly for their optical and electronic properties, but also for their high biocompatibility and simplicity and versatility of preparation. Beside this, their chemistry is complex and it yields structures with different molecular weight and composition ranging from oligomers, to polymers as well as nanoparticles (NP). The comprehension of the correlation of the different compositions and morphologies to the optical properties of melanin is still incomplete and challenging, even if it is fundamental also from a technological point of view. In this minireview we focus on scientific papers, mostly recent ones, that indeed examine the link between composition and structural feature and photophysical and photochemical properties proposing this approach as a general one for future research. [ABSTRACT FROM AUTHOR]

Elastic organic single crystals with light‐emitting and multi‐faceted bending properties are extremely rare. They have potential application in optical materials and have attracted the extensive attention of researchers. In this paper, we reported a structurally simple barbituric derivative DBDT, which was easily crystallized and gained long needle‐like crystals (centimeter‐scale) in DCM/CH3OH (v/v=2/8). Upon applying or removing the mechanical force, both the (100) and (040) faces of the needle‐like crystal showed reversible bending behaviour, showing the nature of multi‐faceted bending. The average hardness (H) and elastic modulus (E) were 0.28±0.01 GPa and 4.56±0.03 GPa for the (040) plane, respectively. Through the analysis of the single crystal data, it could be seen that the van der waals (C−H⋅⋅⋅π and C−H⋅⋅⋅C), H‐bond (C−H⋅⋅⋅O) and π⋅⋅⋅π interactions between molecules were responsible for the generation of the crystal elasticity. Interestingly, elastic crystals exhibited optical waveguide characteristics in straight or bent state. The optical loss coefficients measured at 627 nm were 0.7 dBmm−1 (straight state) and 0.9 dBmm−1 (bent state), while the optical loss coefficient (α) were 1.5 dBmm−1 (straight state) and 1.8 dBmm−1 (bent state) at 567 nm. Notably, the elastic organic molecular crystal based on barbituric derivative could be used as the candidate for flexible optical devices. [ABSTRACT FROM AUTHOR]

Monoalkylated derivatives of the unusually polar all‐cis 2,3,4,5,6‐ pentafluorocyclohexyl (Janus face) motif are prepared starting from an aryl hydrogenation of 2,3,4,5,6‐ pentafluorophenylacetate methyl ester 15. The method used Zeng's Rh(CAAC) carbene catalyst 4 in the hydrogenation following the protocol developed by Glorius. The resultant Janus pentafluorocyclohexylacetate methyl ester 16 was converted to the corresponding alcohol 18, aldehyde 13, bromide 29 and azide 14 through functional group manipulations, and some of these building blocks were used in Ugi‐multicomponent and Cu‐catalysed click reactions. NBoc protected pentafluoroarylphenylalanine methyl ester 35 was also subject to an aryl hydrogenation, and then deprotection to generate the Janus face β‐pentafluorocyclohexyl‐alanine amino acid 15, which was incorporated into representative members of an emerging class of candidate antiviral compounds. Log P measurements demonstrate that the all‐cis 2,3,4,5,6‐pentafluorocyclohexyl ring system is more polar than a phenyl ring. In overview the paper introduces new building blocks containing this Janus ring and demonstrates their progression to molecules typically used in bioactives discovery programmes. [ABSTRACT FROM AUTHOR]

During the past few decades, radiotherapy and chemotherapy have been the standard approaches for tumor treatments. However, the potential toxic effect and side effects of both radiotherapy and chemotherapy on the human body still cannot be neglected. Given this, the Fenton reaction has become one of the most effective treatment strategies to combat tumor cells. This review aims to summarize the recent advances comprehensively and systematically in chemodynamic therapy (CDT) via the Fenton reaction. In addition, a host of the advanced nano‐multifunctional materials and engineering bacteria used in the Fenton reaction were also summarized. This paper would be helpful to provide guidance and lay firm foundations for future tumor treatment. [ABSTRACT FROM AUTHOR]