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The development of photoinduced luminescent radicals with dynamic emission color is still challenging. Herein we report a novel molecular radical system (TBIQ) that shows photo-controllable luminescence, leading to a wide range of ratiometric color changes via light excitation. The conjugated skeleton of TBIQ is decorated with steric-demanding tertiary butyl groups that enable appropriate intermolecular interaction to make dynamic intermolecular coupling possible for controllable behaviors. We reveal that the helicenic pseudo-planar conformation of TBIQ experiences a planarization process after light excitation, leading to more compactly stacked supermolecules and thus generating radicals via intermolecular charge transfer. The photo-controllable luminescent radical system is employed for a high-level information encryption application. This study may offer unique insight into molecular dynamic motion for optical manufacturing and broaden the scope of smart-responsive materials for advanced applications.

Developing new materials for the fabrication of resistive random-access memory is of great significance in this period of big data. Herein, we present a novel design strategy of embedding donor (D) and acceptor (A) fragments into imine-linked frameworks to construct resistive switching covalent organic frameworks (COFs) for high-performance memristors. Two D-A-type two-dimensional COFs, COF-BT-TT and COF-TT-TVT, were designed and synthesized using a conventional solvothermal approach, and high-quality thin films of these materials deposited on ITO substrate exhibited great potential as an active layer for memristors. Rewritable memristors based on 100 nm thick COF-TT-BT and COF-TT-TVT films showed a high ON/OFF current ratio (ca. 105 and 104 ) and low driving voltage (1.30 and 1.60 V). The cycle period and retention time for COF-TT-BT-based rewritable devices were as high as 319 cycles and 3.3×104 s at a constant voltage of 0.1 V (160 cycles and 1.2×104 s for the COF-TT-TVT memristor).

Platinum (Pt) is the most effective bench-marked catalyst for producing renewable and clean hydrogen energy by electrochemical water splitting. There is demand for high HER catalytic activity to achieve efficient utilization and minimize the loading of Pt in catalysts. In this work, we significantly boost the HER mass activity of Pt nanoparticles in Pt x /Co to 8.3 times higher than that of commercial Pt/C by using Co/NC heterojunctions as a heterogeneous version of electron donors. The highly coupled interfaces between Co/NC and Pt metal enrich the electron density of Pt nanoparticles to facilitate the adsorption of H + , the dissociation of Pt-H bonds and H 2 release, giving the lowest HER overpotential of 6.9 mV vs. RHE at 10 mA/cm 2 in acid among reported HER electrocatalysts. Given the easy scale-up synthesis due to the stabilization of ultrafine Pt nanoparticles by Co/NC solid ligands, Pt x /Co can even be a promising substitute for commercial Pt/C for practical applications.

Unprecedented threading kinetics were revealed between viologen-based guests and conformationally adaptive oxatub[4]arene. Three representative conformations of oxatub[4]arene are involved in the kinetic and thermodynamic products which follow the opposite orders in their rankings. Consequently, error correction was involved and a complex kinetic process was observed in a simple two-component system. Moreover, it was found that some viologen-based guests have much faster threading kinetics than those of DABCO-based with the same stoppers. This was enabled by an unprecedented threading mechanism in which a tilted conformation of the guests is adopted by involving one linear alkyl group on the 3,5-dialkoxybenzyl stoppers, the viologen core, and the methylene spacers in the transition states. This new mechanism even allows the viologen-based guests with the 3,5-dicetyloxybenzyl stoppers to form a pseudorotaxane with oxatub[4]arene.

Self-assembly of host molecules in aqueous media via metal-ligand coordination is well developed. However, the preparation of purely covalent counterparts in water has remained a formidable task. An anionic tetrahedron cage was successfully self-assembled in a [4+4] manner by condensing a trisamine and a trisformyl in water. Even although each individual imine bond is rather labile and apt to hydrolyze in water, the tetrahedron is remarkably stable or inert due to multivalence. The tetrahedral cages, as well as its neutral counterparts dissolved in organic solvent, have homochirality, namely that their four propeller-shaped trisformyl residues adopt the same rotational conformation. The cage is able to take advantage of hydrophobic effect to accommodate a variety of guest molecules in water. When a chiral guest was recognized, the formation of one enantiomer of the cage became more favored relative to the other. As a consequence, the cage could be produced in an enantioselective manner. The tetrahedron is able to maintain its chirality after removal of the chiral guest-probably on account of the cooperative occurrence of intramolecular forces that restrict the intramolecular flipping of phenyl units in the cage framework.

Modulating intermolecular charge-transfer (ICT) interactions between specific donor and acceptor species in host-guest systems is a big challenge and full of research value in supramolecular chemistry and materials science. In this work, a strategy to modulate the supramolecular ICT interactions in the solid state is developed by compressing the binding cavity of a macrocyclic host named perethylated leaning pillar[6]arene (p-EtLP6). The solid-state ICT affinities of p-EtLP6 toward multi-types of electron-deficient planar guests could be significantly enhanced by transforming the macrocyclic backbone from the original para-bridged mode into a hybrid para- and meta-bridged isomeric form (m-EtLP6). X-ray single-crystal structural analyses incorporating theoretical calculation demonstrate that the improved ICT affinities are mainly attributed to the superior host-guest size fit arising from the compressed binding cavity in m-EtLP6 as compared with p-EtLP6.

Improving the stability of sensitive catalytic systems is an emerging research topic in the catalysis field. However, the current design of heterogeneous catalysts mainly improves their catalytic performance. This paper presents a single-atom catalyst (SAC) strategy to improve the cobalt-catalysed fluorination of acyl chlorides. A stable Co-F intermediate can be formed through the oxidative fluorination of Co

Herein, we report the self-assembly of an anionic homochiral octahedral cage by condensing six Ga3+ cations and four trisacylhydrazone ligands. The robust nature of the hydrazone bond renders the cage stable in water, where it can take advantage of the hydrophobic effect for host-guest recognition. In addition to the internal binding site, namely, the inner cavity, the octahedral cage possesses four "windows", each of which represents an external binding site allowing peripheral complexation. These internal and external binding sites endow the cage with the capability to bind a broad range of guests whose sizes could either be smaller than or exceed the volume of the cage's inner cavity. Upon accommodation of a chiral guest, one of the two cage enantiomers becomes more favored than the other, producing circular-dichroism (CD) signals. The CD signal intensity of the cage is observed to be proportional to the ee value of the chiral guest, allowing a quantitative determination of the latter.

Deep-ultraviolet nonlinear optical (DUV NLO) materials are attracting increasing attention because of their structural diversity and complexity. Using the two-dimensional (2D) crystal structure prediction method combined with the first-principles calculations, here we propose layered 18-membered-ring (18MR) boron oxide B2O3 polymorphs as high-performance NLO materials. 18MR-B2O3 with the AA and AB stackings are potential DUV NLO materials. The superior performing 18MR-B2O3AB has an unprecedentedly high second harmonic generation coefficient of 1.63 pm V-1, the largest among the DUV NLO materials, three times larger than that of the advanced DUV NLO material KBe2BO3F2 and comparable to that of beta-BaB2O4. Its unusually large birefringence of 0.196 at 400 nm guarantees the phase-matching wavelength lambda(PM) to reach this material's extreme absorption edge of approximate to 154 nm.

Condensation of an inherently C3 -symmetric polychlorotriphenylmethyl (PTM) radical trisaldehyde with tris(2-aminoethyl)amine (TREN) yields a [4+4] tetrahedral radical cage as a racemic pair of homochiral enantiomers in 75 % isolated yield. The structure was characterized by X-ray crystallography, confirming the homochirality of each cage framework. The homochirality results from intramolecular [CH⋅⋅⋅π] and hydrogen-bonding interactions within the cage framework. The four PTM radicals in a cage undergo weak through-space coupling. Magnetic measurements demonstrated that each cage bears 3.58 spins.

Self-assembly by imine condensation in aqueous media is a formidable task because of the labile nature of imines in the presence of water. Here, by taking advantage of multivalence and ligand preorganization, basket-shaped triscationic cage molecules are self-assembled in high yields in both water and organic solvent, by condensing a hexaformyl and bisamine. These cages, especially the chiral ones, are stable or inert in aqueous solution, that is, no decomposition was observed upon dilution, precipitation, or exposure to competitive amines or aldehydes. Such water-compatibility allows the hosts to take advantage of the hydrophobic effect to accommodate hydrophobic guests. The chiral cage S-23+ selectively binds and distinguishes one of two enantiomers, opening up opportunities for applications such as chiral compound separation. Chiral narcissistic self-sorting and sergeants-and-soldiers effects occur during cage formation when two amino precursors are involved in self-assembly.

Leupeptin is a bacterial small molecule that is used worldwide as a protease inhibitor. However, its biosynthesis and genetic distribution remain unknown. We identified a family of leupeptins in gammaproteobacterial pathogens, including Photorhabdus, Xenorhabdus, and Klebsiella species, amongst others. Through genetic, metabolomic, and heterologous expression analyses, we established their construction by discretely expressed ligases and accessory enzymes. In Photorhabdus species, a hypothetical protein required for colonizing nematode hosts was established as a new class of proteases. This enzyme cleaved the tripeptide aldehyde protease inhibitors, leading to the formation of "pro-pyrazinones" featuring a hetero-tricyclic architecture. In Klebsiella oxytoca, the pathway was enriched in clinical isolates associated with respiratory tract infections. Thus, the bacterial production and proteolytic degradation of leupeptins can be associated with animal colonization phenotypes.

Organic solid-state semiconductor lasers are attracting ever-increasing interest for their potential application in future photonic circuits. Despite the great progress made in recent years, an organic laser from 3D chiral structures has not been achieved. Now, the first example of an organic nano-laser from the micro-helix structure of an achiral molecule is presented. Highly regular micro-helixes with left/right-handed helicity from a distyrylbenzene derivative (HM-DSB) were fabricated and characterized under microscope spectrometers. These chiral micro-helixes exhibit unique photonic properties, including helicity-dependent circularly polarized luminescence (CPL), periodic optical waveguiding, and length-dependent amplified spontaneous emission (ASE) behavior. The successful observation of laser behavior from the organic micro-helix extends our understanding to morphology chirality of organic photonic materials and provides a new design strategy towards chiral photonic circuits.

Regulation of cellular oxidative stress plays a critical role in revealing the molecular mechanisms of cellular activities and thus is a potential strategy for tumor treatment. Optical methods have been employed for intelligent regulation of oxidative stress in tumor regions. However, long-time continuous irradiation inevitably causes damage to normal tissues. Herein, a ferrocene-containing nucleic acid-based energy-storage nanoagent was designed to achieve the continuous photo-regulation of cellular oxidative stress in the dark. Specifically, the photoenergy stored in the agent could convert effectively and accelerate Fenton-like reaction continuously, augmenting cellular oxidative stress. This nanoagent could also silence oxidative damage repair genes to further amplify oxidative stress. This strategy not only provides oxidative stress regulation for studying the molecular mechanisms of biological activities, but also offers a promising step toward tumor microenvironment modulation.

Covalent organic frameworks (COF) possess a robust and porous crystalline structure, making them an appealing candidate for energy storage. Herein, we report an exfoliated polyimide COF composite (P-COF@SWCNT) prepared by an in situ condensation of anhydride and amine on the single-walled carbon nanotubes as advanced anode for potassium-ion batteries (PIBs). Numerous active sites exposed on the exfoliated frameworks and the various open pathways promote the highly efficient ion diffusion in the P-COF@SWCNT while preventing irreversible dissolution in the electrolyte. During the charging/discharging process, K

The self-assembly of triazole-amphiphiles has been examined in homogenous solution, in the solid state and in the bilayer membranes. Single-crystal X-ray diffraction structures show that stacked protonated Triazole-quartets-T4 quartets are mutually stabilized by strong recognition with two inner anions. Anion Hbonding/ion-pairing are combined with anion-π recognition to produce columnar architectures, resulted through anion-π interactions between anions and triazole moieties of vicinal T 4 quartets. In bilayer membranes, low transport activity is observed when the T 4 channels are operated as H + /Xtranslocators, but higher transport activity is observed when Xtranslocation was performed in the presence of K +carrier valinomycin. The anions channel results are interpreted as arising from discrete stacks of T-quartets where transport of would occur through the stacked T 4 macrocycles. These self-assembled channels presenting amazing structural behaviours, directionality, strong anion encapsulation via H-bonding supported with vicinal anion-π interactions are proposed as artificial supramolecular channels that transport anions across lipid bilayer membranes.

Heterasumanenes 4-6 containing chalcogen (S, Se, and Te) and phosphorus atoms have been synthesized in a one-pot reaction from trichalcogenasumanenes 1-3 by replacing one chalcogen atom with a P=S unit. The P=S unit makes 4-6 almost planar and shrinks the HOMO-LUMO gap as compared to 1-3. The bonding between Ag+ and S atom on P=S brings about a distinct change to the optical properties of 4-6; 4 in particular shows a selective fluorescence response toward Ag+ with LOD of 0.21 μm. Compounds 4-6 form complexes with AgNO3 to be (4)2 ⋅AgNO3 , (5)2 ⋅AgNO3 , and (6)2 ⋅(AgNO3 )3 . In complexes, the coordination between Ag+ and P=S is observed, which leads to shrinkage of C-P and C-X (X=S, Se, Te) bond lengths. As a result, 4, 5, and 6 are all bowl-shaped in complexes with bowl-depths reaching to 0.66 A, 0.42 A, and 0.40 A, respectively. There are Ag-Te dative bonds between Ag+ and Te atom on telluorophene in (6)2 ⋅(AgNO3 )3 .

Oxime, whose dynamic nature was reported to be switchable between ON/OFF by tuning the acidity, is employed in a novel type of dynamic covalent approach that is amenable to use in water for self-assembly of purely organic molecules with complex topology. In strongly acidic conditions, the dynamic nature of oxime is turned ON, allowing occurrence of error-checking and therefore a catenane and a macrocycle self-assembled in high yields. In neutral conditions, oxime ceases to be dynamic, which helps to trap the self-assembled products even when the driving forces of their formation are removed. We envision that this switchable behaviour might help, at least partially, to resolve a commonly encountered drawback of dynamic covalent chemistry, namely that the intrinsic stability of the self-assembled products containing dynamic bonds, such as imine or hydrazone, are often jeopardized by their reversible nature.

As a new type of heterogeneous catalyst with "homogeneous-like" activity, single-site transition-metal materials are usually treated as integrated but separate active centers. A novel grouping effect is reported for single Ni-N4 sites in nitrogen-doped carbon (Ni/NC), where an effective ligand-stabilized polycondensation method endows Ni/NC nanocatalysts with a high content of single-site Ni up to 9.5 wt %. The enhanced electron density at each single Ni-N4 site promotes a highly efficient hydrogen transfer, which is exemplified by the coupling of benzyl alcohol and aniline into N-benzylaniline with a turnover frequency (TOF) value of 7.0 molN-benzylaniline molmetal-1 h-1 ; this TOF outpaces that of reported stable non-noble-metal-based catalysts by a factor of 2.

The exploitation of metal-free organic polymers as electrodes for water splitting reactions is limited by their presumably low activity and poor stability, especially for the oxygen evolution reaction (OER) under more critical conditions. Now, the thickness of a cheap and robust polymer, poly(p-phenylene pyromellitimide) (PPPI) was rationally engineered by an in situ polymerization method to make the metal-free polymer available for the first time as flexible, tailorable, efficient, and ultra-stable electrodes for water oxidation over a wide pH range. The PPPI electrode with an optimized thickness of about 200 nm provided a current density of 32.8 mA cm-2 at an overpotential of 510 mV in 0.1 mol L-1 KOH, which is even higher than that (31.5 mA cm-2 ) of commercial IrO2 OER catalyst. The PPPI electrodes are scalable and stable, maintaining 92 % of its activity after a 48-h chronoamperometric stability test.

Small-molecule regulation is a powerful switching tool to manipulate cell signal transduction for a desired function; however, most available methods usually require genetic engineering to endow cells with responsiveness to user-defined small molecules. Herein, we demonstrate a nongenetic approach for small-molecule-controlled receptor activation and consequent cell behavior manipulation that is based on DNA-mediated chemically induced dimerization (D-CID). D-CID uses a programmable chemical-responsive DNA nanodevice to trigger DNA strand displacement and induce the activation of c-Met, a tyrosine kinase receptor cognate for hepatocyte growth factor, through dimerization. Through the use of various functional nucleic acids, including aptamers and DNAzymes, as recognition modules, the versatility of D-CID in inducing c-Met signaling upon addition of various small-molecular or ionic cues, including ATP, histidine, and Zn2+ , is demonstrated. Moreover, owing its multi-input properties, D-CID can be used to manipulate the behaviors of multiple cell populations simultaneously in a selective and programmable fashion.

Die Halbleiter-Photokatalyse ist eine vielversprechende Methode fur die Nutzung von Sonnenlicht fur Energieumwandlungen. Ihre Effizienz ist derzeit jedoch aufgrund einer begrenzten Lichtreaktion und/oder der ausgepragten Rekombination der Ladungstrager noch unbefriedigend. Moderne Charakterisierungstechniken sowie Berechnungen der elektronischen Struktur zeigen, dass selbst winzige Konzentrationen von Sauerstoff-Leerstellen (“oxygen vacancies”, OVs) auf der Oberflache realer Photokatalysatoren deren Kinetik und Energetik sowie die Mechanismen photokatalytischer Reaktionen entscheidend beeinflussen konnen. Dieser Aufsatz stellt die inharente photokatalytische Funktionalitat von OVs auf BiOCl-Oberflachen auf molekularer Ebene dar. Die Korrelation zwischen der Struktur der OVs und Reaktivitat sowie Selektivitat photokatalytischer Reaktionen wird am Beispiel von OVs auf prototypischen BiOCl-Flachen eingehend diskutiert.

The regioselective transformation of heterobuckybowl trichalcogenasumanenes 1 a,b at peripheral butoxy groups afforded trichalcogenasumanene ortho-quinones 2 a,b. Compounds 2 a,b are distinct from 1 a,b in terms of their molecular geometry and electronic state; that is, they have a shallower bowl depth and show absorbance in the NIR region. The reaction of 2 a,b with diamines resulted in a variety of heteropolycycles, including molecular spoon 3 a–6 a, planar π-systems 3 b–6 b, and highly twisted [7-6-6]-fused systems 7 a,b. These new heteropolycycles had different optical/electrical properties: 4 a,b showed hole mobility of approximately 0.002 cm2 V−1 s−1, 6 a displayed red emission in both solution and the solid state, and 7 a,b formed tight stacks of the curved π-surface.

The atomic layer deposition (ALD) of iron sulfide (FeSx ) is reported for the first time. The deposition process employs bis(N,N'-di-tert-butylacetamidinato)iron(II) and H2 S as the reactants and produces fairly pure, smooth, and well-crystallized FeSx thin films following an ideal self-limiting ALD growth behavior. The FeSx films can be uniformly and conformally deposited into deep narrow trenches with aspect ratios as high as 10:1, which highlights the broad applicability of this ALD process for engineering the surface of complex 3D nanostructures in general. Highly uniform nanoscale FeSx coatings on porous γ-Al2 O3 powder were also prepared. This compound shows excellent catalytic activity and selectivity in the hydrogenation of azo compounds under mild reaction conditions, demonstrating the promise of ALD FeSx as a catalyst for organic reactions.