Multicolor recordable and erasable photonic crystals based on on-off thermoswitchable mechanochromism toward inkless rewritable paper.

Mechanochromic photonic crystals are attractive due to their force-dependent structural colors; however, showing unrecordable color and unsatisfied performances, which significantly limits their development and expansion toward advanced applications. Here, a thermal-responsive mechanochromic photonic crystal with a multicolor recordability-erasability was fabricated by combining non-close-packing mechanochromic photonic crystals and phase-change materials. Multicolor recordability is realized by pressing thermal-responsive mechanochromic photonic crystals to obtain target colors over the phase-change temperature followed by fixing the target colors and deformed configuration at room temperature. The stable recorded color can be erased and reconfigured by simply heating and similar color-recording procedures respectively due to the thermoswitchable on-off mechanochromism of thermal-responsive mechanochromic photonic crystals along with solid-gel phase transition. These thermal-responsive mechanochromic photonic crystals are ideal rewritable papers for ink-freely achieving multicolor patterns with high resolution, difficult for conventional photonic papers. This work offers a perspective for designing color-recordable/erasable and other stimulus-switchable materials with advanced applications.

Metal-organic framework photonic crystals with bidisperse particles-based brilliant structural colors and high optical transparency for elaborate anti-counterfeiting.

Photonic crystals (PCs) have attracted great interest and wide applications in displays, printing, anti-counterfeiting, etc. However, two main challenges significantly hinder their applications: 1) the tradeoff between high optical transparency across the whole visible range and brilliant colors requiring a large refractive index contrast (Δn), and 2) the way of regulating structural colors by altering tens of different sizes. To address these issues, a new type of metal-organic framework (MOF)-based transparent photonic crystal (TPC) has been fabricated through self-assembling MOF particles into three-dimensional ordered structures which were then infiltrated by polydimethylsiloxane (PDMS). Compared to conventional PCs, these TPCs exhibit 1) both brilliant forward iridescent structural colors and high transmittance (>75 %) across the whole visible spectra range, and 2) conveniently adjustable colors based on bidisperse particles. The unique color-generating mechanism of the light diffraction by each plane lattice and the small Δn between MOF particles and PDMS are the keys to TPCs' characteristics. Moreover, the prepared invisible anti-counterfeit labels can reversibly hide-reveal patterns with elaborate and exchangeable color contrast in a non-destructive way, showing potential applications in anti-counterfeiting, information encryption, and optical devices.

Smart colloidal photonic crystal sensors.

Smart colloidal photonic crystals (PCs) with stimuli-responsive periodic micro/nano-structures, photonic bandgaps, and structural colors have shown unique advantages (high sensitivity, visual readout, wireless characteristics, etc.) in sensing by outputting diverse structural colors and reflection signals. In this review, smart PC sensors are summarized according to their fabrications, structures, sensing mechanisms, and applications. The fabrications of colloidal PCs are mainly by self-assembling the well-defined nanoparticles into the periodical structure (supersaturation-, polymerization-, evaporation-, shear-, interaction-, and field-induced self-assembly process). Their structures can be divided into two groups: closely packed and non-closely packed nano-structures. The sensing mechanisms can be explained by Bragg's law, including the change in the effective refractive index, lattice constant, and the order degree. The sensing applications are detailly introduced according to the analytes of the target, including solvents, vapors, humidity, mechanical force, temperature, electrical field, magnetic field, pH, ions/molecules, and so on. Finally, the corresponding challenges and the future potential prospects of artificial smart colloidal PCs in the sensing field are discussed.

Mechanochromic and Solvomechanochromic Fluorescent Photonic Crystals for Dual-Mode Modulating Fluorescence and Multilevel Anticounterfeiting.

Fluorescent photonic crystals (FPCs) are ideal candidates for regulating dyes' fluorescence through their unique photonic band gaps (PBGs). However, challenges, including the lack of dynamic regulation of fluorescence, dye release in solvents, and instability, dramatically limit their practical applications. Here, we report mechanochromic and solvomechanochromic rhodamine B (RhB)-based FPCs with dynamic regulation of photoluminescence (PL) by stretching and swelling, brilliant fluorescent and structural colors, and no release of the RhB in solvents. The FPCs with force/solvent-responsive nonclose-packing structures were fabricated by (1) preparing RhB-silica particles by combining click chemistry and cohydrolysis processes and (2) self-assembling these particles in poly(ethylene glycol) phenyl ether acrylate followed by a photopolymerization. Maximal PL inhibition (37%, stretching strain of 6.8%) and enhancement (150%, swelling time of 8 min) were gained when PBGs and their blue edges are precisely adjusted to the PL peak position, respectively. Compared with stretching, PL regulation is more efficient by swelling. These characteristics benefit from the rational design and combination of unique compositions, chemical bonds, nonclosely packed micro/nanostructures, and solvents for swelling. Moreover, these FPCs have been used to encrypt photonic patterns, which display background/strain/angle/UV-dependent color contrasts, showing their potential applications in multilevel anticounterfeiting, optical devices, wireless sensors, etc.

Genome-Wide Identification and Expression Patterns of Cucumber Invertases and Their Inhibitor Genes.

Invertases and their inhibitors play important roles in sucrose metabolism, growth and development, signal transduction, and biotic and abiotic stress tolerance in many plant species. However, in cucumber, both the gene members and functions of invertase and its inhibitor families remain largely unclear. In this study, in comparison with the orthologues of Citrullus lanatus (watermelon), Cucumis melo (melon), and Arabidopsis thaliana (Arabidopsis), 12 invertase genes and 12 invertase inhibitor genes were identified from the genome of Cucumis sativus (cucumber). Among them, the 12 invertase genes were classified as 4 cell wall invertases, 6 cytoplasmic invertases, and 2 vacuolar invertases. Most invertase genes were conserved in cucumber, melon, and watermelon, with several duplicate genes in melon and watermelon. Transcriptome analysis distinguished these genes into various expression patterns, which included genes CsaV3_2G025540 and CsaV3_2G007220, which were significantly expressed in different tissues, organs, and development stages, and genes CsaV3_7G034730 and CsaV3_5G005910, which might be involved in biotic and abiotic stress. Six genes were further validated in cucumber based on quantitative real-time PCR (qRT-PCR), and three of them showed consistent expression patterns as revealed in the transcriptome. These results provide important information for further studies on the physiological functions of cucumber invertases (CSINVs) and their inhibitors (CSINHs).

Metabolomics and Transcription Profiling of Pumpkin Fruit Reveals Enhanced Bioactive Flavonoids and Coumarins in Giant Pumpkin (Cucurbita maxima).

Atlantic giant (AG, Cucurbita maxima) is a type of giant pumpkin in the Cucurbitaceae family and has the world's largest fruit. AG possesses excellent ornamental and economic value due to its well-known large fruit. However, giant pumpkins are usually thrown away after viewing, thus generating a waste of resources. To explore the additional value of giant pumpkins, a metabolome assay was performed between AG and Hubbard (a small fruit pumpkin) fruits. We found that bioactive compounds, especially flavonoids (including 8-prenylnaringenin, tetrahydrocurcumin, galangin, and acacetin) and coumarins (including coumarin, umbelliferone, 4-coumaryl alcohol, and coumaryl acetate), with extensive antioxidant and pharmacological functions, showed higher accumulation in AG fruit than in Hubbard fruits. Comparative transcriptomics of the two pumpkin fruits indicated that the differentially expressed genes (DEGs) encoding PAL, C4H, 4CL, CSE, HCT, CAD, and CCoAOMT were relatively highly expressed, which promoted an increased accumulation of the identified flavonoids and coumarins in giant pumpkins. In addition, the construction of a co-expression network and cis-element analysis of the promoter demonstrated that differentially expressed MYB, bHLH, AP2, and WRKY transcription factors might play vital roles in regulating the expression of DEGs involved in the biosynthesis of several flavonoids and coumarins. Our current results provide new insights into the accumulation of active compounds in giant pumpkins.

Structure-property-performance relationship of transition metal doped WO3 mixed oxides for catalytic degradation of organic pollutants.

Transition metal doped WO3 mixed oxides (named as W-M-O, M = Nb, Fe, Cr, Cu, Ti or Sn, respectively) with high structure stability were synthesized by modified sol-gel method using citric acid as organic crosslinking agent, and were evaluated for catalytic elimination of low-concentration toluene, monochlorobenzene and 1,2-dichloroethance with high toxicity and relatively stable molecule structure, as the typical examples for the pollutants of various volatile organic compounds (VOCs). Results of the structure-property-performance relationship research showed that mesoporous structure and nanocrystalline/amorphous state were formed, and binary metal components were dispersed into each other, which contributed to promoting the metal/metal electron interaction and adjusting the physicochemical properties of mixed metal oxides. The sequence of apparent catalytic activity for toluene degradation was: W-Nb-O＞W-Fe-O＞W-Cr-O, W-Cu-O＞W-Ti-O＞W-Sn-O＞WO3, and the sequence for monochlorobenzene degradation was: W-Nb-O＞W-Fe-O＞W-Cr-O, W-Ti-O＞W-Cu-O＞W-Sn-O＞WO3. There existed cooperative catalytic effect: mesopore and surface acid sites of catalysts facilitated adsorption, activation and breakage of the C-X bond, and then redox sites of catalysts promoted deep oxidation of a series of reaction intermediates to transform into CO2 and H2O. Especially, the optimized W-Nb-O catalyst deserved more attention, since it represented remarkable catalytic activity, selectivity and durability for three typical VOCs degradation along with good resistance to water vapor and corrosion of HCl.

Formation of n-Hexane-in-DMF Nonaqueous Pickering Emulsions: ABC Triblock Worms versus AB Diblock Worms.

Nonaqueous Pickering emulsions exhibit promising applications in many industrial areas but have been relatively less studied in the past. In this study, n-hexane-in-DMF nonaqueous Pickering emulsions stabilized by core cross-linked copolymer worms with mixed shells are demonstrated for the first time. Core cross-linked copolymer worms with mixed shells were prepared by seeded reversible addition-fragmentation chain transfer (RAFT) quasi-solution polymerization. Specifically, polystyrene-poly(4-vinylpyridine) (PS-P4VP) diblock copolymer worms were first prepared via RAFT-mediated dispersion polymerization in toluene under the given conditions using PS as both the macro-CTA and the stabilizer block. After the chemical cross-linking of P4VP cores, PS-P4VP diblock copolymer worms were chain-extended with LMA in DMF/toluene (1:9, weight ratio) mixed solvents, producing core cross-linked PS-P4VP-PLMA worms with PS/PLMA mixed shells. The as-prepared core cross-linked PS-P4VP-PLMA worms with mixed PS/PLMA shells were further utilized as Pickering emulsifiers for the generation of nonaqueous n-hexane-in-DMF Pickering emulsions. The emulsifying performances of mixed-shell copolymer worms were compared with those of their spherical and linear analogues with entirely identical chemical compositions as well as PS-P4VP diblock copolymer worm precursors, respectively.

Simultaneously Enhancing Catalytic Performance and Increasing Density of Bifunctional CuN3 Active Sites in Dopant-Free 2D C3N3Cu for Oxygen Reduction/Evolution Reactions.

Atomically dispersed M-N-C has been considered an effective catalyst for various electrochemical reactions such as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), which faces the challenge of increasing metal load while simultaneously maintaining catalytic performance. Herein, we put forward a strategy for boosting catalytic performances of a single Cu atom coordinated with three N atoms (CuN3) for both ORR and OER by increasing the density of connected CuN3 moieties. Our calculations first show that a single CuN3 moiety exhibiting no catalytic performance for ORR and OER can be activated by increasing the density of metal centers, which weakens the binding affinity to *OH due to the lowered d-band center of the metal atoms. These findings stimulate the further theoretical design of a two-dimensional compound of C3N3Cu with a high concentration of homogeneously distributed CuN3 moieties serving as bifunctional active sites, which demonstrates efficient catalytic performance for both ORR and OER as reflected by the overpotentials of 0.71 and 0.43 V, respectively. This work opens a new avenue for designing effective single-atom catalysts with potential applications as energy storage and conversion devices possessing high density of metal centers independent of the doping strategy and defect engineering, which deserves experimental investigation in the future.

CuCl2·2H2O/TBHP mediated synthesis of ß-enaminones via coupling reaction of vinyl azides with aldehydes.

A facile and efficient oxidative functionalization of vinyl azides with aldehydes furnishing a diverse array of ß-acylated enaminones was developed. The cross coupling was accomplished in the presence of CuCl2·2H2O/TBHP and produced the desired ß-acylated enaminones in a (Z)-stereo-selective and atom-economic manner, which make this protocol particularly attractive. In the transformation, the new C-C and C-N bonds were formed via a one-pot strategy including the process of radical addition and recombination.

An efficient domino strategy for synthesis of 3-substituted 4-oxo-4,5-dihydro-1H-pyrrolo[3,2-c]pyridine derivatives in water.

A strategy for catalyst-free domino reaction of 4-aminopyridin-2(1H)-ones, arylglyoxal hydrates and different 1,3-dicarbonyl compounds in water has been established. The mild and efficient procedure afforded pyrrolo[3,2-c]pyridine derivatives with 76-94% yields after simple crystallization. The present procedure shows promising characteristics, such as readily available starting materials, the use of water as reaction media, simple and efficient one-pot operation, and avoiding the need for any hazardous or expensive catalysts.

H2O2-mediated room temperature synthesis of 2-arylacetophenones from arylhydrazines and vinyl azides in water.

An environmentally benign, cost-efficient and practical methodology for the room temperature synthesis of 2-arylacetophenones in water has been discovered. The facile and efficient transformation involves the oxidative radical addition of arylhydrazines with α-aryl vinyl azides in the presence of H2O2 (as a radical initiator) and PEG-800 (as a phase-transfer catalyst). From the viewpoint of green chemistry and organic synthesis, the present protocol is of great significance because of using cheap, non-toxic and readily available starting materials and reagents as well as amenability to gram-scale synthesis, which provides an attractive strategy to access 2-arylacetophenones.

Metallic C5N monolayer as an efficient catalyst for accelerating redox kinetics of sulfur in lithium-sulfur batteries.

Lithium-sulfur battery is one of the most promising applicants for the next generation of energy storage devices whose commercial applications are impeded by the key issue of the shuttle effect. To overcome this obstacle, various two-dimensional (2D) carbon-based metal-free compounds have been proposed to serve as anchoring materials for immobilizing soluble lithium polysulfides (LiPs), which however suffer from low electronic conductivity implying unsatisfactory performance for catalyzing sulfur redox. Therefore, we have predicted metallic C5N monolayers, possessing hexagonal (H) and orthorhombic (O) phases, exhibiting excellent performance for suppressing the shuttle effect. First-principles simulations demonstrate that O-C5N could serve as a bifunctional anchoring material due to its strong adsorption capability to LiPs and excellent catalytic performance for sulfur redox with active sites from both basal plane and zigzag edges. Furthermore, the rate of Li2S oxidation over O-C5N is fast due to the low energy barrier of 0.93 eV for Li2S decomposition. While for H-C5N, only N atoms located at the armchair edges can efficiently trap LiPs and boost the formation and dissociation of Li2S during discharge and charge processes, respectively. The current work opens an avenue of designing 2D metallic carbon-based anchoring materials for lithium-sulfur batteries, which deserves further experimental research efforts.

Pickering Emulsions Stabilized by Diblock Copolymer Worms Prepared via Reversible Addition-Fragmentation Chain Transfer Aqueous Dispersion Polymerization: How Does the Stimulus Sensitivity Affect the Rate of Demulsification?

Responsive Pickering emulsions exhibit promising application in industry owing to the integration of the high storage stability with on-demand demulsification. In this study, stimuli-responsive Pickering emulsions stabilized by poly[oligo(ethylene glycol) methyl ether methacrylate]15-b-poly(diacetone acrylamide)120 (E15D120) worms were indicated, in which E15D120 worms were prepared via reversible addition-fragmentation chain transfer-based aqueous dispersion polymerization using thermo-sensitive POEGMA15 as both the stabilizer block and macro-chain transfer agent. The factors influencing the morphologies of copolymers during polymerization-induced self assembly have been investigated. A series of different morphological polymer nanoparticles including spheres, worms, and vesicles could be produced through rational synthesis. E15D120 worms demonstrated excellent emulsifying performances and could be used as emulsifiers to form n-dodecane-in-water Pickering emulsions at a low content. The formed n-dodecane-in-water Pickering emulsions revealed a slow demulsification at pH 10 or 70 °C or pH 10/70 °C combinations, and several hours were needed for the demulsification of Pickering emulsions. However, n-dodecane-in-water Pickering emulsions displayed a rapid demulsification (∼10 min) at an elevated temperature, such as 90 °C. The different demulsification rates were attributed to different sensitivities of E15D120 worms to external stimuli. Pickering emulsions integrating a rapid responsive demulsification with a slow one would be well satisfactory on different occasions.

Vertical growth of SnS2 nanobelt arrays on CuSbS2 nanosheets for enhanced photocatalytic reduction of CO2.

Two-dimensional SnS2 nanobelt arrays vertically grown on two-dimensional CuSbS2 nanosheet (2D SnS2⊥2D CuSbS2) heterostructures were synthesized via a facile solution-phase growth route. The resultant SnS2⊥CuSbS2 heterostructures showed enhanced photocatalytic activity for CO2 reduction because of unique structural advantages and the p-n heterojunction with matched energy band alignment.

Simple and efficient one-pot multi-step strategy for the synthesis of 2-substituted (1,2,5-triarylpyrrolo[3,2-c]pyridin-3-yl)-N-arylacetamide derivatives in water.

A novel one-pot multi-step domino strategy for the synthesis of functionalized 2-substituted acetic acids, 2-substituted (1,2,5-triarylpyrrolo[3,2-c]pyridin-3-yl)acetates and 2-substituted-(1,2,5-triarylpyrrolo[3,2-c]pyridin-3-yl)-N-arylacetamides has been established from inexpensive and readily available starting materials. The reaction can be easily performed by employing different substrates via a one-pot multi-step domino reaction. The target products can be easily obtained with satisfactory yields by only simple recrystallization from a mixture of hot 95% ethanol and N,N-dimethylformamide. The reaction features of readily available starting materials, broad substrate scope, bond-forming efficiency, simple one-pot multi-step synthesis as well as green reaction media, make the procedure highly useful for the construction of potential pharmacological heterocyclic molecules.

Amphiphilic Double-Brush Copolymers with a Polyurethane Backbone: A Bespoke Macromolecular Emulsifier for Ionic Liquid-in-Oil Emulsion.

The study on ionic liquid (IL)-based emulsions is very interesting due to the "green" quality and potential wide applications of ILs, whereas the emulsifiers for the formation of IL-based emulsions are extremely limited and mainly centered on low molecular weight surfactants. In this work, synthesis of amphiphilic double-brush copolymers (DBCs) and their application as bespoke macromolecular emulsifiers for the formation of IL-containing non-aqueous emulsions are described. DBCs consisted of a polyurethane (PU) backbone and poly(N,N-dimethyl acrylamide) (PDMA) and poly(methyl methacrylate) (PMMA) chains that were grafted simultaneously at the same reactive site along the PU backbone (PU-g-PDMA/PMMA), which were synthesized through the combination of polyaddition and the reversible-deactivation radical polymerization reactions. Highly stable [Bmim][PF6]-in-benzene emulsions could be gained by adopting PU-g-PDMA/PMMA DBCs as macromolecular emulsifiers at a low content, such as 0.025 wt %. On the basis of the stability and the size of emulsion droplets, PU-g-PDMA/PMMA DBCs exhibited much better emulsifying performances than their analogues, including PU-g-PDMA, PU-g-PMMA, and PDMA-b-PMMA copolymers. Such excellent emulsifying performances of PU-g-PDMA/PMMA DBCs were due to high interfacial activities. PU-g-PDMA/PMMA DBCs exhibited higher capabilities in lowering the interfacial tension of the [Bmim][PF6]-benzene interface than their analogues. A large energy barrier to desorption of adsorbed PU-g-PDMA/PMMA DBCs from the interface contributed to high stability of the [Bmim][PF6]-in-benzene emulsion.

Cobalt(ii)-catalyzed hydroarylation of 1,3-diynes and internal alkynes with picolinamides promoted by alcohol.

The Co(ii)-catalyzed selective C-H alkenylation of picolinamides with 1,3-diynes has been developed. This protocol can be applied to a variety of 1,3-diynes. In addition, both symmetrical and unsymmetrical internal alkynes were well tolerated, affording the corresponding alkenyl arenes. Moreover, control experiments indicated that C-H bond cleavage may be involved in the rate-determining step. Furthermore, a deuterium incorporation product was achieved when deuterated alcohol was employed as the solvent, which suggested that alcohol was essential for the final protonolysis.

Janus-Like Single-Chain Polymer Nanoparticles as Two-in-One Emulsifiers for Aqueous and Nonaqueous Pickering Emulsions.

The exploration of Pickering emulsions is very significant owing to their versatile and important applications in many scopes. In this study, synthesis of a novel kind of single-chain polymer nanoparticle (SCPN) and its stabilized Pickering emulsions were demonstrated. To this end, linear-dendritic diblock copolymers consisting of poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA) blocks and four-generation dendritic aliphatic polyester blocks (G4) have been first synthesized by the combination of click chemistry and reversible addition-fragmentation chain transfer (RAFT) polymerization reaction. The subsequent intramolecular cross-linking of the PDMAEMA block of PDMAEMA-b-G4 copolymers in DMF using 1,4-diiodobutane as cross-linkers afforded Janus-like SCPNs that exhibited a cross-linked PDMAEMA head tethered by a short dendritic tail. The molecular weight and distribution together with the structure of polymers were carefully characterized by GPC and NMR spectroscopy. By the employment of the as-synthesized Janus-like SCPNs as Pickering emulsifiers, aqueous and nonaqueous Pickering emulsions including water-in-oil and oil-in-oil as well as ionic liquid-in-oil were generated. Under the same conditions, it was found that the long-term stabilities of Pickering emulsions stabilized by Janus-like SCPNs were superior to those of Pickering emulsions stabilized by their linear quaternized PDMAEMA-b-G4 by CH3I analogous.

Chitosan modified Ti-PILC supported PdOx catalysts for coupling reactions of aryl halides with terminal alkynes.

Biopolymer of chitosan (CS) and titanium pillared clays (Ti-PILCs) have been combined in a hybrid as advanced supports for immobilization of PdOx=0,1 species to prepare novel PdOx=0,1@Ti-PILC/CS nano-composite catalysts. The Ti-PILC materials showed high specific surface areas and abundant meso-porous structure with many irregular pore channels caused by collapses of layered structure of clay during Ti pillaring process. Both CS chains and sub-nano sized PdOx particles were successfully incorporated into the pore channels of Ti-PILC, resulting in a decrease in both the specific surface areas and uniform distribution of pore size. Besides conventional methods characterizations, the strong interactions between PdOx species and Ti-PILC/CS support were further evidenced with positron annihilation lifetime spectroscopy studies. The resultant PdOx@Ti-PILC/CS catalyst was highly active for the coupling reactions of aryl halides with phenyl acetylenes. It was recyclable and gave excellent yield up to 13 runs with low leaching of Pd species.