Millimeter-Sized K2MnF6:Si4+, NH4+ Red-Luminescent Crystals with High Absorption Efficiency (AEmax of 93.5%) and External Quantum Efficiency (EQEmax of 68.9%) Grown by Cooling-Induced Crystallization.

Luminescent bulk crystals exhibit fewer grain boundaries and defects compared with conventional microsized powdery ones. Herein, targeting Mn4+-activated fluoride crystals with a sharp line-type red luminescence spectrum, we propose a new cooling-induced crystallization method to grow the fluoride crystals. By this new method, we successfully grew millimeter-sized K2MnF6:Si4+, NH4+ crystals, featuring an AEmax (absorption efficiency) of 93.5% and an EQEmax (external quantum efficiency) of 68.9%, which are among the best values for Mn4+-activated fluoride red phosphors. The influence of doping Si4+ and/or NH4+ in K2MnF6 on the local coordination structure and luminescence properties was studied. The anomalous thermal quenching behaviors were discussed, the luminescence decay from the excited state was compared, and the origin for the high quantum efficiencies was analyzed.

Light-assisted anti-wrinkling on azobenzene-containing polyblend films.

Undesired surface wrinkling is a persistent issue far from being resolved. Here, we report a simple light-assisted strategy to prevent surface wrinkling on azobenzene-containing polyblend films, which is based on the unique photo-responsive behaviors of azobenzene moieties. Upon visible light irradiation, the mechanical strain-induced surface wrinkling of the azo-based polyblend film attached on a pre-strained compliant substrate can be effectively suppressed. The influence of light irradiation conditions and polyblend composition on the wrinkling resistance has been systematically investigated. Notably, empirical scaling laws that can quantify the connection of the critical wrinkling conditions with external and internal factors are derived. This spatiotemporal light-assisted strategy combined with the simple universal blending method would provide a general guideline for the anti-wrinkling purpose in diverse functional material systems/devices.

Polarization-Dependent Ultrasensitive Dynamic Wrinkling on Floating Films Induced by Photo-Orientation of Azopolymer.

Ubiquitous surface wrinkling has been well-studied theoretically and experimentally. How to modulate the stress state of a liquid-supported system for the unexploited wrinkling capabilities remains a challenge. Here we report a simple linearly-polarized-light illumination to spatiotemporally trigger ultrasensitive in situ dynamic wrinkling on a floating azo-film. The smart combination of the liquid substrate with photoresponsive azo-moieties leads to the light-induced ultrafast wrinkling evolution, accompanied by unprecedented sequential wrinkling orientation conversion (from polarization-parallel to polarization-perpendicular). The involved different polarization-dependent sequential photo-orientation for azo side chains and azo-grafted main chains of azopolymers is disclosed experimentally for the first time. Meanwhile, programmable dynamic wrinkling with all-optical switchable surface topographies is available, which has wide application potentials in photoresponsive soft photonics.

BaTiF6:Mn4+ Red Phosphor: Synthesis of Single Crystals at Room Temperature and the High Hydrolysis-Resistant Property.

Due to the low solubility of BaF2, the BaTiF6:Mn4+ phosphor for whitelight-emitting diodes application has been generally synthesized by the hydrothermal route, during which process the valence of the manganese dopant is difficult to be controlled as tetravalent. In this paper, a new synthesis method that proceeded at room temperature was reported. This method uses BaTiOF4 as the precursor and allows for the control of the phase transformation rate from BaTiOF4 to BaTiF6 in the K2MnF6/HF acid solution. Benefitting from that, we successfully prepared red-emitting BaTiF6:Mn4+ elongated crystals with a single-crystal nature up to a record-breaking length of 200-300 µm. The effects of the crystallinity of the BaTiOF4 precursor on its phase transformation rate into BaTiF6 and on the optimal Mn4+ doping concentration were studied. The BaTiF6:Mn4+ single-crystal phosphor exhibits relatively excellent hydrolysis-resistant behavior after being immersed in water for 3 h, at which condition the commercial K2SiF6:Mn4+ has become brown. This study may inspire the room-temperature preparation of other hydrolysis-resistant alkali earth fluorotitanate or fluorosilicate phosphors with stable tetravalent manganese doping.

Light-Associated Surface Wrinkling-Based Metrology for the Photosoftening Characterization in Azobenzene-Polymer Supramolecular Complexes.

As an intriguing characteristic of azobenzene-containing materials (azo-materials), photoinduced changes in mechanical properties (e.g., photosoftening) have stimulated many efforts both theoretically and experimentally. Here a simple yet powerful tool (i.e., a light-associated surface wrinkling-based method) to study the photosoftening effect in azobenzene-polymer (azo-polymer) supramolecular complexes is reported. The photo-induced modulus decrease of supramolecular complex films is deduced by analyzing the change of critical wrinkle wavelength of strain-induced surface wrinkling, in the case of varying experiment parameters. In particular, thanks to the facile modular tunability of the supramolecular system, the photosoftening effect has been systematically investigated as a function of azo-moiety content and the molecular weight of the host polymer. Notably, a photosoftening coefficient that is related to the chemical composition/structure of azo-polymers is introduced, and a simple formula that can quantify the connection of the photosoftening with external irradiation conditions and internal chemical factors of azo-polymers is derived for the first time. The obtained results are of great importance not only to enhance understanding of the photosoftening mechanism, but also to thoroughly apply it in diverse smart fields.

Microsized Red Luminescent MgAl2O4:Mn4+ Single-Crystal Phosphor Grown in Molten Salt for White LEDs.

A single-crystalline defect-less phosphor is desired for efficient luminescence of the therein doped optical activators. In this paper, microsized MgAl2O4:Mn4+ single-crystal phosphors with bright red luminescence were grown in molten LiCl salt at 950 °C, for application in blue LED pumped white lighting. By comparing the phosphor formation from various Mg2+- and Al3+-bearing sources, both the template-formation and the dissolution-diffusion processes were evidenced to account for the formation of the microsized MgAl2O4:Mn4+ crystallites. Using nano γ-Al2O3 as the Al3+-bearing precursor, the uniform MgAl2O4:Mn4+ microcrystallites with a {111} planes-exposed tetragonal bipyramid morphology were obtained. The photoluminescence property was studied at various temperatures, and Mg ↔ Al anti-site disorder induced luminescence broadening was discussed. The Mn4+ 2Eg → 4A2g transition in MgAl2O4 shows a quite short luminescence wavelength peaking at 651 nm and ultrabroadband emission extending to 850 nm. The luminescence is relatively robust against thermal effect with relatively high thermal quenching temperature of 400 K and activation energy of 0.23 eV. Employing the red-emitting MgAl2O4:Mn4+ crystallites, blue LED pumped white lighting prototypes were fabricated which simulate the solar-like spectrum and show neutral to warm white.

Intense deep-red zero phonon line emission of Mn4+ in double perovskite La4Ti3O12.

Phosphors that emit in the deep-red spectral region are critical for plant cultivation light-emitting diodes. Herein, ultrabroadband deep-red luminescence of Mn4+ in La4Ti3O12 was studied, which showed intense zero phonon line emission. The double-perovskite structural La4Ti3O12 simultaneously contains two Ti4+ sites forming slightly- and highly-distorted TiO6 octahedra, respectively. The influence of octahedral distortion on the Mn4+ emission energy in the two distinct Ti4+ sites was studied both experimentally and theoretically. The spectral measurements indicated that Mn4+ in La4Ti3O12 showed intense zero phonon line emission (ZPL) at deep-red 710-740 nm under excitation of 400 nm charging the O2-→ Mn4+ charge transfer transition. The splitting of the ZPL of the Mn4+ 2Eg→4A2g transition as well as the intensity of ZPL relative to the vibronic phonon sideband emissions were found to be greatly influenced by the degree of octahedral distortion. The crystal-field strength and Racah parameters of Mn4+ in each Ti4+ site were also estimated. The Mn4+ 2Eg→4A2g luminescence exhibited severe thermal quenching, which was explained by the low-lying 4T2g level and charge-transfer state.

Redox-Switchable Surface Wrinkling on Polyaniline Film.

Here the redox-driven switch between the wrinkled and dewrinkled states on poly-aniline (PANI) film is reported. This switch is derived from the reversible transition in different intrinsic redox states of polyaniline (e.g., between emeraldine salt (ES) and leucoemeraldine base (LEB) or between ES and pernigraniline base (PB)) that are involved in the redox reaction, coupled with the corresponding volume expansion/shrinkage. Interestingly, the as-wrinkled ES film becomes deswollen and dewrinkled when reduced to the LEB state or oxidized to the PB state. Conversely, oxidation of the LEB film or reduction of the PB film into the swollen ES film leads to the reoccurrence of surface wrinkling. Furthermore, the reducibility of the dewrinkled LEB film and the oxidizability of the dewrinkled PB film are well utilized respectively to yield various wrinkled PANI-based composite films.

Patterning Surfaces on Azo-Based Multilayer Films via Surface Wrinkling Combined with Visible Light Irradiation.

Here, a simple combined strategy of surface wrinkling with visible light irradiation to fabricate well tunable hierarchical surface patterns on azo-containing multilayer films is reported. The key to tailor surface patterns is to introduce a photosensitive poly(disperse orange 3) intermediate layer into the film/substrate wrinkling system, in which the modulus decrease is induced by the reversible photoisomerization. The existence of a photoinert top layer prevents the photoisomerization-induced stress release in the intermediate layer to some extent. Consequently, the as-formed wrinkling patterns can be modulated over a large area by light irradiation. Interestingly, in the case of selective exposure, the wrinkle wavelength in the exposed region decreases, while the wrinkles in the unexposed region are evolved into highly oriented wrinkles with the orientation perpendicular to the exposed/unexposed boundary. Compared with traditional single layer-based film/substrate systems, the multilayer system consisting of the photosensitive intermediate layer offers unprecedented advantages in the patterning controllability/universality. As demonstrated here, this simple and versatile strategy can be conveniently extended to functional multilayer systems for the creation of prescribed hierarchical surface patterns with optically tailored microstructures.

Tuning and Erasing Surface Wrinkles by Reversible Visible-Light-Induced Photoisomerization.

Periodic wrinkling across different scales has received considerable attention because it not only represents structure failure but also finds wide applications. How to prevent wrinkling or create desired wrinkling patterns is non-trivial because the dynamic evolution of wrinkles is a highly nonlinear problem. Herein, we report a simple yet powerful method to dynamically tune and/or erase wrinkling patterns with visible light. The light-induced photoisomerization of azobenzene units in azopolymer films leads to stress release and consequently to the erasure of the wrinkles. The wrinkles in unexposed regions are also affected and oriented perpendicular to the exposed boundary during the stress reorganization. Theoretical models were developed to understand the dynamics of the reversible photoisomerization-induced wrinkle evolution. This method can be applied for designing functional materials/devices, for example, for the reversible optical writing/erasure of information as demonstrated here.

Cation substitution dependent bimodal photoluminescence in whitlockite structural Ca(3-x)Sr(x)(PO4)2:Eu(2+) (0 ≤ x ≤ 2) solid solution phosphors.

Cation substitution dependent tunable bimodal photoluminescence behavior was observed in the Ca3-xSrx(PO4)2:Eu(2+) (0 ≤ x ≤ 2) solid solution phosphors. The Rietveld refinements verified the phase purity and whitlockite type crystal structure of the solid solutions. The tunable photoluminescence evolution was studied as a function of strontium content, over the composition range 0.1 ≤ x ≤ 2. In addition to the emission band peak at 416 nm in Ca3(PO4)2:Eu(2+), the substitution of Ca(2+) by Sr(2+) induced the emerging broad-band peak at 493-532 nm. A dramatic red shift of the emission peak located in the green-yellow region was observed on an increase of x in the samples with 0.75 ≤ x ≤ 2.00. The two emission bands could be related to the EuOn-Ca9 and EuOn-Ca9-xSrx emitting blocks, respectively. The values for the two kinds of emitting blocks in the solid solutions can be fitted well with the observed intensity evolution of the two emission peaks.

New yellow-emitting Whitlockite-type structure Sr(1.75)Ca(1.25)(PO4)2:Eu(2+) phosphor for near-UV pumped white light-emitting devices.

New compound discovery is of interest in the field of inorganic solid-state chemistry. In this work, a whitlockite-type structure Sr1.75Ca1.25(PO4)2 newly found by composition design in the Sr3(PO4)2-Ca3(PO4)2 join was reported. Crystal structure and luminescence properties of Sr1.75Ca1.25(PO4)2:Eu(2+) were investigated, and the yellow-emitting phosphor was further employed in fabricating near-ultraviolet-pumped white light-emitting diodes (w-LEDs). The structure and crystallographic site occupancy of Eu(2+) in the host were identified via X-ray powder diffraction refinement using Rietveld method. The Sr1.75Ca1.25(PO4)2:Eu(2+) phosphors absorb in the UV-vis spectral region of 250-430 nm and exhibit an intense asymmetric broadband emission peaking at 518 nm under λex = 365 nm which is ascribed to the 5d-4f allowed transition of Eu(2+). The luminescence properties and mechanism are also investigated as a function of Eu(2+) concentration. A white LED device which is obtained by combining a 370 nm UV chip with commercial blue phosphor and the present yellow phosphor has been fabricated and exhibit good application properties.

Transcriptome analysis of the Bombyx mori fat body after constant high temperature treatment shows differences between the sexes.

Ambient temperature plays a large role in insect growth, development and even their distribution. The elucidation of the associated molecular mechanism that underlies the effect of constant high temperature will enables us to further understand the stress responses. We constructed four digital gene expression libraries from the fat body of female and male Bombyx mori. Differential gene expression was analyzed after constant high temperature treatment. The results showed that there were significant changes to the gene expression in the fat body after heat treatment, especially in binding, catalytic, cellular and metabolic processes. Constant high temperature may induce more traditional cryoprotectants, such as glycerol, glycogen, sorbitol and lipids, to protect cells from damage, and induce heat oxidative stress in conjunction with the heat shock proteins. The data also indicated a difference between males and females. The heat shock protein-related genes were up-regulated in both sexes but the expression of Hsp25.4 and DnaJ5 were down-regulated in the male fat body of B. mori. This is the first report of such a result. Constant high temperature also affected the expression of other functional genes and differences were observed between male and female fat bodies in the expression of RPS2, RPL37A and MREL. These findings provide abundant data on the effect of high temperature on insects at the molecular level. The data will also be beneficial to the study of differences between the sexes, manifested in variations in gene expression under high temperature.

Application of proteomics to determine the mechanism of ozone on sweet cherries (Prunus avium L.) by time-series analysis.

This research investigated the mechanism of ozone treatment on sweet cherry (Prunus avium L.) by Lable-free quantification proteomics and physiological traits. The results showed that 4557 master proteins were identified in all the samples, and 3149 proteins were common to all groups. Mfuzz analyses revealed 3149 candidate proteins. KEGG annotation and enrichment analysis showed proteins related to carbohydrate and energy metabolism, protein, amino acids, and nucleotide sugar biosynthesis and degradation, and fruit parameters were characterized and quantified. The conclusions were supported by the fact that the qRT-PCR results agreed with the proteomics results. For the first time, this study reveals the mechanism of cherry in response to ozone treatment at a proteome level.

Highly stable lithium sulfur batteries enhanced by flocculation and solidification of soluble polysulfides in routine ether electrolyte.

Lithium-sulfur batteries (LSBs) are among the most promising next-generation high energy density energy-storage systems. However, practical application has been hindered by fundamental problems, especially shuttling by the higher-order polysulfides (PSs) and slow redox kinetics. Herein, a novel electrolyte-based strategy is proposed by adding an ultrasmall amount of the low-cost and commercially available cationic antistatic agent octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate (SN) into a routine ether electrolyte. Due to the strong cation-anion interaction and bridge-bonding with SN, rapid flocculation of the soluble polysulfide intermediates into solid-state polysulfide-SN sediments is found, which significantly inhibited the adverse shuttling effect. Moreover, a catalytic effect was also demonstrated for conversion of the polysulfide-SN intermediates, which enhanced the redox kinetics of Li-S batteries. Encouragingly, for cells with only 0.1 % added SN, an initial specific capacity of 783.6 mAh/g and a retained specific capacity of 565.7 mAh/g were found at 2C after 200 cycles, which corresponded to an ultralow capacity decay rate of only 0.014 % per cycle. This work may provide a simple and promising regulation strategy for preparing highly stable Li-S batteries.

Enhanced triethylamine-sensing properties of hierarchical molybdenum trioxide nanostructures derived by oxidizing molybdenum disulfide nanosheets.

A 3D α-MoO3 nanostructure for high-performance triethylamine (TEA) detection was synthesized via the facial oxidation of MoS2 nanoflowers (NFs) obtained by a hydrothermal process. The influence of the time of hydrothermal process in growing MoS2 on the morphologies of the final MoO3 obtained after calcination was investigated. As-obtained MoO3 and their precursors were systematically characterized by various techniques, such as X-ray diffraction, Raman, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and N2 adsorption-desorption isotherms. Results showed that MoO3 with a hierarchical layered nanostructure was successfully obtained. After hydrothermal treatment of the MoS2 precursor for 20 h, the typical MoO3-based sensor (called M20) exhibited a high response of 2.42 at a very low TEA concentration of only 0.1 ppm at 240 °C. The M20 sensor response to 50 ppm TEA was as high as 125 with a fast response/recovery time of 14/22 s. Moreover, the sensor had a high stability and reproducibility as well as a high selectivity against other interfering VOCs or gases. Due to the tendency of TEA to adsorb to active oxygen sites of MoO3, the enhanced sensing properties of MoO3 can be ascribed to the remarkable hierarchical structure and large surface area. MoO3 obtained after calcination of hydrothermally grown MoS2 is thus a promising sensing material for enhanced TEA gas detection.

Effects of Atmospheric Cold Plasma Treatment on the Storage Quality and Chlorophyll Metabolism of Postharvest Tomato.

Atmospheric cold plasma (ACP) is a potential green preservation technology, but its preservation mechanism is still unclear, and the effects of different plasma intensities on postharvest tomatoes are little studied. In this study, the effects of different ACP treatments (0 kV, 40 kV, 60 kV, and 80 kV) on the sensory quality, physiological indexes, key enzyme activities, and gene expression related to the chlorophyll metabolism of postharvest tomatoes were investigated during the storage time. The results showed that compared with the control group, the tomatoes in the plasma treatment group had a higher hardness and total soluble solid (TSS) and titratable acid (TA) contents, a lower respiratory intensity and weight loss rate, a higher brightness, and a lower red transformation rate, especially in the 60 kV treatment group. In addition, chlorophyll degradation, carotenoid accumulation, and chlorophyllase and pheophorbide a mono-oxygenase (PAO) enzyme activities in the postharvest tomatoes were inhibited in the 60 kV treatment group, and the expressions of three key genes related to chlorophyll metabolism, chlorophyll (CLH1), pheophytinase (PPH), and red chlorophyll catabolic reductase (RCCR) were down-regulated. The results of the correlation analysis also confirmed that the enzyme activity and gene expression of the chlorophyll metabolism were regulated by the ACP treatment, aiming to maintain the greenness of postharvest tomatoes.

High temperature induced S vacancies in natural molybdenite for robust electrocatalytic nitrogen reduction.

Defect engineering is an important strategy to regulate electronic structure of electrocatalysts for electrochemical N2 fixation, aiming at improving the electron state density and enhancing the adsorption and activation of inert N2. In this paper, a high-temperature strategy to anneal the natural molybdenite under Ar atmosphere was developed, and the as-obtained molybdenite with S vacancies boosted a high activity for N2 reduction reaction. In 0.1 M HCl, the catalyst annealed at 800 °C exhibits a high Faradic efficiency of 17.9% and a NH3 yield of 23.38 µg h-1 mg-1cat. at -0.35 V versus reversible hydrogen electrode, two times higher than that of the pristine molybdenite. The facile one-step annealing method introduces the defects (e.g., S vacancies) in the surface of the natural molybdenite particles to prepare catalysts for generating ammonia by reducing nitrogen at room temperature under ordinary pressure, promoting the development of low-carbon economic prospect.

Microwave-assisted synthesis of hierarchically porous Co3O4/rGO nanocomposite for low-temperature acetone detection.

Acetone sensors with high response and excellent selectivity are of enormous demand for monitoring the diabetes. This paper has reported a novel porous 3D hierarchical Co3O4/rGO nanocomposite synthesized by a microwave-assisted method, by which Co3O4 nanoparticles are rapidly and uniformly anchored on rGO nanosheets. The phase composition, surface morphology of the Co3O4/rGO composites and the effect of rGO on their acetone-sensing performance were systematically investigated. The results show that the sample with an optimized content of rGO (Co3O4/rGO-1) achieves the highest stability and response to acetone (0.5 ~ 200 ppm) at a relatively low temperature (~160 °C). Also, the Co3O4/rGO-1 exhibits a high acetone-sensing selectivity against the gases (or vapors) of H2S, H2, CH4, HCHO, CH3OH, C3H8O and C2H5OH. The enhanced acetone-sensing performance of the Co3O4/rGO composite can be attributed to the Co3O4/rGO p-p heterojunction and the Co3+-C coupling effect between Co3O4 and rGO, improving transport of carriers. In addition, the unique 3D hierarchically porous structure and large surface areas are favorable to adsorption and desorption of gas molecules. This facile microwave-assisted method provides a charming strategy to develop smart rGO-based nanomaterials for real-time detection of harmful gases and rapid medical diagnosis.

Effects of ozone treatment on the antioxidant capacity of postharvest strawberry.

Strawberries are highly popular around the world because of their juicy flesh and unique taste. However, they are delicate and extremely susceptible to peroxidation of their membrane lipids during storage, which induces water loss and rotting of the fruit. This study investigated the effects of ozone treatment on the physiological traits, active oxygen metabolism, and the antioxidant properties of postharvest strawberry. The results revealed that the weight loss (WL) and respiration rate (RR) of strawberry were inhibited by ozone treatment (OT), while the decline of firmness (FIR) and total soluble solids (TSS) were delayed. Ozone also reduced the generation rate of superoxide radical anions , and the content of hydrogen peroxide (H2O2) enhanced the activity of superoxidase (SOD), catalase (CAT), ascorbate peroxidase (APX), and monodehydroascorbate reductase (MDHAR), as well as promoted the accumulation of ascorbic acid (ASA), glutathione (GSH), and ferric reducing/antioxidant power (FRAP). In addition, a total of 29 antioxidant-related proteins were changed between the OT group and control (CK) group as detected by label-free proteomics during the storage time, and the abundance associated with ASA-GSH cycle was higher in the OT group at the later stage of storage, and the qRT-PCR results were consistent with those of proteomics. The improvement of the antioxidant capacity of postharvest strawberry treated with ozone may be achieved by enhancing the activity of the antioxidant enzymes and increasing the expression of the antioxidant proteins related to the ascorbic acid-glutathione (ASA-GSH) cycle.