Search

A series of single‐chain random heteropolymer (RHP)‐derived artificial ion channels with both high K+ selectivity and controllable pH‐gated behaviors were fabricated by a facile "one‐pot" polymerization method. The benzo‐18‐crown‐6 moieties appended on lateral chains of RHPs can form ion‐permeable nanopores and transport K+ over Na+ through the lipid bilayers. The ion permeation selectivity was significantly enhanced by incorporating a cholesterol group to serve as a membrane anchor. Interestingly, similar to natural gated protein channels, on–off switchable characteristics were also realized by integrating an additional acid‐sensitive alkylamine group into the RHP‐derived channel. The unique design strategies have endowed the RHP‐derived ion channels with facile synthetic procedures, desirable membrane compatibility, high K+ selectivity, and tunable pH‐gated properties. This work provides an entry point for future design of novel functional nanochannels. [ABSTRACT FROM AUTHOR]

A series of single‐chain random heteropolymer (RHP)‐derived artificial ion channels with both high K+ selectivity and controllable pH‐gated behaviors were fabricated by a facile "one‐pot" polymerization method. The benzo‐18‐crown‐6 moieties appended on lateral chains of RHPs can form ion‐permeable nanopores and transport K+ over Na+ through the lipid bilayers. The ion permeation selectivity was significantly enhanced by incorporating a cholesterol group to serve as a membrane anchor. Interestingly, similar to natural gated protein channels, on–off switchable characteristics were also realized by integrating an additional acid‐sensitive alkylamine group into the RHP‐derived channel. The unique design strategies have endowed the RHP‐derived ion channels with facile synthetic procedures, desirable membrane compatibility, high K+ selectivity, and tunable pH‐gated properties. This work provides an entry point for future design of novel functional nanochannels. [ABSTRACT FROM AUTHOR]

Summary: In this paper, we propose an iterative learning control strategy to track a desired trajectory for a class of uncertain systems governed by nonlinear differential inclusions. By imposing Lipschitz continuous condition on a set‐valued mapping described by a closure of the convex hull of a set and using D‐type and PD‐type updating laws with initial iterative learning, we establish the iterative learning process and give a new convergence analysis with the help of Steiner‐type selector. Finally, numerical examples are provided to verify the effectiveness of the proposed method with suitable selection of set‐valued mappings. An application to the speed control of robotic fish is also given. [ABSTRACT FROM AUTHOR]

A supramolecular nanocapsule was constructed by the ternary host–guest complexation of azobenzene (Azo) and methylviologen (MV) to cucurbit[8]uril (CB[8]) and the subsequent self-assembly. The supramolecular nanocapsule with both glutathione peroxidase (GPx) and superoxide dismutase (SOD) activities can mimic the intracellular enzymatic reactive oxygen species (ROS) defense system. [ABSTRACT FROM AUTHOR]

• The different roles of spin-state Fe species in O 2 -H 2 O 2 –1O 2 reaction were revealed. • 1O 2 was efficiently generated by a novel nonradical activation of H 2 O 2. • FIS/CN-V n /in-situ H 2 O 2 /vis process contributed to selective water decontamination. The development of 1O 2 -dominanted selective decontamination for water purification was hampered by extra H 2 O 2 consumption and poor 1O 2 generation. Herein, we proposed the reconstruction of Fe spin state using near-range N atom and long-range N vacancies to enable efficient generation of H 2 O 2 and sequential activation of H 2 O 2 into 1O 2 after visible-light irradiation. Theoretical and experimental results revealed that medium-spin Fe(III) strengthened O 2 adsorption, penetrated e g electrons to antibonding p-orbital of oxygen, and lowered the free energy of O 2 activation, enabling the oxygen protonation for H 2 O 2 generation. Thereafter, the electrons of H 2 O 2 could be extracted by low-spin Fe(III) and rapidly converted into 1O 2 in a nonradical path. The developed 1O 2 -dominated in-situ photo-Fenton-like system had an excellent pH universality and anti-interference to inorganic ions, dissolved organic matter, and even real water matrixes (e.g., tap water and secondary effluent). This work provided a novel insight for sustainable and efficient 1O 2 generation , which motivated the development of new-generation selective water treatment technology. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract In this paper, we present a numerical solution for a finite time complete tracking problem based on the iterative learning control technique for dynamical systems governed by partial differential inclusions of parabolic type with noninstantaneous impulses. By imposing a standard Lipschitz condition on a set-valued mapping and applying conventional P-type updating laws with an initial iterative learning mechanism, we successfully establish an iterative learning process for the tracking problem and conduct a novel convergence analysis with the help of Steiner-type selectors. Sufficient conditions are presented for ensuring asymptotical convergence of the tracking error to zero. Numerical examples are provided to verify the effectiveness of the proposed method with a suitable selection of set-valued mappings. [ABSTRACT FROM AUTHOR]

Summary: In this paper, we propose five iterative learning control (ILC) schemes for noninstantaneous impulsive fractional‐order systems with randomly varying trial lengths. We introduce a domain alignment operator to establish a rigorous convergence analysis for nonlinear fractional‐order systems. This operator guarantees that the input, state, output, and tracking error are constrained in a function space that is designed in advance. Moreover, with the help of this operator, we extend the conventional ILC scheme from discrete systems to continuous and algebraic systems with incorporating redundant tracking information. In addition, nonlinear ILC schemes are also presented with a geometric analysis concept. All proposed schemes are shown to be convergent to the desired tracking trajectory. Two illustrative examples are provided to verify the theoretical results. [ABSTRACT FROM AUTHOR]

In this paper, we utilize fractional calculus, theory of semigroup and fixed point approach to prove existence and approximate controllability results for a class of fractional differential equations (FDEs) with noninstantaneous impulses by constructing a suitable composite control function, imposing that the associated linear problem is approximately controllable on the terminal subinterval and dividing our global task into many subtasks on each subinterval. Next, we apply P-type iterative learning control (ILC) updating law to generate a sequence of control functions to find a desired control function to guarantee the error between the output and the desired reference trajectories tending to zero via a suitable norm in the sense of uniform convergence. As a result, the limit of the sequence of control functions is the required control to guarantee the above problem is approximately controllable. In addition, a numerical example is illustrated to demonstrate ILC scheme to solve approximate controllability of time fractional impulsive PDEs via tracking the given continuous and discontinuous trajectory. [ABSTRACT FROM AUTHOR]

In this paper, we design learning law with high-order internal models for fractional order differential equations to track the varying reference accurately by adopting a few iterations in a finite time interval. We establish sufficient conditions of convergence for the P-type and PD-type updating law for different fractional order differential equations. Finally, we give some numerical examples to demonstrate the validity of the designed method. [ABSTRACT FROM AUTHOR]

This paper is concerned on optimal control problems for systems governed semilinear fractional differential equations with not instantaneous impulses in the infinite dimensional spaces. We utilize fractional calculus, semigroup theory and fixed point approach to present the solvability of the corresponding control system by using the new introduced concept of mild solutions. Next, we give the existence result of optimal controls for Lagrange problem under the suitable conditions. Finally, an example is given to illustrate the effectiveness of our results. [ABSTRACT FROM AUTHOR]

With the increasing intelligence of automobiles, vehicle pre-ventilation can be better controlled. In summer, cars parked in the open air are directly exposed to sunlight; thus, a high-temperature environment is formed in the occupant cabin, which seriously affects the passengers and driver's riding and driving experience. Meanwhile, lowering the temperature of the passenger compartment from a very high temperature to a comfortable temperature consumes a lot of energy. Therefore, it is increasingly important to study the pre-ventilation of the cabin in order to improve the thermal comfort of the occupant cabin and reduce energy consumption. In this paper, a new theoretical model of a cabin temperature control system is proposed. To support the theoretical model, an outdoor parking temperature rise test was carried out. Environmental parameters were obtained and used as the boundary conditions of the subsequent simulation. Based on the mechanism of the cabin temperature rise, the convective heat transfer coefficient on the body surface, the equivalent heat transfer model of the cabin, the solar radiation model and the physical properties of the air, a computational simulation of the temperature rise in the occupant cabin was carried out, and a simulation of the temperature rise in the occupant cabin exposure was studied. The simulation results were compared with the experimental findings to verify the accuracy of the simulation, which provided a reference for the design of the pre-cooling function of the occupant cabin. This study revealed that the pre-ventilation model developed reduces the vehicle cabin temperature through optimal control of air supply volumes and air supply angles. Furthermore, the developed pre-ventilation model is capable of reducing energy consumption, thereby reducing greenhouse gas emissions. [ABSTRACT FROM AUTHOR]

In this paper, a new class of stochastic impulsive differential equations involving Bernoulli distribution is introduced. For tracking the random discontinuous trajectory, a modified tracking error associated with a piecewise continuous variable by zero-order holder is defined. In the sequel, a new random ILC scheme by adopting global and local iteration average operators is designed too. Sufficient conditions to guarantee the convergence of modified tracking error are obtained by using the tools of mathematical analysis via an impulsive Gronwall inequality. Finally, two illustrative examples are presented to demonstrate the performance and the effectiveness of the averaging ILC scheme to track the random discontinuous trajectory. [ABSTRACT FROM AUTHOR]

In order to track the discontinuous reference trajectory accurately using a few iterations in a finite time interval, we design a P-type iterative learning control law with initial state learning for a noninstantaneous impulsive fractional-order system. The convergent sufficient conditions of open-loop and closed-loop iterative learning schemes are established. Finally, two numerical examples are given to illustrate our results. [ABSTRACT FROM AUTHOR]

[Display omitted] • Bioinspired supramolecular peroxidase-like nanozyme was precisely fabricated. • Nanozymes showed a high k cat[Heme] /K m of 572.2 s−1 M−1 per single heme molecule. • Nanozymes exhibited more superior stability than natural HRP. • A glucose detection system was constructed with extremely low levels of nanozymes. Construction of biomimetic nanozymes has attracted considerable attention because these artificial enzymes not only exhibited catalytic effects similar to those of natural enzymes, but were also more economical and stable than natural enzymes for a wide range of practical applications. Herein, a peroxidase-like nanozyme was constructed by supramolecular co-assembled strategy, in which horseradish peroxidase active sites (histidine-heme-histidine) were loaded on giant supramolecular tubular scaffolds. The giant nanotube carried a large number of histidine-heme-histidine active sites on the surface thus exhibiting admirable activity with the high apparent second-order rate constant (k cat[Heme] /K m) of 572.2 M−1s−1 per single heme molecule and also showing high stability. Furthermore, the nanozyme was further applied to detect glucose through test paper by loading with extremely low levels of nanozyme, revealing its potential application in the rapid diagnosis of diabetes. [ABSTRACT FROM AUTHOR]

The selective disruption of nutritional supplements and the metabolic routes of cancer cells offer a promising opportunity for more efficient cancer therapeutics. Herein, a biomimetic cascade polymer nanoreactor (GOx/CAT-NC) was fabricated by encapsulating glucose oxidase (GOx) and catalase (CAT) in a porphyrin polymer nanocapsule for combined starvation and photodynamic anticancer therapy. Internalized by cancer cells, the GOx/CAT-NCs facilitate microenvironmental oxidation by catalyzing endogenous H2O2 to form O2, thereby accelerating intracellular glucose catabolism and enhancing cytotoxic singlet oxygen (1O2) production with infrared irradiation. The GOx/CAT-NCs have demonstrated synergistic advantages in long-term starvation therapy and powerful photodynamic therapy (PDT) in cancer treatment, which inhibits tumor cells at more than twice the rate of starvation therapy alone. The biomimetic polymer nanoreactor will further contribute to the advancement of complementary modes of spatiotemporal control of cancer therapy. [ABSTRACT FROM AUTHOR]

In the past few decades, enormous efforts have been made to synthesize covalent polymer nano/microstructured materials with specific morphologies, due to the relationship between their structures and functions. Up to now, the formation of most of these structures often requires either templates or preorganization in order to construct a specific structure before, and then the subsequent removal of previous templates to form a desired structure, on account of the lack of "self-error-correcting" properties of reversible interactions in polymers. The above processes are time-consuming and tedious. A template-free, self-assembled strategy as a "bottom-up" route to fabricate well-defined nano/microstructures remains a challenge. Herein, we introduce the recent progress in template-free, self-assembled nano/microstructures formed by covalent two-dimensional (2D) polymers, such as polymer capsules, polymer films, polymer tubes and polymer rings. [ABSTRACT FROM AUTHOR]

[Display omitted] • Novel eye-sensitive Ba 3 Nb 2 O 2 F 12 (H 2 O) 2 :Tb3+/Mn4+ were synthesized by simple co-precipitation strategy. • Red phosphor presents extremely strong ZPL at ∼ 625 nm and high color purity. • Red and green phosphors exhibit inherently outstanding thermal stability and moisture resistance. • Red and green phosphors coated directly on UV chip can achieve white emission. • The fabricated WLED devices show excellent electroluminescent properties. Novel eye-sensitive Ba 3 Nb 2 O 2 F 12 (H 2 O) 2 :Tb3+ green and Ba 3 Nb 2 O 2 F 12 (H 2 O) 2 :Mn4+ red oxyfluoride phosphors with extremely strong absorption in the UV region were designed and synthesized by simple co-precipitation strategy. Particularly, Tb3+ ions were doped in this matrix for the first time, which greatly improves their absorption efficiency in the near ultraviolet region (367 nm) and emits sharp green light (544 nm). In addition, the Ba 3 Nb 2 O 2 F 12 (H 2 O) 2 :Mn4+ red phosphors have strong zero phonon line (ZPL) emission at 625 nm, which is conducive to improving the sensitivity of human eye and color purity. Meanwhile, the optical properties of the red phosphor are significantly enhanced via doping K+ cations as charge compensators. Crystal field environment and nephelauxetic effect of the as-prepared phosphors before and after K+ cation doping were systematically analyzed. Moreover, these synthesized red/green phosphors have good thermal stability and moisture resistance. Remarkably, the as-prepared Ba 3 Nb 2 O 2 F 12 (H 2 O) 2 :5%Mn4+ or K 0.9 Ba 2.1 Nb 2 O 2 F 12 (H 2 O) 2 :5%Mn4+ red phosphors can be directly mixed with the as-synthesized Ba 3 Nb 2 O 2 F 12 (H 2 O) 2 :13%Tb3+ green phosphor coating on 365 nm near-ultraviolet LED chip to package WLED devices with excellent electroluminescence performance. These findings are conducive to opening an avenue for screening the unique structure of optical materials. [ABSTRACT FROM AUTHOR]

The characteristics of chloroplasts harvesting solar energy and conducting energy transfer have inspired chemists to mimic similar processes. However, accurate manipulation to gain regularly displayed antenna chromophores in mimicking chloroplasts is a great challenge. Herein, a rational design is presented that combines orderly arranged chromophores with aggregation‐induced emission (AIE) to develop artificial light‐harvesting systems. Tetraphenyl ethylene (TPE) molecules, which exhibited strong AIE properties, are considered as building blocks to fabricate high emissive 2D nanosheets and nanovesicles, respectively. Furthermore, the well‐aligned TPE molecules are also developed as donor chromophores in light‐harvesting processes. After subsequent surface modification by porphyrin molecules as acceptor chromophores, an efficient light‐harvesting system has been integrally constructed. This study demonstrates a novel strategy to utilize AIE feature to mimic chloroplasts process in nature. [ABSTRACT FROM AUTHOR]

[Display omitted] • Efficient 1O 2 nanogenerator was precisely constructed by regulating Fe spin state. • Low spin-state Fe induced nonradical conversion from H 2 O 2 to 1O 2. • The 1O 2 -dominated system selectively removed low ionization potential contaminants. • Stable Fh/BiOI transformed high-toxic contaminant into low-toxic products. • Fh/BiOI exhibited excellent mineralization performance towards secondary effluent. The hydrogen peroxide (H 2 O 2)-based photo-Fenton-like was a promising technology for the generation of singlet oxygen (1O 2), which was highly desirable in water purification. However, the yield of 1O 2 in traditional radical system was low due to the radical competition. Targeted construction of the non-radical system could solve the above issue, but it has been a challenge. In this study, we targetedly regulated the Fe spin state to efficiently generate 1O 2 in a nonradical path. The experimental and theoretical results demonstrated that low-spin FeIII enhanced H 2 O 2 adsorption, directly extracted electrons from H 2 O 2 to Fe center, and rapidly cleaved O–H bond to accelerate the recombination of *OOH with H 2 O 2 for efficient 1O 2 generation. This unique nonradical process differed obviously from the traditional radical pathway for 1O 2 generation. The developed 1O 2 -dominant 50Fh/BiOI/H 2 O 2 /vis system degraded 98.4% of TCH, which was higher than that in •OH-dominant Fh/H 2 O 2 /vis system (84.2%) and it had excellent resistance to various substances, including inorganic ions, dissolved organic matter and real water matrix (tap water and secondary effluent). This study enhanced our understanding of spin-state-dependent photo-Fenton-like reaction and inspired the targeted development of a new-generation selective wastewater treatment technology. [ABSTRACT FROM AUTHOR]

Herein, a new organic cationic matrix [N(CH3)4]3MoO3F3 suitable for Mn4+ doping was constructed. Due to the large steric hindrance of N[CH3]4+ (TMA), charge compensation defects can be effectively prevented in the heterovalent Mn4+-doping process, and a high IQE (91.05%) was obtained. Through the cation co-doping strategy, Mg2+/Zn2+/Li+ cations were introduced into the Mo6+ cationic site, which improved the crystallinity of the matrix and reduced energy losses, so as to improve luminescence intensity, QE, thermal stability, water stability and other spectral properties. Meanwhile, [N(CH3)4]2TiF6:Mn4+ phosphors with the same TMA organic cation and equivalent Mn4+ doping were synthesized for comparison, and the effects of the Mg2+ cation co-doping strategy on the spectral properties of phosphors with different matrix types (fluoride/oxyfluoride) and substitution types (equivalent/non-equivalent) were analyzed. These findings provide the basis for the preparation of new luminescent materials. Furthermore, according to the optical properties exhibited by these phosphors, they are packaged into WLED devices with excellent photoelectric properties, which are suitable for indoor lighting and display fields. [ABSTRACT FROM AUTHOR]

Orthogonal dynamic covalent self‐assembly is used as a facile method for constructing polymer hollow nanocapsules (NCs) and thin films. The bifunctional precursor 4‐formylphenylboronic acid is symmetrically installed with a boronic acid group for the boroxine linkage, and an aldehyde group for the Schiff base reaction which can react with twofold symmetry linkers ethylenediamine and para phenylenediamine to attain polymer NCs and nanosheets. Owing to the reversibility of the imine linkages, the mutual morphological transformation between polymer NCs and thin films via an amine‐imine‐exchange strategy is successfully achieved. Multiple reversible covalent bonds allow the control the release of the load in polymer NCs using different techniques. This may be useful for designing stimulus‐responsive smart materials. [ABSTRACT FROM AUTHOR]

An important issue in the area of multi-operation systems is the observation of a discontinuous trajectory. In order to track a discontinuous output trajectory, we choose impulsive differential systems to generate a series of local continuous state trajectories, which become a set of output trajectories via the action of the output functions. Concerning impulsive differential control systems, we design proportional–derivative (PD-type) and proportional plus one order derivative and fractional order derivative (PDDα-type) iterative learning control laws with initial state learning. In particular, the PDDα-type law is more flexible due to the impact of a certain fractional order factor α. Thereafter, we give the associated convergence characteristics by establishing sufficient conditions on open-loop and closed-loop iterative learning schemes in the sense of λ-norm under mild assumptions. Finally, several numerical examples, including an application to robotic fish, are given to illustrate our results. [ABSTRACT FROM AUTHOR]

In this paper, a Pythagorean-Hodograph (PH) curve-based pick-and-place operation trajectory planning method for Delta parallel robots is proposed, which realizes the flexible control of pick-and-place operations to meet the requirements of various practical scenarios. First, according to the geometric relationship of pick-and-place operation path, different pick-and-place operations are classified. Then trajectory planning is carried out for different situations, respectively, and in each case, the different polynomial motion laws adopted by the linear motion segment and the curved motion segment are solved. Trajectory optimization is performed with the motion period as optimization objective. The proposed method is easier to implement, and at the same time satisfies the safety, optimization, mobility, and stability of the robot; that is, the proposed method realizes obstacle avoidance, optimal time, flexible control of the robot trajectory, and stable motion. Simulations and experiments verify the effectiveness of the method proposed in this paper. The proposed method can not only realize the fast, accurate, and safe operation in intelligent manufacturing fields such as rapid classification, palletizing, grasping, warehousing, etc., but its research route can also provide a reference for trajectory planning of intelligent vehicles in logistics system. [ABSTRACT FROM AUTHOR]

The atomically monodispersed dual‐atom nanozyme not only possesses the advantages of homogeneous active centers and high atomic utilization efficiency but also exhibits amazing synergistic effect for higher catalytic activities than single‐atom nanozyme. However, how to construct dual‐atom nanozyme with multi‐enzyme cascade capacity for protecting against brain tissue damage is a great challenge. Herein, for coping with the secondary damage to brain tissue caused by the explosive generation of reactive oxygen species(ROS) during cerebral ischemia‐reperfusion, a multi‐enzyme cascade antioxidant system is constructed by encapsulating dual‐Fe‐atom nanozyme (Fe2NC) in a selenium‐containing MOF (Se‐MOF) shell layer. The designed dual‐Fe‐atom nanozyme exhibits higher superoxide dismutase‐like, catalase‐like, and even oxidase‐like activities than single‐atom Fe (Fe1NC) nanozyme, and moreover, the Se‐MOF shell layer not only acts as a glutathione peroxidase mimic, but also improves the stability and biocompatibility of the Fe2NC nanozyme obviously. The synergistic effect of Fe2NC has been demonstrated to be the main reason for the higher activity by density functional theory calculations. In vitro and in vivo results reveal that the multifunctional antioxidant Fe2NC@Se nanoparticles can counteract oxidative damage and inhibit neural apoptosis after cerebral ischemia‐reperfusion injury by effectively eliminating intracellular ROS and potentially inhibiting the ASK1/JNK apoptotic signaling pathway. [ABSTRACT FROM AUTHOR]

[Display omitted] • An energy band-matched efficient photo-Fenton-like reactor was constructed. • Graphitic carbon ring induced successive built-in electric field for PMS activation. • CoWO 4 /GD-CN universally degraded representative contaminants in different fields. • The reaction mechanism enhanced by gradient graphitic carbon rings was proposed. The heterojunction with matched energy band enables efficient peroxymonosulfate (PMS)-based photo-Fenton-like reaction. Nevertheless, the rapid photogenerated charge separation and transfer has been challenging. Herein, we precisely constructed an efficient heterogeneous photo-Fenton-like reactor with successive built-in electric field by gradient doping of coplanar graphitic carbon rings (C gra) into cobalt tungstate/graphitic carbon nitride (CoWO 4 /GD-CN) heterostructure. The as-prepared CoWO 4 /GD-CN exhibited remarkable enhancement with a tetracycline hydrochloride degradation rate constant (0.776 min−1) higher than that of CoWO 4 /CN (0.507 min−1). Theoretical and experimental results demonstrated that the successive built-in electric field enhanced by gradient-doped coplanar C gra ring accelerated photogenerated electrons transfer from the innermost to the outmost layer of CoWO 4 /GD-CN. This transfer drove Co(III)/Co(II) conversion for accelerated PMS activation, leading to enhanced degradation reactivity. CoWO 4 /GD-CN had excellent degradability towards representative contaminants, including carbamazepine (1.0 min−1), 4-chlorophenol (0.920 min−1), sulfamethoxazole (0.90 min−1), bisphenol A (0.933 min−1), atrazine (0.829 min−1), ciprofloxacin (0.589 min−1) and norfloxacin (0.617 min−1) in CoWO 4 /GD-CN/PMS/vis system, respectively. This work provided a novel insight into the gradient-dope modulated photo-Fenton-like reaction and guided the design of efficient photo-Fenton-like reactor. [ABSTRACT FROM AUTHOR]

An artificial signal transduction model with a supramolecular recognition headgroup, a membrane anchoring group, and a pro-enzyme catalysis endgroup was constructed. The transmembrane translocation of the transducer can be reversibly regulated by competitive host–guest complexations as an input signal to control an enzyme reaction inside the lipid vesicles. [ABSTRACT FROM AUTHOR]

Breaking hydrogen bond in metal free carbon nitride (CN) to increase peroxymonosulfate (PMS) adsorption for surface-mediated electron transfer has been challenging. Herein, we incorporated N−C N monomer into CN to break hydrogen bond by the introduction of polyvinylpyrrolidone (PVP). The developed nonradical oxidation system achieved selective decomposition of highly hydrophilic contaminants and efficient removal of chemical oxygen demand (58.0%), total phosphorus (88.1%), ammonia nitrogen (100.0%) and total nitrogen (67.8%) from the secondary effluent in a continuous flow reactor. This was attributed to that the breakage of hydrogen bond accelerated the redistribution of electron densities at C and N sites, leading to an increase in the adsorption energy of N site to PMS. This promoted the formation of PVP/CN-PMS* complex for the selective and efficient removal of organics and inorganics. This work provided a new perspective for the selective and long-term treatment of practical wastewater. [Display omitted] • Surface-mediated electron transfer system was constructed by breaking hydrogen bond. • The effect of hydrogen bond in carbon nitride on PMS activation pathway was revealed. • PVP/CN/PMS/vis system selectively remove highly hydrophilic contaminants. • The efficient and continuous flow treatment of practical wastewater was achieved. [ABSTRACT FROM AUTHOR]

The superoxide radical (•O 2 −)-mediated peroxymonosulfate (PMS)-based photo-Fenton-like reaction enables highly selective water decontamination. Nevertheless, the targeted construction of •O 2 −-mediated photo-Fenton-like system has been challenging. Herein, we developed an electron-rich/-poor dual sites driven •O 2 −-mediated cascade photo-Fenton-like system by modulating electron density. Experimental and theoretical results demonstrated that PMS was preferentially adsorbed on electron-poor Co site. This adsorption promoted O−O bond cleavage of PMS to generate hydrogen peroxide (H 2 O 2), which then migrated to electron-rich O site to extract e g electrons for O−H bond cleavage, rather than competing with PMS for Co site. The developed versatile cascade reaction system could selectively eliminate contaminants with low n-octanol/water partition constants (K OW) and dissociation constants (pKa) and remarkably resist inorganics (Cl−, H 2 PO 4 − and NO 3 −), humic acid (HA) and even real water matrices (tap water and secondary effluent). This finding provided a novel and plausible strategy to accurately and efficiently generate •O 2 − for the selective water decontamination. [Display omitted] • Redistributing electron density to construct dual sites accelerated cascade reaction. • The contaminants selective degradation behavior by •O 2 − was revealed. • The CuCoO/O-CN/PMS/vis system was stable and resistant to environmental interference. • The effect of oxygen dope on the contaminant degradation pathway was demonstrated. [ABSTRACT FROM AUTHOR]

The La 2 LiTaO 6 :xMn4+ red phosphors with double perovskite structure were prepared by traditional solid-state method. The broad absorption band of the La 2 LiTaO 6 :0.003Mn4+ phosphor is located at ultraviolet and blue light in the range of 200–600 nm, and the emission band of deep red light is located at 711 nm under excitation of near-ultraviolet light. The phosphor has a high color purity of 95.5% and an excellent thermal stability of 85.7%. To further enhance the performance of the phosphor, a cation doping method was adopted in this paper to synthesize La 2 LiTaO 6 :0.003Mn4+, 0.005 R (R = Zn2+, Mg2+, Ca2+, Na+, K+) phosphors. The luminescence intensity of the samples was enhanced after doping with different cations, and the related mechanism was discussed. The optimized La 2 LiTaO 6 :0.003Mn4+, 0.01Zn2+ phosphor has good luminescence performance and thermal stability of 91.5%. The emission spectrum of the sample matches with phytochrome P FR and is suitable for indoor plant lighting. The prepared WLED exhibits relatively low color temperature (3928 K), high color rendering index (84.5) and produces good photostability under different driving currents. Therefore, the La 2 LiTaO 6 :0.003Mn4+, 0.01Zn2+ phosphor has the potential to be applied as a deep red component in LED. • Deep red phosphor La 2 LiTaO 6 :Mn4+ were prepared by high temperature solid state method in air atmosphere for WLEDs and plant cultivation. • The co-doping of various cations (Zn2+, Mg2+, Na+, K+, Ca2+) improves the luminescence performance and thermal stability of La 2 LiTaO 6 :0.3%Mn4+. • La 2 LiTaO 6 :Mn4+, Zn2+ phosphors have excellent thermal stability of 91.5% at 473 K and water stability of 90.3% after being immersed in water for six days. [ABSTRACT FROM AUTHOR]

• Magnetic p-n Bi 2 WO 6 /CuFe 2 O 4 for efficient photo-Fenton-like was fabricated. • Different ROS-dominated dark-and photo-Fenton-like reactions were explored. • Possible degradation pathways of TCH and products toxicity were analyzed. The extensive use of tetracycline hydrochloride (TCH) poses a threat to human health and the aquatic environment. Here, magnetic p-n Bi 2 WO 6 /CuFe 2 O 4 catalyst was fabricated to efficiently remove TCH. The obtained Bi 2 WO 6 /CuFe 2 O 4 exhibited 92.1% TCH degradation efficiency and 50.7% and 35.1% mineralization performance for TCH and raw secondary effluent from a wastewater treatment plant in a photo-Fenton-like system, respectively. The remarkable performance was attributed to the fact that photogenerated electrons accelerated the Fe(III)/Fe(II) and Cu(II)/Cu(I) conversion for the Fenton-like reaction between Fe(II)/Cu(I) and H 2 O 2 , thereby generating abundant •OH for pollutant oxidation. Various environmental factors including H 2 O 2 concentration, initial pH, catalyst dosage, TCH concentration and inorganic ions were explored. The reactive oxidation species (ROS) quenching results and electron spin resonance (ESR) spectra confirmed that •O 2 − and •OH were responsible for the dark and photo-Fenton-like systems, respectively. The degradation mechanisms and pathways of TCH were proposed, and the toxicity of products was evaluated. This work contributes a highly efficient and environmentally friendly catalyst and provides a clear mechanistic explanation for the removal of antibiotic pollutants in environmental remediation. [Display omitted] [ABSTRACT FROM AUTHOR]

K 3 MoO 2 F 5 ·2H 2 O:Mn4+ (KMOFM) oxyfluoride red phosphor was synthesized by co-precipitation strategy. Due to the non-equivalent doping of Mn4+, the phosphor has a strong ZPL emission peak at 623 nm with high color purity (97%). The crystal field strength and nephelauxetic effect were systematically discussed. By optimizing the synthesis process, the optimal doping concentration of Mn4+ was determined to be 0.02. The surface modification of organic reagents (paraffin wax (PW), oleic acid (OA) and methyl silicone oil (MSO)) can effectively enhance the luminescence intensity and moisture resistance of the phosphors, and the possible surface modification mechanism was also proposed. Meanwhile, the as-synthesized sample exhibits distinguished UV light-induced stability, and the surface modification can also improve the photoinduced stability. Moreover, the luminescence thermal stability and the thermal quenching mechanism were analyzed in detail. Furthermore, the CCT and CRI of the warm WLED devices prepared by the red KMOFM/surface-modified phosphors and yellow Y 3 Al 5 O 12 :Ce3+ phosphor are improved obviously, indicating that the prepared sample is a promising red phosphor applied to WLED lighting field. Noticeably, based on the characteristics of high PLQY (63.09%), high color purity (97%) and short fluorescence lifetime (< 4 ms) of the phosphor, we also fabricated a WLED device with wide color gamut (105.1% NTSC value), indicating that the phosphor can also be well applied to the field of wide color gamut fast response backlight display, which greatly expands the application value of the phosphor. [Display omitted] • Red phosphor K 3 MoO 2 F 5 ·2 H 2 O:Mn4+ was synthesized by simple co-precipitation method. • Phosphor presents strong ZPL at ~623 nm, high color purity (98.5%) and PLQY (63.09%). • Emission intensity and moisture resistance was enhanced by surface modification. • The fabricated warm WLED devices show excellent photoelectric performance. • WLED device with wide color gamut (NTSC value of 105.1%) was implemented. [ABSTRACT FROM AUTHOR]

Mn4+ activated K 2 SiF 6 red phosphors have attracted widespread attention, while the poor moisture resistance restrains their further applications. In order to optimize the luminescence intensity of the K 2 SiF 6 :Mn4+ red phosphors immersed in water, we synthesized K 2 SiF 6 :Mn4+, Li + red phosphors with LiF as lithium source. The luminous intensity of K 2 SiF 6 :Mn4+, Li+ phosphor is approximately 133% of K 2 SiF 6 :Mn4+ red phosphors. By coating BaSO 4 layer on the surface of K 2 SiF 6 :Mn4+, Li+ samples, the luminous intensity of K 2 SiF 6 :Mn4+, Li+@BaSO 4 red phosphor maintains 83% of the initial intensity after soaking in water for 6 h. In addition, the K 2 SiF 6 :Mn4+, Li+@0.8 BaSO 4 red phosphor has higher luminous intensity at 150 °C. Finally, by combining with InGaN blue chip and yellow phosphor (YAG:Ce3+) to fabricate warm white LED devices, the warm white LED device based on K 2 SiF 6 :Mn4+, Li+@0.8 BaSO 4 red phosphor has excellent performance (CCT = 3558 K, CRI = 91.4). [Display omitted] • The luminescent properties and water resistance of K 2 SiF 6 :Mn4+ were optimized by doping Li+ and coating BaSO 4. • The red phosphor KSFM:3%Li+@0.8 BaSO 4 has good waterproof stability. • The KSFM:3%Li+@0.8 BaSO 4 phosphors have excellent photoelectric performance for LED application. [ABSTRACT FROM AUTHOR]

The establishment of new enzymatic function in an existing scaffold is a great challenge for protein engineers. In previous work, a highly efficient artificial selenoenzyme with controllable activity was constructed, based on a Ca2+‐responsive recoverin (Rn) protein. In this study, a design strategy combining docking, molecular dynamics, and MM‐PBSA is presented, to predict the catalytically active site of glutathione peroxidase (GPx) on the allosteric domain of Rn. The energy contributions of the binding hot spot residues are evaluated further by energy decomposition analysis to determine the detailed substrate recognition mechanism of Rn, which provides clear guidance for artificial enzyme design for improved substrate binding (Michaelis–Menten constant, Km). [ABSTRACT FROM AUTHOR]

Herein, we demonstrate a supramolecular nanochannel formed by intermolecular π stacking of pyridine–pyridazine helical oligomers, wherein alkali ions could be easily recognized and transported. Importantly, this nanochannel also revealed reversible collection and triggered-release behaviors via modulating the folded and unfolded states of helical pyridine–pyridazine oligomers. [ABSTRACT FROM AUTHOR]

Redox responsive vesicles were constructed based on self-assembly of a supra-amphiphile built by the host- guest interaction between β-cyclodextrin and a ferrocene derivative. The structure and destruction-reconstruction reversibility of the 'smart' vesicles were clearly characterized by electron microscopy and dynamic light scattering. Notably, these vesicles were proved to be capable of controlled release function and bringing protease resistance to the enzyme, showing great biocompatibility and promising applications. [ABSTRACT FROM AUTHOR]

Constructing a highly selective photothermal antibacterial system based on covalent self-assembly monolayered nanosheets. The nanosheets could be converted to radical anions in the presence of facultative anaerobic E. coli , which showed excellent photothermal conversion efficiency under NIR irradiation. The highly selective photothermal antibacterial activity could be realized by the different amplification of radical anions for E. coli and B. subtilis. [Display omitted] • Monolayered nanosheets bearing perylene diimide derivative and pillar[5]arene were constructed through covalent assembly strategy. • Nanosheets could be converted to radical anions in the presence of facultative anaerobic E. coli. • Selective photothermal antibacterial activity was realized by different amplification of radical anions for E. coli and B. subtilis. • Intelligent photothermal nanosheets with excellent biocompatibility. Bacterial infection is one of the most serious physiological conditions threatening human health. There is an increasing demand for selective antibacterial therapy through noninvasive approaches recently years. Herein, a novel strategy for fabrication of positively charged, monolayered nanosheets (P5PD) bearing perylene diimide derivative (DAPDI) was reported through covalent self-assembly with laterally-brominated pillar[5]arene (LBP5). Mannose derivative (Man-HQA) was further immobilized to P5PD nanosheets (named as mP5PD) through host–guest complexation with LBP5 for improving biocompatibility and recognition with microbes. It was found that the mP5PD nanosheets could be converted to radical anions in the presence of E. coli in terms of their excellent reductive surroundings, which showed excellent photothermal conversion efficiency under the 0.5 W/cm2 of 808 nm laser irradiation. Moreover, the selective photothermal antibacterial activity could be realized by the different ability of amplifying radical anions for facultative anaerobic E. coli and aerobic B. subtilis. Importantly, the mP5PD nanosheets exhibited excellent biocompatibility to mammalian cells even at high concentration, which held great potential for developing intelligent photothermal nanomaterials in future biomedical fields. [ABSTRACT FROM AUTHOR]

A rapid and effective enzymatic strategy for the fabrication of a supramolecular polymer is presented for the first time, in which a bifunctional ternary host–guest supramonomer is first prepared followed by subsequent enzymatic coupling of supramonomers. [ABSTRACT FROM AUTHOR]

A pH-responsive artificial selenoenzyme was constructed by reversible binding between organoselenium compound 1 and CB[6] to form a pseudorotaxane-based molecular switch in response to pH stimuli. The glutathione peroxidase (GPx) activity of the artificial selenoenzyme can be switched on/off in a mild and body suitable environment between pH = 7 and pH = 6. [ABSTRACT FROM AUTHOR]

Limited peroxymonosulfate (PMS, HSO 4 −) activation efficiency resulted from slow metal reduction has been a challenge in visible-light (vis) assisted sulfate radical-based oxidation. Herein, a Z-scheme photocatalyst composed of nitrogen-defect-rich graphitic carbon nitride nanosheets embedded with nickel cobaltate nanoparticles (NiCo 2 O 4 /g-C 3 N 4 -N vac) was elaborately designed to accelerate Ni(III)/Ni(II) and Co(III)/Co(II) cycles for PMS activation in PMS/vis system. The NiCo 2 O 4 /g-C 3 N 4 -N vac exhibited remarkable enhancement with a tetracycline hydrochloride (TCH) degradation rate constant (0.1168 min−1), higher than those of NiCo 2 O 4 /g-C 3 N 4 (0.0724 min−1) and g-C 3 N 4 (0.0233 min−1), respectively. Also, the removal efficiencies of 95.5%, 94.2%, 98.0% and 91.4% for carbamazepine, 4-chlorophenol, atrazine and p-nitrophenol were achieved within 30 min, respectively. Theoretical and experimental results suggested that nitrogen (N) vacancies modulated electric structure to build Z-scheme-charge-transfer platform for rapid reduction of Ni(III) and Co(III), thereby accelerating PMS activation for remarkable removal of emerging pollutants. NiCo 2 O 4 /g-C 3 N 4 -N vac exhibited excellent stability and corresponding electrical energy per order (EE/O) in different water matrix was evaluated. Additionally, TCH degradation behavior, pathways and toxicity of products were analyzed, respectively. This work provided an novel paradigm to design the efficient photo-activator of PMS for environmental remediation. [Display omitted] • Z-scheme NiCo 2 O 4 /g-C 3 N 4 -N vac was designed to accelerate PMS activation. • N vacancies lower barrier for achieving Z-scheme charge transfer route. • NiCo 2 O 4 /g-C 3 N 4 -N vac had remarkable performance for various emerging pollutants. • Lower EE/O values in different water matrix engendered more economic benefits. • Degradation pathway and toxicity of products was proposed. [ABSTRACT FROM AUTHOR]

Highlights from the article: Keywords: artificial enzymes; enzyme design; enzymes; GPx mimics; molecular modeling; substrate recognition Molecular modeling, substrate recognition, enzymes, enzyme design, artificial enzymes, GPx mimics.