Poly (vinyl alcohol)/sodium alginate/carboxymethyl chitosan multifunctional hydrogel loading HKUST-1 nanoenzymes for diabetic wound healing.

Bacterial infection, hyperinflammation and hypoxia, which can lead to amputation in severe cases, are frequently observed in diabetic wounds, and this has been a critical issue facing the repair of chronic skin injuries. In this study, a copper-based MOF (TAX@HKUST-1) highly loaded with taxifolin (TAX) with a drug loading of 41.94 ± 2.60 % was prepared. In addition, it has excellent catalase activity, and by constructing an oxygen-releasing hydrogel (PTH) system with calcium peroxide (CaO2), it can be used as a nano-enzyme to promote the generation of oxygen from hydrogen peroxide (H2O2) to provide sufficient oxygen to the wound, and at the same time, solve the problem of the oxidative stress damage caused by excess H2O2 to the cells during the oxygen-releasing process. On the other hand, TAX and HKUST-1 in PTH synergistically promoted antimicrobial and anti-oxidative stress properties, and the bacterial inhibition rate against Staphylococcus aureus and Escherichia coli reached 90 %. In vivo experiments have shown that PTH hydrogel is able to treat diabetic skin repair by inhibiting the expression of inflammation-related proteins and promoting epidermal neogenesis, angiogenesis and collagen deposition.

Adsorption of chloramphenicol from water using Carex meyeriana Kunth-derived hierarchical porous carbon with open channel arrays.

A carbon material with both open macrochannel arrays and abundant micro/mesopores was prepared, characterized, and applied for removing chloramphenicol (CAP) from water. In the preparation process, Carex meyeriana Kunth (CM) with natural channel arrays was used as the precursor for producing the biochar, and NaOH was used for removing silicon and formatting micro- and mesopores of the porous carbon. The product (PCCM) exhibited the highest specific surface area (2700.24 m2 g-1) among the reported CM-derived porous carbons. The adsorption performances of PCCM were evaluated through batch adsorption experiments. The maximum adsorption capacity of PCCM toward CAP was 1659.43 mg g-1. The adsorption mechanism was investigated with the aid of theoretical calculations. Moreover, PCCM exhibited better performance than other porous carbon adsorbents in fixed-bed experiments, which may be due to its structural advantages.

A Weed-Derived Hierarchical Porous Carbon with a Large Specific Surface Area for Efficient Dye and Antibiotic Removal.

Adsorption is an economical and efficient method for wastewater treatment, and its advantages are closely related to adsorbents. Herein, the Abutilon theophrasti medicus calyx (AC) was used as the precursor for producing the porous carbon adsorbent (PCAC). PCAC was prepared through carbonization and chemical activation. The product activated by potassium hydroxide exhibited a larger specific surface area, more mesopores, and a higher adsorption capacity than the product activated by sodium hydroxide. PCAC was used for adsorbing rhodamine B (RhB) and chloramphenicol (CAP) from water. Three adsorption kinetic models (the pseudo-first-order, pseudo-second-order, and intra-particle diffusion models), four adsorption isotherm models (the Langmuir, Freundlich, Sips, and Redlich-Peterson models), and thermodynamic equations were used to investigate adsorption processes. The pseudo-second kinetic and Sips isotherm models fit the experimental data well. The adsorption mechanism and the reusability of PCAC were also investigated. PCAC exhibited a large specific surface area. The maximum adsorption capacities (1883.3 mg g-1 for RhB and 1375.3 mg g-1 for CAP) of PCAC are higher than most adsorbents. Additionally, in the fixed bed experiments, PCAC exhibited good performance for the removal of RhB. These results indicated that PCAC was an adsorbent with the advantages of low-cost, a large specific surface area, and high performance.

Study on the Preparation of Estrone Molecularly Imprinted Polymers and Their Application in a Quartz Crystal Microbalance Sensor via a Computer-Assisted Design.

Computer simulations are widely used for the selection of conditions for the synthesis of molecularly imprinted polymers and can rapidly reduce the experimental cycle time and save labor and materials. In this paper, estrone molecularly imprinted polymers (E1-MIPs) are designed at the M062X/6-311+G(d,p) level with itaconic acid (IA) as the functional monomer. The imprinted molar ratio between E1 and IA was optimized, cross-linkers and solvents were screened, and the nature of interactions between E1 and IA was explored. The simulated results showed that pentaerythritol triacrylate was the best cross-linker. Meanwhile, when the imprinted molar ratio between E1 and IA was 1:4, the E1-IA complex had the largest amount of hydrogen bonds, the lowest binding energy, and the strongest stability. Using the simulation results as guidance, the E1-MIPs were prepared to modify the electrons of a quartz crystal microbalance (QCM) sensor. The experimental studies showed that the E1-MIPs-QCM sensor had the highest adsorption capacity to E1 in comparison with their analogues, and the lowest detection value of the sensor was 16.00 µg/L. The computer simulations and experimental studies could provide guidance for synthesize novel E1-MIPs materials. It also could provide important references and directions for the application of E1-MIPs.

Preparation of a quartz microbalance sensor based on molecularly imprinted polymers and its application in formaldehyde detection.

Quartz crystal microbalances (QCMs) have been widely used in the food industry, environmental monitoring, and biomedicine. Here, a molecularly imprinted QCM sensor was prepared and used for formaldehyde detection. Using polyvinyl chloride as the embedding material and tetrahydrofuran as the solvent, a QCM electrode was modified with HCHO molecularly imprinted polymers (HCHO-MIPs). The detection conditions of the sensor were optimized, and its selectivity was investigated. The theoretical calculation results revealed that the acrylamide and pentaerythritol triacrylate were potential candidate functional monomer and cross-linking agent, respectively, in the preparation of HCHO-MIPs with high adsorbability, superselectivity, and stability. According to the calculated results, a sensor had been prepared. When the pH was 7, the added mass of the HCHO-MIPs (or NIPs) was 20 mg, and the amount of PVC coating was 20 µL, the sensor exhibited good adsorption, selectivity, repeatability, high sensitivity, high accuracy, and a short response time. The lowest detection limit was 10.72 ng mL-1. The sensor exhibited higher selectivity for HCHO than for propionaldehyde and benzaldehyde. The HCHO contents in fresh shrimp samples were detected using the sensor for four cycles, and the detection rates were in the range of 97.56-98.60%. This study provided a theoretical and experimental basis for the rapid detection of HCHO.

Design, preparation and adsorption performances of norfloxacin molecularly imprinted polymers.

Here, norfloxacin (NOR) molecularly imprinted polymers (MIPs) exhibiting improved adsorption and selectivity properties were prepared via simulation and experiment. NOR and methacrylic acid (MAA) were employed as the imprinting molecule and functional monomer, respectively. The imprinting ratio, as well as cross-linking agents of the NOR-MIPs, had been optimised via the LC-ωPBE/6-31G(d,p) method. The nature and mechanism of the interaction between MIPs and MAA, as well as the selectivity of the NOR-MAA stable complex (1:1), were also discussed. Based on the simulation results, the effects of the different imprinting ratios and cross-linking agents on the adsorption of NOR-MIPs were also investigated. Concurrently, the affinity, selectivity and stability of NOR-MIPs were analysed via dynamic, static and selective adsorption, as well as thermogravimetry. The calculated and experimental results demonstrated that the stable complexes comprising NOR and MAA were formed via hydrogen bonding. The complex comprising NOR and MAA in an interaction ratio of 1:6 exhibited the highest number of hydrogen bonds and the lowest binding energy. Trihydroxymethylpropyl trimethylacrylate was more appropriate for the synthesis of NOR-MIPs compared with the two other cross-linking agents. NOR-MIPs achieved the excellent selective adsorption of NOR in single and multiple adsorption systems. This design and synthesis strategy availed a new idea for the efficient preparation of s with specific adsorption performance.

Design of sensitizer with suitable frontier molecular orbital via substitution on starburst triphenylamine derivative.

Herein, a series of organic molecules were designed through locating different substituents on the compound (WD8-c-1) to develop their performances used as the sensitizers in the field of dye-sensitized solar cells. The geometry and relevant electronic properties of WD8-c-1 and its derivatives were simulated at the B3LYP/6-31G(d,p) level. The absorption spectra were calculated using the TD-PBE0/6-31+G(d,p) method. These calculated results show that the type and position of the substituents strongly affected the distributions of frontier molecular orbitals and the energy gaps for the WD8-c-1-derived molecules. The reorganization energies results reveal that their hole charge transfer rates are higher than that of the representative hole transport material. Moreover, the mobility of the representative WD8-c-1 derivative also has been simulated. The starburst triphenylamine with suitable substituent has the more suitable FMO energy to match those of TiO2, broad absorption region, smaller reorganization energies, and high hole mobility.

A theoretical approach of star-shaped molecules with triphenylamine core as sensitizer for their potential application in dye sensitized solar cells.

This work is supplying an in-depth investigation of the optical, electronic, and charge transfer properties for heteroatom effects on the starburst triphenylamine derivative, molecule WD8-c-1, which has been studied in our previous work. The geometry and relevant electronic properties of WD8-c-1 and its derivatives in ground state for photovoltaic applications were simulated by the B3LYP/6-31G (d,p) method. Their absorption spectra have been calculated at the TD-PBE0/6-31 + G (d,p) level. The results indicate that the oxygen and sulfur atom substituents affect the distributions of frontier molecular orbitals and energy gap of WD8-c-1 significantly. Moreover, the electron could transfer from excited sensitizer into the conduction band (CB) of TiO2. The heteroatom substituent affect the absorption spectra of WD8-c-1 significantly. The hole transfer rates of WD8-c-1 and its derivatives are higher than that of N,N'-diphenyl-N,N'-bis(3-methlphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD) and WD8-c-1-S owns the smallest hole reorganization energy (λh) value among the investigated molecules. The introducing of heteroatom affect the short-circuit current density and open-circuit photovoltage properties of WD8-c-1 and its derivatives significantly.

Theoretical and experimental research on self-assembly system of molecularly imprinted polymers formed via chloramphenicol and methacrylic acid.

Chloramphenicol was chosen as the imprinting molecule and the methacrylic acid was chosen as the functional monomer to prepare molecularly imprinted polymers. Ethylene glycol dimethacrylate, pentaerythritol triacrylate, and trimethylolpropane trimethylacrylate were used as the cross-linking agents, respectively. The interaction processes between chloramphenicol and methacrylic acid were simulated by using the ωB97XD/6-31G (d,p) method. The self-assembled configuration, bonding sites, binding number, binding energy, and interaction principle of stable complex formed by chloramphenicol and methacrylic acid with different molar ratios have been studied. The selectivity of the most stable complex formed from chloramphenicol and methacrylic acid was discussed with the thiamphenicol and florfenicol as the analogues of chloramphenicol. The results showed that chloramphenicol and methacrylic acid were interacted through the hydrogen bonds. When the molar ratio was 1:10 and pentaerythritol triacrylate as the cross-linking agent, the ordered complex formed by chloramphenicol and methacrylic acid has the largest amount of hydrogen bonds and the lowest binding energy. Scatchard analysis showed that the maximum apparent adsorption capacity was 173.3 mg/g (0.536 mol/g), and the selection factor of florfenicol was the largest. This study provides a reliable theoretical and experimental basis for the design, preparation, and characterization of chloramphenicol molecularly imprinted polymers.

Study on Dicyandiamide-Imprinted Polymers with Computer-Aided Design.

With the aid of theoretical calculations, a series of molecularly imprinted polymers (MIPs) were designed and prepared for the recognition of dicyandiamide (DCD) via precipitation polymerization using acetonitrile as the solvent at 333 K. On the basis of the long-range correction method of M062X/6-31G(d,p), we simulated the bonding sites, bonding situations, binding energies, imprinted molar ratios, and the mechanisms of interaction between DCD and the functional monomers. Among acrylamide (AM), N,N'-methylenebisacrylamide (MBA), itaconic acid (IA), and methacrylic acid (MAA), MAA was confirmed as the best functional monomer, because the strongest interaction (the maximum number of hydrogen bonds and the lowest binding energy) occurs between DCD and MAA, when the optimal molar ratios for DCD to the functional monomers were used, respectively. Additionally, pentaerythritol triacrylate (PETA) was confirmed to be the best cross-linker among divinylbenzene (DVB), ethylene glycol dimethacrylate (EGDMA), trimethylolpropane trimethylacrylate (TRIM), and PETA. This is due to the facts that the weakest interaction (the highest binding energy) occurs between PETA and DCD, and the strongest interaction (the lowest binding energy) occurs between PETA and MAA. Depending on the results of theoretical calculations, a series of MIPs were prepared. Among them, the ones prepared using DCD, MAA, and PETA as the template, the functional monomer, and the cross-linker, respectively, exhibited the highest adsorption capacity for DCD. The apparent maximum absorption quantity of DCD on the MIP was 17.45 mg/g.

Design of Acceptors with Suitable Frontier Molecular Orbitals to Match Donors via Substitutions on Perylene Diimide for Organic Solar Cells.

A series of perylene diimide (PDI) derivatives have been investigated at the CAM-B3LYP/6-31G(d) and the TD-B3LYP/6-31+G(d,p) levels to design solar cell acceptors with high performance in areas such as suitable frontier molecular orbital (FMO) energies to match oligo(thienylenevinylene) derivatives and improved charge transfer properties. The calculated results reveal that the substituents slightly affect the distribution patterns of FMOs for PDI-BI. The electron withdrawing group substituents decrease the FMO energies of PDI-BI, and the electron donating group substituents slightly affect the FMO energies of PDI-BI. The di-electron withdrawing group substituents can tune the FMOs of PDI-BI to be more suitable for the oligo(thienylenevinylene) derivatives. The electron withdrawing group substituents result in red shifts of absorption spectra and electron donating group substituents result in blue shifts for PDI-BI. The -CN substituent can improve the electron transport properties of PDI-BI. The -CH3 group in different positions slightly affects the electron transport properties of PDI-BI.

Theoretical study of photophysical properties of 1,4-dihydropyrrolo[3,2-b]pyrrole-cored branched molecules with thienylenevinylene arms toward broad absorption spectra for solar cells.

A series of oligo(thienylenevinylene) derivatives with 1,4-dihydropyrrolo[3,2-b]pyrrole as core has been investigated at the PBE0/6-31G(d) and the TD-PBE0/6-31+G(d,p) levels to design materials with high performances such as broad absorption spectra and higher balance transfer property. The results show that position and amount of arm affect the electronic density contours of frontier molecular orbitals significantly. The molecule with four arms owns the narrowest energy gap and the largest maximum absorption wavelength, and the molecule with two arms in positions a and c has the broadest absorption region among the designed molecules. Calculated reorganization energies of the designed molecules indicate that the molecules with two arms can be good potential ambipolar transport materials under proper operating conditions.

Bis[tris(2,2'-bipyridyl-κ2N,N')cobalt(II)] cyclo-tetravanadate undecahydrate.

The title compound, [Co(C(10)H(8)N(2))(3)](2)[V(4)O(12)]·11H(2)O, is composed of two symmetry-related cations containing octahedrally coordinated Co(II) ions, a centrosymmetric [V(4)O(12)](4-) anion with an eight-membered ring structure made up of four VO(4) tetrahedra, and 11 solvent water molecules. The Co(II) cations and vanadate anions are isolated and build cation and anion layers, respectively. In addition, the title compound exhibits a three-dimensional network through intra- and intermolecular hydrogen-bond interactions between water molecules and O atoms of the anions, and the crystal structure is stabilized mainly by hydrogen bonds.

A sodalite-type porous metal-organic framework with polyoxometalate templates: adsorption and decomposition of dimethyl methylphosphonate.

A sodalite-type porous metal-organic framework with polyoxometalate templates, H(3)[(Cu(4)Cl)(3)(BTC)(8)](2)[PW(12)O(40)]·(C(4)H(12)N)(6)·3H(2)O (NENU-11; BTC = 1,3,5-benzenetricarboxylate), was obtained by a hydrothermal reaction. As a reasonable candidate for eliminating nerve gas, NENU-11 displays good adsorption behavior for dimethyl methylphosphonate (15.5 molecules per formula unit). In virtue of the catalytic activity of polyoxometalate guests, this nerve gas mimic could be facilely decomposed by a hydrolysis reaction.

Reactivity of polyoxoniobates in acidic solution: controllable assembly and disassembly based on niobium-substituted germanotungstates.

The reactivity of polyoxoniobates has been studied in acidic solution by grafting niobium onto trivacant Keggin-type germanotungstates. Four niobium-containing compounds were obtained in the course of this study. Cs(6.5)K(0.5)[GeW(9)(NbO(2))(3)O(37)]·6H(2)O (Cs(6.5)K(0.5)-1) synthesized by the reaction of K(7)H[Nb(6)O(19)] and A-α-Na(10)[GeW(9)0(34)] in H(2)O(2) solution is a tris(peroxoniobium)-substituted A-α-GeW(9) derivative. Cs(6.5)K(0.5)[GeW(9)Nb(3)O(40)]·10H(2)O (Cs(6.5)K(0.5)-2) is a peroxo-free compound obtained by eliminating the peroxo groups in 1. Monomers 1 and 2 as precursors can each afford two nanoscale POMs, dimer Cs(5)[H(15)Ge(2)W(18)Nb(8)O(88)]·18H(2)O (Cs(5)-3) and tetramer Cs(8)K(3)H(9)[Ge(4)W(36)Nb(16)O(166)]·27H(2)O (Cs(8)K(3)H(9)-4), through the formation of Nb-O-Nb bridges. Disassembly through the cleavage of Nb-O-Nb bonds from 4 to 2 and 1 was achieved by controlling the pH and by adding H(2)O(2), respectively. The transition from 1 to 2 can be achieved by simply adding H(2)O(2) to a solution of 1. All four compounds were characterized in the solid state by elemental analysis, infrared spectroscopy, thermogravimetry, and single-crystal X-ray diffraction. (183)W NMR analysis proved that the solid-state structures of polyanions 1-4 were retained after dissolution. Disassembly from 4 to 1 and 2 in solution was observed by (183)W NMR spectroscopy. The UV/Vis spectra of 1 at different pH confirmed that it is stable in the pH range of 0.1-14.0 at room temperature.

Highly stable crystalline catalysts based on a microporous metal-organic framework and polyoxometalates.

A series of remarkable crystalline compounds [Cu(2)(BTC)(4/3)(H(2)O)(2)](6)[H(n)XM(12)O(40)].(C(4)H(12)N)(2) (X = Si, Ge, P, As; M = W, Mo) were obtained from the simple one-step hydrothermal reaction of copper nitrate, benzentricaboxylate (BTC), and different Keggin polyoxometalates (POMs). In these compounds, the catalytically active Keggin polyanions were alternately arrayed as noncoordinating guests in the cuboctahedral cages of a Cu-BTC-based metal-organic framework (MOF) host matrix. X-ray crystallographic analyses, TG, FT-IR, UV-vis, N(2) adsorption studies, and acid-base titration demonstrated their high stability and toleration for thermal and acid-base conditions. No POM leaching or framework decomposition was observed in our study. The representative acid catalytic performance of a compound containing PW(12) species was assessed through the hydrolysis of esters in excess water, which showed high catalytic activity and can be used repeatedly without activity loss. Moreover, catalytic selectivity, which is dependent on the molecular size of substrates, and substrate accessibility for the pore surface were observed. It is the first time that the well-defined, crystalline, MOF-supported POM compound has behaved as a true heterogeneous acid catalyst. The unique attributes of MOF and well-dispersed level of POMs prohibited the conglomeration and deactivation of POMs, which allowed for the enhancement of their catalytic properties.

Two Dawson-templated three-dimensional metal-organic frameworks based on oxalate-bridged binuclear cobalt(II)/Nickel(II) SBUs and Bpy linkers.

The Dawson anion P 2W 18O 62 (6-) has been used as a noncoordinating polyoxoanion template for the construction of two metal-organic frameworks, namely, [M 2(bpy) 3(H 2O) 2(ox)][P 2W 18O 62]2(H 2-bpy). nH 2O (M = Co(II), n = 3 ( 1); M = Ni(II), n = 2 ( 2)) (bpy = 4,4'-bipyridine; ox = C 2O 4 (2-)). Single-crystal X-ray analysis reveals that both of the structures exhibit 3D host frameworks constructed from the oxalate-bridged binuclear superoctahedron secondary building units (SBUs) and bpy linkers and the voids of which are occupied by Dawson anions, guest bpy, and water molecules. Magnetic studies reveal that there are antiferromagnetic exchange interactions among the transition-metal centers in compounds 1 and 2. Furthermore, a compound 1-modified carbon paste electrode ( 1-CPE) displays good electrocatalytic activity toward the reduction of nitrite.