Dynamic changes of Th1/Th2/Th17 cytokines and hBD-2/3 in erosive oral lichen planus patients saliva before and after prednisone acetate treatment.

Objective: This study aimed to investigate the expression of T helper 1 (Th1)/Th2/Th17- related cytokines and human beta defensins 2 and 3 (hBD-2 and -3) in the saliva of patients with erosive oral lichen planus (EOLP) and to explore their role in the pathogenesis of EOLP and the effects of glucocorticoids on EOLP. Methods: A total of 30 patients with EOLP and 20 age- and sex-matched healthy individuals were included in this study. The patients were treated with prednisone at a dose of 0.4 mg/(kg·d) for 1 week and examined before and after treatment. Unstimulated whole saliva samples were collected to determine the levels of cytokines (interleukin 1 beta [IL-1ß], tumour necrosis factor alpha [TNF]-α, interferon gamma [IFN-γ], IL-4, IL-6, IL-10 and IL-17) by cytometric bead array and those of hBD-2 and -3 b y enzyme-linked immunosorbent assay. In addition, oral rinse samples were collected to detect Candida load. Results: The levels of salivary IL-1ß, IL-6, hBD-2 and hBD-3 were higher and the IFN-γ/IL-4 and IL-1ß/IL-6 ratios were lower in patients with EOLP than in healthy individuals. In patients with EOLP, hBD-2 levels were positively correlated with IFN-γ levels and negatively correlated with IL-17 levels, whereas hBD-3 levels were negatively correlated with IL-17 and IL-10 levels. In addition, the prevalence of EOLP was positively correlated with IL-6 levels and negatively correlated with the IFN-γ/IL-4 ratio. The levels of IL-1ß, TNF-α, IFN-γ, IL-6, hBD-2 and hBD-3 and the IFN-γ/IL-4 ratio decreased after treatment with prednisone for 1 week. The levels of IL-6, hBD-2 and hBD-3 were significantly higher in EOLP patients than in healthy individuals; while TNF-α levels and the IFN-γ/IL-4 ratio were significantly lower in EOLP patients than in healthy individuals. Furthermore, the oral counts of Candida spp. (colony forming unit [CFU]) were negatively correlated with TNF-α levels. Numerical Rating Scale(NRS) and Sign scores decreased in EOLP patients after treatment. Approximately 80 % of patients were effectively treated. Salivary TNF-α levels were significantly higher in the treatment-ineffective group than in the treatment-effective group before treatment with prednisone, and differences in salivary IL-6 levels before and after treatment were significantly higher in the treatment-effective group than in the treatment-ineffective group. Conclusions: High expression of IL-1ß, IL-6, hBD-2 and Th1/Th2 imbalance in saliva may be associated with the pathogenesis of EOLP. IFN-γ/IL-4 balance may serve as a protective factor for EOLP. Glucocorticoids significantly alleviate the symptoms of EOLP and inhibit the expression of Th1/Th2 cytokines.

Guiding Zn Uniform Deposition with Polymer Additives for Long-lasting and Highly Utilized Zn Metal Anodes.

The parasitic side reaction on Zn anode is the key issue which hinders the development of aqueous Zn-based energy storage systems on power-grid applications. Here, a polymer additive (PMCNA) engineered by copolymerizing 2-methacryloyloxyethyl phosphorylcholine (MPC) and N-acryloyl glycinamide (NAGA) was employed to regulate the Zn deposition environment for satisfying side reaction inhibition performance during long-term cycling with high Zn utilization. The PMCNA can preferentially adsorb on Zn metal surface to form a uniform protective layer for effective water molecule repelling and side reaction resistance. In addition, the PMCNA can guide Zn nucleation and deposition along 002 plane for further side reaction and dendrite suppression. Consequently, the PMCNA additive can enable the Zn//Zn battery with an ultrahigh depth of discharge (DOD) of 90.0 % for over 420 h, the Zn//active carbon (AC) capacitor with long cycling lifespan, and the Zn//PANI battery with Zn utilization of 51.3 % at low N/P ratio of 2.6.

Modulating the Coordination Environment of Lithium Bonds for High Performance Polymer Electrolyte Batteries.

The new-generation lithium metal batteries require polymer electrolytes with high ionic conductivity and mechanical properties. However, the performance of the polymer electrolytes is severely influenced by the lithium bond formation between the functional groups and lithium ions (Li+), which has barely been considered in the past. Herein, a lithium bond enriched polymer gel (PAEV) is elaborately designed by copolymerizing 4-acryloylmorpholine (ACMO) and 1-vinyl-3-ethyl imidazolium bis(trifluoromethylsulfonyl)imide ([VEIM][TFSI]) in 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]) with the presence of LiFSI. The lithium bonds formed between LiFSI and carbonyl groups in PACMO can be regulated by the Li+ coordination number, and further weakened by the hydrogen bonds with [EMIM][TFSI] and poly[VEIM][TFSI], to effectively render the polymer electrolyte with adjustable ionic conductivity and tunable mechanical property. In addition, with the regulated coordination environment of Li+, the LiF and Li3N layer can be uniformly formed on the Li surface to facilitate Li+ nucleation and deposition. As a consequence, the PAEV electrolyte confers the Li/LiFePO4 (LFP) battery with high capacity of 124 mA h g-1 at 1 C under 25 °C, and 152 mA h g-1 under 50 °C. This work can promote the development of high performance polymer electrolyte via lithium bond manipulation.

Proton-Reservoir Hydrogel Electrolyte for Long-Term Cycling Zn/PANI Batteries in Wide Temperature Range.

Advanced aqueous batteries are promising for next generation flexible devices owing to the high safety, yet still requiring better cycling stability and high capacities in wide temperature range. Herein, a polymeric acid hydrogel electrolyte (PAGE) with 3 M Zn(ClO4 )2 was fabricated for high performance Zn/polyaniline (PANI) batteries. With PAGE, even at -35 °C the Zn/Zn symmetrical battery can keep stable for more than 1 500 h under 2 mA cm-2 , and the Zn/PANI battery can provide ultra-high stable specific capacity of 79.6 mAh g-1 for more than 70 000 cycles at 15 A g-1 . This can be mainly ascribed to the -SO3 - H+ function group in PAGE. It can generate constant protons and guide the (002) plane formation to accelerate the PANI redox reaction kinetics, increase the specific capacity, and suppress the side reaction and dendrites. This proton-supplying strategy by polymeric acid hydrogel may further propel the development of high performance aqueous batteries.

Gel Electrolyte Constructing Zn (002) Deposition Crystal Plane Toward Highly Stable Zn Anode.

Zinc (Zn) metal anode has been widely evaluated in aqueous Zn batteries. Nevertheless, the dendrite formation issue and consecutive side reactions severely impede the practical applications of Zn metal at high current densities. Herein, it is reported that engineering the gel electrolyte with multifunctional charged groups by incorporating a zwitterionic gel poly(3-(1-vinyl-3-imidazolio) propanesulfonate) (PVIPS) can effectively address the abovementioned issues. The charged groups of sulfonate and imidazole in the gel electrolyte can texture the Zn2+ nucleation and deposition plane to (002), which possesses a high activation energy to resist side reactions and induce uniform growth of Zn metal for a dendrite-free structure. In addition, the Zn2+ solvation structure can be manipulated by the charged groups to further eliminate side reactions for high rate performance Zn batteries. Consequently, the polyzwitterionic gel electrolyte enables a stable cycling with a cumulative capacity of 3000 mA h cm-2 at high density of 7.5 mA cm-2 for the symmetrical Zn battery, and a long-term cycling life for more than 1000 cycles at 5 C of Zn/MnO2 full battery. It is envisioned that the design of the gel electrolyte will provide promising feasibility on safe, flexible, and wearable energy storage devices.

Immunizing Aqueous Zn Batteries against Dendrite Formation and Side Reactions at Various Temperatures via Electrolyte Additives.

Aqueous Zn-ion batteries own great potential on next generation wearable batteries due to the high safety and low cost. However, the uncontrollable dendrites growth and the negligible subzero temperature performance impede the batteries practical applications. Herein, it is demonstrated that dimethyl sulfoxide (DMSO) is an effective additive in ZnSO4 electrolyte for side reactions and dendrites suppression by regulating the Zn-ion solvation structure and inducing the Zn2+ to form the more electrochemical stable (002) basal plane, via the higher absorption energy of DMSO with Zn2+ and (002) plane. Moreover, the stable reconstructed hydrogen bonds between DMSO and H2 O dramatically lower the freezing point of the electrolyte, which significantly increases the ionic conductivity and cycling performance of the aqueous batteries at subzero temperatures. As a consequence, the symmetrical Zn/Zn cell can be kept stable for more than 2100 h at 20 °C and 1200 h at -20 °C without dendrite and by-products formation. The Zn/MnO2 batteries can perform steadily for more than 3000 cycles at 20 °C and 300 cycles at -20 °C. This work provides a facile and feasible strategy on designing high performance and dendrite free aqueous Zn-ion batteries for various temperatures.

A stable Ln(iii)-functionalized Cd(ii)-based metal-organic framework: tunable white-light emission and fluorescent probe for monitoring bilirubin.

A novel anionic Cd(ii)-based metal-organic framework, H2[Cd9(DDB)4(BPP)4(H2O)14]·4H2O·2DMA (1), was successfully obtained with a rigid carboxylate ligand 3,5-di(2',4'-dicarboxylphenyl)benzoic acid (H5DDB) and a flexible pyridyl ligand 1,3-bis(4-pyridyl)propane (BPP). Complex 1 contains two-dimensional (2D) honeycomb structures and one-dimensional (1D) chain structures. The adjacent 2D structures are linked by strong intermolecular hydrogen bonds to form an ABAB 3D supramolecular structure, where the 1D chain structures traverse the channels of the 2D structures. Due to the anionic framework, Ln(iii) ions (Ln = Eu and Tb) can be encapsulated in the framework of 1 by a post-synthetic modification process to obtain Ln(iii)@1, where 1.09Eu(iii)@1 (1a) and 0.658Tb(iii)@1 (1b) can be obtained by soaking complex 1 in a Eu(NO3)3·6H2O or Tb(NO3)3·6H2O aqueous solution for 48 h. The liquid-state emission spectra of Ln(iii)@1 can be tuned to be a white light emission by changing the Eu(iii)/Tb(iii) molar ratio in solution. Moreover, 1b can be used as a "turn-off" fluorescent probe for bilirubin with a low detection limit of 0.250 µM in phosphate buffer solution (pH = 7.4), which presents excellent sensitivity, high selectivity, and reusability. Furthermore, the devised fluorescent probe in serum also exhibits the fluorescence "turn-off" process with a low detection limit of 0.279 µM, and the recovery rate of bilirubin is 99.20-101.9%. The possible mechanisms of the fluorescence "turn-off" process can be explained by resonance energy transfer, and the weak interaction between 1b and bilirubin.

Recent advances in metal-organic frameworks for pesticide detection and adsorption.

The large-scale use of pesticides such as organophosphate pesticides (OPPs) and organochlorine pesticides (OCPs) has led to serious environmental problems worldwide, and their high toxicity could cause serious damage to human health. It is crucial to remove and track them precisely in the environment and food resources. As novel nanomaterials, metal-organic frameworks (MOFs) have attracted significant attention in the fields of adsorption and luminescence sensing due to their rich topology, tunable pore size and shape, high surface area, and abundant active sites. Luminescent metal-organic frameworks (LMOFs) have sprung up as great potential chemical sensors to detect pesticides with fast response, high sensitivity, high selectivity and easy operation. Therefore, in this highlight, we focus on recent progress of MOFs in sensing and adsorbing pesticides, as well as in the possible mechanism of sensing, so as to attract more attention to pesticide detection and adsorption.

A water-stable zinc(ii)-organic framework as a multiresponsive luminescent sensor for toxic heavy metal cations, oxyanions and organochlorine pesticides in aqueous solution.

A novel metal-organic framework with the formula [Zn3(DDB)(DPE)]·H2O (1) (H5DDB = 3,5-di(2',4'-dicarboxylphenyl)benzoic acid and DPE = 1,2-di(4-pyridyl)ethylene) has been solvothermally synthesized by employing a rigid carboxylate ligand H5DDB to assemble with Zn(ii) ions in the presence of a flexible bis(pyridyl) linker DPE. The Zn-MOF is a 3D framework with six-nuclear clusters and possesses remarkable water stability and pH stability. Interestingly, complex 1 can sensitively and selectively sense Fe(iii), Cr(iii), Cr(vi), Mn(vii) and the pesticide 2,6-Dich-4-NA with low detection limits in aqueous solution. Moreover, complex 1 also exhibits selectivity for 2,6-Dich-4-NA detection in real samples including carrot, grape and nectarine extracts, and its detection ability is almost unchanged in the presence of the surfactant sodium dodecyl sulfate (SDS). The possible mechanisms of luminescence quenching have been explained by the weak affinity of nitrogen atoms, resonance energy transfer, and photoinduced electron transfer. To our knowledge, this is the first example of a MOF-based multiresponsive fluorescent probe for the simultaneous detection of Fe(iii), Cr(iii/vi), Mn(vii) and the pesticide 2,6-Dich-4-NA in aqueous solution.

Two novel metal-organic frameworks based on pyridyl-imidazole-carboxyl multifunctional ligand: selective CO2 capture and multiresponsive luminescence sensor.

Two novel metal-organic frameworks, formulated as [Mn(CIP-)2] (1) and [Ag(CIP-)] (2) (HCIP = 4-(4-carboxylphenyl)-2,6-di(4-imidazol-1-yl)phenyl)pyridine), were solvothermally synthesized based on a pyridyl-imidazole-carboxyl multifunctional ligand. The single-crystal X-ray diffraction analysis shows that complex 1 is a 3D microporous framework with uncoordinated imidazole groups, and complex 2 is a 2D + 2D → 2D 3-fold parallel interpenetrated network. Complex 1 exhibited excellent CO2 selective absorption over N2 and CH4. IAST calculations revealed that the selectivities of 1 for the CO2/CH4 (50 : 50) and CO2/N2 (15 : 85) mixtures were 8.0 and 117 at 273 K under 1 bar, respectively. Moreover, the luminescence investigations displayed that complex 2 is an excellent MOF-based multiresponsive fluorescent probe for Fe3+, CrO42-/Cr2O72- and the pesticide 2,6-Dich-4-nitroaniline, with high selectivity and sensitivity. Notably, complex 2 exhibited a highly sensitive sensing ability (5.2 × 104 M-1) and a low detection limit (1.7 × 10-7 M) for 2,6-Dich-4-nitroaniline. To the best of our knowledge, this is the first Ag-MOF-based fluorescent sensor that can simultaneously detect metal ions, inorganic anions and pesticides.