In Vitro Anti-Inflammatory Activity of Three Peptides Derived from the Byproduct of Rice Processing.

Inflammation is a contributing factor to the initiation and progression of many diseases, and some food-derived biofunctional peptides show high anti-inflammatory activity. In our previous study, we demonstrated that peptides derived from trypsin hydrolysis of rice protein show good immunological activity. In the present study, proteins of broken rice were extracted and identified by macroporous resin fractionation and liquid chromatography/tandem mass spectrometry (LC-MS/MS). Subsequently, a bioinformatics prediction and in silico simulation approach was used to screen for peptides showing anti-inflammatory activity, including inhibition of the production of nitric oxide and proinflammatory cytokines (interleukin-1ß, interleukin-6, and tumor necrosis factor-α) by lipopolysaccharide-stimulated RAW264.7 mice macrophages. Three peptides (DNIQGITKPAIR, IAFKTNPNSMVSHIAGK, and IGVAMDYSASSKR) that demonstrated the highest binding affinity were synthesized, and their in vitro anti-inflammatory activity was investigated. This is the first study that integrates LC-MS/MS identification and bioinformatics prediction for reporting the anti-inflammatory activity of anti-inflammatory peptides derived from broken rice protein. The study findings revealed that the peptides derived from the byproduct of rice milling could be potentially used as natural anti-inflammatory alternativities.

Peroxidase-mimetic activity of a nanozyme with uniformly dispersed Fe3O4 NPs supported by mesoporous graphitized carbon for determination of glucose.

A Fe3O4/mesoporous graphitized carbon (Fe3O4/m-GC) composite was prepared through a facile calcination method with iron-based metal-organic frameworks (Fe-MOFs) as a sacrificial template. After carbonization, the Fe3O4 nanoparticles were uniformly dispersed in the mesoporous carbon support, resulting in spatial structural stability. The mesoporous carbon support obtained was highly graphitized and exhibited eminent electrical conductivity, which accelerated the electron transfer between the Fe3O4 nanoparticles by Fe(II)/Fe(III) redox cycles and m-GC by C = Csp2/C-Csp3 redox cycles, leading to the excellent peroxidase-mimetic activity of Fe3O4/m-GC. Km values for tetramethylbenzidine (TMB) and H2O2 were 26.8 and 15.8 times lower than that of natural horseradish peroxidase, respectively. Taking advantage of the peroxidase-mimetic activity of Fe3O4/m-GC, a colorimetric assay was fabricated for detecting glucose in the range 0.5 ~ 200 µM, with a limit of detection of 0.24 µM. Fig 1 A Schematic illustration of the preparation process of Fe3O4/m-GC, B schematic illustration of a proposed synergistic catalytic mechanism of TMB oxidation by Fe3O4/m-GC.

Recent Advances in Porphyrin-Based Materials for Metal Ions Detection.

Porphyrins have planar and conjugated structures, good optical properties, and other special functional properties. Owing to these excellent properties, in recent years, porphyrins and their analogues have emerged as a multifunctional platform for chemical sensors. The rich chemistry of these molecules offers many possibilities for metal ions detection. This review mainly discusses two types of molecular porphyrin and porphyrin composite sensors for metal ions detection, because porphyrins can be functionalized to improve their functional properties, which can introduce more chemical and functional sites. According to the different application materials, the section of porphyrin composite sensors is divided into five sub-categories: (1) porphyrin film, (2) porphyrin metal complex, (3) metal-organic frameworks, (4) graphene materials, and (5) other materials, respectively.

Metal-Organic Frameworks of MIL-100(Fe, Cr) and MIL-101(Cr) for Aromatic Amines Adsorption from Aqueous Solutions.

MIL-100(Fe, Cr) and MIL-101(Cr) were synthesized by the hydrothermal method and applied to the adsorptions of five aromatic amines from aqueous solutions. These three metal-organic frameworks (MOFs) were well characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA) and surface area analysis. The adsorption mechanism of three MOFs and the effects of the structures of MOFs on the adsorption of aromatic amines were discussed. The results show that the cavity system and suitable hydrogen bond acceptor were important factors for the adsorption for five aromatic amines of aniline, 1-naphthalamine, o-toluidine, 2-amino-4-nitrotoluene and 2-nitroaniline: (a) the saturated adsorption capacity of aniline, 1-naphthylamine and o-toluidine on MIL-100(Fe) were 52.0, 53.4 and 49.6 mg/g, respectively, which can be attributed to the intermolecular hydrogen bond interaction and cavity system diffusion. (b) The adsorption capacity of 2-nitroaniline and 2-amino-4-nitrotoluene on MIL-101(Cr) were 54.3 and 25.0 mg/g, respectively, which can be attributed to the more suitable pore size of MIL-101(Cr) than that of MIL-100(Fe, Cr). The MOFs of MIL-100(Fe) and MIL-101(Cr) can be potential materials for removing aromatic amines from aqueous solutions.

Wheel-Like Icosanuclear Peroxotitanate-A Stable Water-Soluble Catalyst for Oxygen Transfer Reactions.

Water-soluble wheel-like icosanuclear peroxotitanate K16[Ti20(µ-O)8(HO2)8(O2)12( R, R-tart)12]·52H2O (1) chelated by tartrate has been successfully isolated. As the largest peroxotitanate reported, {Ti20} features 20 (hydro)peroxo groups with three kinds of coordination modes in µ-η1:η2, µ-η2:η2, and η2 fashions. The cluster is stable in solution and solid states. It has been tested for the catalytic oxidations of methyl phenyl sulfide and pyridine with hydrogen peroxide, respectively, which shows reversible elimination and the addition of peroxo groups. This provides a rare example of well-characterized titanium peroxide for homogeneous catalysis and mechanism research.

Exploration of long afterglow luminescent materials composited with graphitized carbon nitride for photocatalytic degradation of basic fuchsin.

The frequent exposure of the widely used dye, basic fuchsin (BF), is seriously threatening the health of human central nervous system. Thus, removing the environmental pollution caused by BF is crucial, and photocatalytic technology recently has been used to degrade the pollutions dye. In this study, the binary composite SrAl2O4:Eu2+, Dy3+/g-C3N4 was prepared by high-temperature calcination and then applied in BF photodegradation. The results confirmed that the composite material had lower band gap value (Eg) and stronger visible light absorption ability. The photocatalytic capacity of the new composite materials was enhanced compared to that of the non-composite materials. By using the new binary-composited materials, 80% of BF could be degraded in 10 min, and the degradation ratio reached 100% in 30 min. More importantly, even the light source was removed, the photocatalytic reaction could continue due to the luminescence of SrAl2O4:Eu2+, Dy3+, and the degradation efficiency of BF could finally reach more than 90% within 3 h. By quenching experiments and electron spin resonance (ESR) spectra analysis, superoxide anion (·O2-) was verified to be the main active substance in this reaction process. Moreover, the excellent stability and recyclability of this catalyst was also proved. Furthermore, the new composite materials were utilized to degrade the BF aqueous solution and actual lake water, and the total organic matter contents (TOC) were measured. TOC values in these two systems decreased after photocatalytic reaction, which indicated that this catalyst has a great development prospect in the removal of organic matter in water. Our study confirmed a new kind of material of high performance with great significance for emergency treatment of water pollution in practical applications.

An iron-based metal-organic framework as a novel dispersive solid-phase extraction sorbent for the efficient adsorption of tetrabromobisphenol A from environmental water samples.

For environmental safety, it is important to establish a simple, rapid, and sensitive method for emerging pollutants. Here, a dispersive solid-phase extraction (d-SPE) method based on an iron-based metal-organic framework (Fe-MIL-88-NH2) combined with high-performance liquid chromatography (HPLC) was developed for tetrabromobisphenol A (TBBPA) in water samples. Fe-MIL-88-NH2 was synthesized using a solvothermal method and completely characterized. Fe-MIL-88-NH2 had good water stability and gave a maximum adsorption capacity of 40.97 mg g-1 for TBBPA. The adsorption of TBBPA on Fe-MIL-88-NH2 followed Langmuir adsorption models and a pseudo-second-order kinetic model. The bromine ion and the hydroxyl group of TBBPA could form strong hydrogen bond interactions with the amino protons around the cavity of Fe-MIL-88-NH2, which was in accord with the molecular simulation calculations. Furthermore, several important d-SPE parameters were optimized, such as the amount of materials, extraction time, pH, ionic strength, elution solvent type, and volume. The established method showed good linearity in the concentration range of 0.005-100 µg g-1 (r2 ≥ 0.9996). This method's limits of detection (LOD) and quantification (LOQ) were 0.001 µg g-1 and 0.005 µg g-1, respectively. The recoveries in spiked water samples ranged from 87.5% to 104.9%. The proposed method was applied successfully to detect TBBPA in environmental water samples.

Exploration of double Z-type ternary composite long-afterglow/graphitic carbon nitride@metal-organic framework for photocatalytic degradation of methylene blue.

Methylene blue (MB) is a very widely used cationic dye for color cotton and silk products. The harmful MB has a complex aromatic structure that is difficult to be degraded in natural aqueous. In this study for the first time, a novel double Z-type ternary composite long-afterglow/graphitic carbon nitride@metal-organic framework (SrAl2O4:Eu2+,Dy3+/g-C3N4@NH2-UiO-66, SGN) has been synthesized by solvothermal method, and was used as a new photocatalyst for removal of MB. The photocatalytic performance of the composited photocatalyst SGN was largely improved compared to that of the non-composite. After 30 min of photocatalysis, the degradation ratio of SGN was 5.86, 4.04 and 10 times more efficient than that of long-afterglow (SAO), g-C3N4 and NH2-UiO-66, respectively. The high photocatalytic activity of the SGN could be ascribed to the double Z-type electron transfer mechanism. More importantly, due to the luminescence of SAO, the degradation ratio of ternary SGN can reach about 50 % after 5 h in the dark. Superoxide anion (·O2-) was verified to be the main active substance in the photocatalytic process by quenching experiments and electron spin resonance (ESR) spectra analysis. The total organic matter contents (TOC) and partial degradation products were measured, which confirmed that some MB was mineralized into H2O and CO2, and some was degraded into smaller molecules. Moreover, the excellent stability and recyclability of this catalyst were also investigated. Here, a new promising material with high degradation performance for water pollution treatment is presented.

Alanine Substitution to Determine the Effect of LR5 and YR6 Rice Peptide Structure on Antioxidant and Anti-Inflammatory Activity.

The relationship between the structure of peptides LR5 (LHKFR) and YR6 (YGLYPR) and their antioxidant and anti-inflammatory activity remains unclear. Herein, leucine, tyrosine, proline, and phenylalanine at different positions in the peptides were replaced by Alanine (Ala), and two new pentapeptides (AR5 and LAR5) and four hexapeptides (AGR6, YAR6, YLR6, and YGR6) were obtained. The effect of Ala replacement on the hydrophobicity, cytotoxicity, NO inhibition rate, and active oxygen radical scavenging ability of these peptides and their antioxidant and anti-inflammatory abilities were investigated. The results indicated that the hydrophobicity of the peptides was associated with their amino acid composition and their specific sequence. However, hydrophobicity had no significant effect on cytotoxicity. Ala replacement was shown to enhance hydrophobicity and consequently increased the antioxidant and anti-inflammatory activity of the peptides. The molecular docking studies indicated that the amino acid interactions of the peptide with the Keap1 protein influenced the hydrophobicity and thus affected the antioxidant activity of the peptide.

Application of an improved hollow fiber liquid phase microextraction technique coupled to LC-MS/MS to studying migration of fluorescent whitening agents from plastic food contact materials.

In this paper, a new hollow fiber liquid-phase microextraction method was developed to improve the extraction of five fluorescent whitening agents that migrated from plastics food contact materials. Influencing factors, such as the types of membrane, the extraction solvent, the stirring speed, the addition of salt ion, and extraction time, were investigated in detail. Under the optimal conditions, high enrichment factors (71-205) can be obtained with 15 µL extraction solvent. The new method is advantageous; the polypropylene hollow fiber membrane modified by sepiolite nanoparticles had excellent solvent binding force and mass transfer effect compared with the conventional extraction technique. The extracts were analyzed by high performance liquid chromatography-tandem mass spectrometry, the limits of detection were 0.3 or 0.9 ng kg-1 with good correlation coefficients (r2 ≥ 0.9940) for the five fluorescent whitening agents. The intra-day and inter-day recoveries ranged between 82.6% and 112%, with a relative standard deviation of less than 12%. The established method was successfully applied to the analysis of fluorescent whitening agent migration from four types of plastic food contact materials immersed in three food simulants.

Photocatalytic degradation of imidacloprid by optimized Bi2WO6/NH2-MIL-88B(Fe) composite under visible light.

Imidacloprid as a widely used neonicotinoid insecticide can cause harmful pesticide residue inevitably. Metal-organic frameworks (MOFs) were innovatively composited to improve the light absorption and degradation performance of Bi2WO6 semiconductor, which expanded the photodegradation application in solving environmental problems. Based on the synergistic effect of Bi2WO6 and NH2-MIL-88B(Fe), a Bi2WO6/NH2-MIL-88B(Fe) (BNM) heterojunction photocatalyst with high-performance of photocatalytic degradation activities was successfully synthesized. The optimized BNM catalyst had a good degradation rate under visible light, which was mainly caused by generation of the active ·OH. Transient photocurrent response and electrochemical impedance tests verified that 1:2 BNM exhibits a highest charge separation and a lowest carrier recombination rate which were favorable to the photocatalytic activity. Cycle experiments show that the composite photocatalyst had good reusability and stability which were very important for potential industry applications.

A nanozyme-linked immunosorbent assay based on metal-organic frameworks (MOFs) for sensitive detection of aflatoxin B1.

In order to avoid the occurrence of false positives and false negatives caused by conventional enzyme-linked immunosorbent assay (ELISA), we established a novel indirect competitive MOF-linked immunosorbent assay (MOFLISA) method for the high throughput and high sensitive detection of aflatoxin B1. This method replaces the natural enzyme with functional MOFs to catalyze a chromogenic system. As a result, the limit of detection (LOD) of the MOFLISA method was 0.009 ng·mL-1 with a linear working range from 0.01 to 20 ng·mL-1. The developed MOFLISA method for AFB1 has a 20-fold improved LOD value compared with the conventional ELISA. The recoveries and relative standard deviations (RSD) ranged from 86.41 to 99.74% and 2.38-9.04%, respectively. The results demonstrate that the recovery rate and accuracy of this detection method is better than that of conventional ELISA, reducing risks offalsepositive andfalsenegativeresults.

Extraction of antioxidant peptides from rice dreg protein hydrolysate via an angling method.

Selective enrichment of the highly active antioxidant peptides is required as the lack of an efficient method leads to long screening processes, hampering the research of antioxidant peptides. A simple synthetic metal-organic framework MIL-53 (Cr) was initially applied to extract specific antioxidant peptides from rice dreg protein hydrolysate. The highest active fraction was further purified by reversed-phase high-performance liquid chromatography. The antioxidant peptides with the highest antioxidant activities were identified as Gly-Asp-Met-Asn-Pro and Leu-Leu-Leu-Arg-Trp by LC-MS. These two peptides were synthesized and also exhibited good scavenging activity on the DPPH free radical, superoxide anion free radical and hydroxyl radical, and good chelating ability on Fe2+. The results confirmed that the angling method was effective for antioxidant peptide enrichment from protein hydrolysates.

New peptides with immunomodulatory activity identified from rice proteins through peptidomic and in silico analysis.

The new food-derived bio-functional peptides are urgently needed globally, but the separation and purification process for obtaining the immunopeptides from food is low efficiency and highly time-consuming. In the present study, rice proteins were extracted and identified by using liquid chromatography/tandem mass spectrometry (LC-MS/MS). Furthermore, a strategy combining immuno-prediction and in silico simulation was used to screen for peptides showing immunomodulatory activity, including inhibition of the release of nitric oxide, tumor necrosis factor-α, and the interleukins IL-6 and IL-1ß in lipopolysaccharide-induced RAW264.7 mouse macrophages. This LC-MS/MS identification and immuno-prediction method may provide insights for the potential identification of more food-derived immunopeptides.

Metal Organic Frame-Upconverting Nanoparticle Assemblies for the FRET Based Sensor Detection of Bisphenol A in High-Salt Foods.

To resolve the occurrence of unfulfillable detection in high-salts foods, we used fluorescence resonant energy transfer (FRET) sensors based on nanoparticle upconversion. In this study, we developed a novel FRET sensor for the detection of bisphenol A (BPA) in high-salt foods. We based this approach on the assembly of aptamer modified upconversion nanoparticles (DNA1-UCNPs) and complementary DNA modified metal organic frames (DNA2-MOFs), which possessed corresponding wavelength absorption. Targeting BPA signal transduction was performed using the BPA aptamer, via competitive recognition between the BPA analyte and complementary DNA sequences in a high-salt solution. Sensor adaption in high-salt samples was attributed to functional hydrophilic groups, modified in the MOFs, and the enhanced colloidal stability of these MOFs. The MOF-UCNP assembly displayed considerable analytical performance in terms of BPA detection, with a linear range of 0.1-100 nM, and a limit of detection (LOD) of 0.02 nM, in a 340 mM NaCl food sample (the energy drink, Gatorade). Thus, this method provides a solid basis for small molecules detection in high-salt foods.

Metal-Organic Frameworks with Double Channels for Rapid and Reversible Adsorption of 1,2-Ethylenediamine and Gases.

Selective liquid and gas adsorptions are important for environmental control and industrial processes. Here, unique porous lanthanide-organic frameworks of [Ln2(1,3-pdta)2(H2O)2]n2n- {Ln = La (1), Ce (2), Pr (3), and Nd (4), 1,3-pdta = CH2[CH2N(CH2CO2H)2]2} are template-synthesized by 1,2-ethylenediamine and fully characterized, which possess hydrophobic and hydrophilic open channels simultaneously. The skeletons are stable up to 200 °C. Obvious downfield shifts have been observed for 1,2-ethylenediamine in the confined channel with solid-state 13C NMR measurement. The ammonium salt is directly used for the removal of 1,2-ethylenediamine in water. Its saturated adsorption capacity is reached in <1 min and can be regenerated easily with a similar uptake capacity. Moreover, the materials can also selectively adsorb O2, CH4, and CO2, respectively, which is useful for CO2/CH4, CO2/H2, and O2/N2 separation. The combined hydrophobic and hydrophilic open channels of the lanthanides make them promising functional materials for the elimination of 1,2-ethylenediamine and gas separations.

Substitution of gadolinium ethylenediaminetetraacetate with phosphites: towards gadolinium deposit in nephrogenic systemic fibrosis.

In neutral media, reactions of gadolinium ethylenediaminetetraacetates with phosphorous acid result in the formation of the mixed-ligand polymeric complex K3n[Gd(EDTA)(HPO3)]n·7nH2O () and dimeric complex Na6[Gd2(EDTA)2(HPO3)2]·2.5NaCl·21H2O () (H4EDTA = ethylenediaminetetraacetic acid) in warm solution. Further substitution with citric acid gives the monomeric gadolinium citrate with EDTA (NH4)2Na[Gd(EDTA)(H2cit)]·4H2O (). The compounds were characterized by elemental analysis, single crystal X-ray diffraction, FT-IR, ESI-MS and thermogravimetric analysis. Structural analysis indicates that three coordinated water molecules in the gadolinium ethylenediaminetetraacetate trihydrates are replaced by phosphite ions (HPO3(2-)) in the compounds and . Gadolinium atoms are octa-coordinated by EDTA and the phosphite ion, the latter links adjacent Gd-EDTA units to generate an infinite one-dimensional chain in compound and a dimeric octatomic ring in . In complex , coordinated water molecules were substituted by the α-hydroxy, α-carboxy and ß-carboxy groups of citrate. Citrate is favourable for inhibiting the formation of Gd-EDTA phosphite. All the complexes are very easily soluble in water. The solution behavior of the isostructural lanthanum complexes was probed with (13)C and (31)P NMR spectra in D2O for comparison. ESI-MS analysis and recrystallization proved that complexes and dissociate to the monomeric unit of Gd-EDTA and free HPO3(2-) in aqueous solution. Substitutions of gadolinium ethylenediaminetetraacetates to and are attributed to be the cause of nephrogenic systemic fibrosis in some way.

α-Hydroxy coordination of mononuclear vanadyl citrate, malate and S-citramalate with N-heterocycle ligand, implying a new protonation pathway of iron-vanadium cofactor in nitrogenase.

Unlike the most of α-alkoxy coordination in α-hydroxycarboxylates to vanadium, novel α-hydroxy coordination to vanadium(IV) has been observed for a series of chiral and achiral monomeric α-hydroxycarboxylato vanadyl complexes [VO(H2cit)(bpy)]·2H2O (1), [VO(Hmal)(bpy)]·H2O (2), [VO(H2cit)(phen)]·1.5H2O (3), [VO(Hmal)(phen)]·H2O (4), and [(Δ)VO(S-Hcitmal)(bpy)]·2H2O (5), [VO(H2cit)(phen)]2·6.5H2O (6), which were isolated from the reactions of vanadyl sulfate with α-hydroxycarboxylates and N-heterocycle ligands in acidic solution. The complexes feature a tridentate citrate, malate or citramalate that chelates to vanadium atom through their α-hydroxy, α-carboxy and ß-carboxy groups; while the other ß-carboxylic acidic group of citrate is free to participate strong hydrogen bonds with lattice water molecule. The neutral α-hydroxy group also forms strong intermolecular hydrogen bonds with water molecule and the negatively-charged α-carboxy group in the environment. The inclusion of a hydrogen ion in α-alkoxy group results in the formation of a series of neutral complexes with one less positive charge. There are two different configurations of citrate with respect to the trans-position of axial oxo group, where the complex with trans-hydroxy configuration seems more stable with less hindrance. The average bond distances of V-Ohydroxy and V-Oα-carboxy are 2.196 and 2.003Å respectively, which are comparable to the VO distance (2.15Å) of homocitrate in FeV-cofactor of V-nitrogenase. A new structural model is suggested for R-homocitrato iron vanadium cofactor as VFe7S9C(R-Hhomocit) (H4homocit=homocitric acid) with one more proton in homocitrate ligand.

Dimeric 1,3-propanediaminetetraacetato lanthanides as the precursors of catalysts for the oxidative coupling of methane.

From neutral solutions, dimeric 1,3-propanediaminetetraacetato lanthanides (NH4)2[Ln2(1,3-pdta)2(H2O)4]·8H2O [Ln = La, 1; Ce, 2] and K2[Ln2(1,3-pdta)2(H2O)4]·11H2O [Ln = La, 3; Ce, 4] (1,3-H4pdta = 1,3-propanediaminetetraacetic acid, C11H18N2O8) were isolated in high yields. The reaction of excess strontium nitrate with 1 resulted in the formation of a two dimensional coordination polymer [La2(1,3-pdta)2(H2O)4]n·[Sr2(H2O)6]n·[La2(1,3-pdta)2(H2O)2]n·18nH2O (5) at 70 °C. Complexes 1-4 show a similar central molecular structure. The lanthanide ions are coordinated by two nitrogen atoms, four carboxy oxygen atoms from one 1,3-pdta ligand, two from the neighboring 1,3-pdta ligand forming a four-membered ring and two water molecules. Complex 5 has two kinds of dimeric lanthanum unit and extends into a 2D coordination polymer through strontium ions and bridged oxygen atoms, and forms a fourteen membered ring linked by oxygen atoms from carboxy groups of pdta. Complexes 1-4 are soluble in water. The (13)C{(1)H} NMR experiments for complex 1 were tested in solution. Thermal products from 1 and 5 show good catalytic activities towards the oxidative coupling reaction of methane (OCM). The conversion of methane and selectivity to C2 reached 29.7% and 51.7% at 750 °C for the product of 5. From TGA, XRD and SEM analyses, the thermal products from 1 and 5 are rod- and poly-shaped, which are assigned as lanthanum oxocarbonate and a mixture of La2O3, SrCO3 and La2O2CO3 for 1 and 5, respectively. The precursor method is favorable for the formation of regular shaped mixed oxides.