Semirigid Highly Conjugated Zirconium-Organic Framework for the Capture of Micropollutants and Solar-Light Photodegradation.

Micro-organic pollutants, particularly organic dyes and personal care products (PPCPs), are widely present in wastewater, and thus pose a serious risk to human health. The capture and solar-light photodegradation of micro-organic pollutants are highly challenging tasks, which require the design and synthesis of microporous materials with specific structures. As we know, organic dyes and PPCPs can be absorbed via π-π* stacking. In this paper, an iron-based metal-organic framework (Fe-UiO-68-terNap) containing semirigid conjugated aromatic ligands is prepared for the capture and solar-light photodegradation of multiple water contaminants. UiO-68-terNap was synthesized based on ternaphthalene with π-π* stacking, which would increase the adsorption capacities of organic micropollutants in wastewater. Additionally, the formation of Fe-O-Zr enhances the charge-separation ability resulting in the successful degradation of micropollutants in 240 min. The novel material has been elucidated by single-crystal X-ray diffraction and Fe K-edge XANES, which provide key insights at a molecular level for the design of novel materials for the capture and photodegradation of organic micropollutants.

A {Cu6}-added polyoxometalate cluster-organic framework: synthesis, structure and application as a solid support for enzyme immobilization.

A new two-dimensional {Cu6}-added polyoxometalate cluster-organic framework (Cu-POMCOF) was prepared by a hydrothermal method from lacunary polyoxoanions and was applied as a solid support for immobilizing MP-11 and Cyt c. The biocomposite complex exhibits higher stability and catalytic activity than the original free enzyme.

GaOOH Crystallite Growth on Liquid Metal Microdroplets in Water: Influence of the Local Environment.

Gallium-based liquid metals form alloys with a melting point close to or below room temperature. On the surface of these liquid metals, a thin oxide skin is formed once in contact with oxygen, and this oxide skin can be leveraged to stabilize liquid metal micro- and nanodroplets in a liquid. During sonication and storage of these droplets in aqueous solution, gallium oxide hydroxide (GaOOH) forms on these droplets, and given enough time or treatment with heat, a full shape transition and dealloying are observed. In this article, we show that GaOOH can be grown at room temperature and that the growth is dependent on both the local environment and temperature. GaOOH growth on liquid metal microdroplets located at the air/water interface is considerably faster than in the bulk phase. Interestingly, hydrolysis to GaOOH is hampered and stops at 15 °C in bulk water after 6 h. In contrast, hydrolysis commences even at 15 °C for liquid metal microdroplets located at the air/water interface, and full surface coverage is obtained after around 24 h (compared to 12 h at 25 °C at the air/water interface). The X-ray photoelectron spectroscopy (XPS) measurement suggests that gallium oxide is dissolved and Ga(OH)3 is formed as a precursor that reacts in a downstream reaction toward GaOOH. This improved understanding of the GaOOH formation can be leveraged to control the liquid metal micro- and nanodroplet shape and composition (i.e., for biomedical applications).

Polyoxometalate-Based Metal-Organic Frameworks as the Solid Support to Immobilize MP-11 Enzyme for Enhancing Thermal and Recyclable Stability.

The immobilization of enzymes has received much attention. Metal-organic framework (MOF) as the adsorbent for enzyme encapsulation provides an effective strategy. However, the encapsulation efficacy is not dependent solely on the specific surface area. Though leading into appropriate substrate with negative charge would enhance the encapsulation efficacy. Polyoxometalates (POMs) as the electron sponge would donate electrons without any structural change. In this study, Keggin-type phosphotungstic acid (PW12) was encapsulated in Zirconium metal-organic framework (PW12@UiO-67) as a heterogeneous adsorbent for the encapsulation of enzyme. Our following data proved that this composite cluster could enhance the adsorption of enzyme and the stability of MP-11 was then significantly improved after immobilization.

Solution-processable, soft, self-adhesive, and conductive polymer composites for soft electronics.

Soft electronics are rising electronic technologies towards applications spanning from healthcare monitoring to medical implants. However, poor adhesion strength and significant mechanical mismatches inevitably cause the interface failure of devices. Herein we report a self-adhesive conductive polymer that possesses low modulus (56.1-401.9 kPa), high stretchability (700%), high interfacial adhesion (lap-shear strength >1.2 MPa), and high conductivity (1-37 S/cm). The self-adhesive conductive polymer is fabricated by doping the poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) composite with a supramolecular solvent (ß-cyclodextrin and citric acid). We demonstrated the solution process-based fabrication of self-adhesive conductive polymer-based electrodes for various soft devices, including alternating current electroluminescent devices, electromyography monitoring, and an integrated system for the visualization of electromyography signals during muscle training with an array of alternating current electroluminescent devices. The self-adhesive conductive polymer-based electronics show promising features to further develop wearable and comfortable bioelectronic devices with the physiological electric signals of the human body readable and displayable during daily activities.

Functional properties of gonad protein isolates from three species of sea urchin: a comparative study.

Sea urchin Mesocentrotus nudus, Glyptocidaris crenularis, and Strongylocentrotus intermedius gonad protein isolates (mnGPIs, gcGPIs, and siGPIs) were extracted by isoelectric solubilization/precipitation (ISP) from the defatted gonads, and their functional properties were compared. Sodium dodecyl sulfate polyacrylamide gel electrophoresis results showed the similar protein pattern between each protein isolate and defatted gonad, indicating the high efficiency of ISP processing for protein recovery. Amino acid profileconfirmed that the mnGPIs and siGPIs could be potential sources of essential amino acid in nature. As regard to functional properties, mnGPIs showed higher water- and oil- holding capacities followed bysiGPIs and gcGPIs and all protein isolates presented great foaming property. As for emulsifying activity index (EAI), mnGPIs, gcGPIs, and siGPIs showed the minimum solubility and EAI at pH 5, 3, and 4, respectively, and behaved a pH-dependent manner. The gcGPIs revealed the highest EAI from pH 6 to 8 among the samples. In addition, circular dichroism showed increased content of ß-sheet at the expense of α-helix and ß-turn, suggesting the structure denaturation of the protein isolates. Indeed, no statistical difference was observed between secondary structure of mnGPIs and siGPIs. Moreover, ISP processing increased free sulfhydryl content of sea urchin protein isolates, but no difference was observed among the samples. Furthermore, siGPIs revealed the highest amount of total sulfhydryl and disulfide bonds, whereas both defatted gonads and protein isolates from G. crenularis presented the maximum surface hydrophobicity. These results suggest that gonad protein isolates from three species of sea urchin possess various functionalities and therefore can be potentially applied in food system. PRACTICAL APPLICATION: Sea urchin M. nudus, G. crenularis, and S. intermedius gonads are edible, whereas the functional properties of protein isolates from sea urchin gonad remain unknown. In this case, the extraction and comparison of three species of sea urchin gonad protein isolates will not only confirm functional properties but also screen food ingredients with suitable functions. In this study, functionalities of protein isolates derived from M. nudus, G. crenularis, and S. intermedius gonads would provide potential application in bakery food and meat products or as emulsifier candidates in food system.

Methylation signature genes identification of cancers occurrence and pattern recognition.

In order to identify the signature genes of tumorigenesis, the pattern-recognition method was used to analyze the gene methylation (ME) data which included only normal and cancer samples and was collected from the TCGA (The Cancer Genome Atlas) database. Here, we analyzed the DNA methylation profiles of the six types of cancer and the ME signature genes for each cancer were selected by means of a combination of correlation, student's t-test and Elastic Net. Modeling by support vector machine, the accuracy of ME signature genes can be as high as 98 % for training set and as high as 97 % for the independent test set, the recognition accuracy of stage I is more than 97 % for training set and more than 98 % for test set. Then, the common signature genes and common pathways emerging in multiple cancers were obtained. A functional analysis of these signature genes indicates that the identified signatures have direct relationship with tumorigenesis and is very important for understanding the pathogenesis of cancer and the early therapy.

Modulation of physicochemical stability and bioaccessibility of ß-carotene using alginate beads and emulsion stabilized by scallop (Patinopecten yessoensis) gonad protein isolates.

The colloidal delivery systems fabricated by emulsion containing natural proteins and lipids have been utilized to protect carotenoids as well as to release the carotenoids in the simulated in vitro gastrointestinal tract (GIT). In this study, ß-carotene (BC) was embedded into emulsions that were stabilized by scallop gonad protein isolates (SGPIs), and the emulsion droplets containing BC were then entrapped into calcium-alginate beads. The results showed that the oil-in-water emulsions coated by SGPIs only showed good stability at pH 7-8, while the emulsion-alginate beads remained relatively intact at pH 3-8. BC encapsulated in emulsions was extremely unstable and prone to degradation when stored at the comparatively higher temperature (37 °C), whereas the stability of BC was greatly enhanced through incorporation into emulsion-alginate beads. The digestion rate and extent of lipid droplets constructed within SGPIs-stabilized emulsion-alginate beads were slower than that in emulsions during GIT. The confocal laser scanning microscopy revealed that the lipid droplets in emulsions were aggregated after exposure to the mouth and gastric phases, while the emulsion-alginate beads maintained their spherical shape after exposure to the oral and gastric phases. Moreover, the free lipid droplets in the emulsions showed a higher bioaccessibility of BC (66%) than that in the emulsion-alginate beads (38%), whereas the BC transformation was on the contrary. The findings in this study indicated that SGPIs-stabilized emulsion in alginate beads can potentially be utilized for the encapsulation and controlled release of lipophilic bioactive compounds.

Simultaneous extraction by acidic and saline solutions and characteristics of the lipids and proteins from large yellow croaker (Pseudosciaena crocea) roes.

The objective of this study was to simultaneously obtain protein isolates and lipids from the dried powder of large yellow croaker (Pseudosciaena crocea) roes (pcRs) to achieve high-value utilization. Protein isolates and lipids were extracted simultaneously from pcRs by saline and acidic solutions. The purity of the protein isolates from the pcRs (pcRPIs) was greater than 70%, with vitellogenin, vitellogenin B and vitellogenin C as the main proteins. The lipids from pcRs (pcRLs) were mainly composed of triglycerides with high levels of EPA and DHA. The pcRPIs exhibited a higher surface hydrophobicity, water/oil holding capacity and emulsifying ability than those of the pcRs. Moreover, pcRPIs had a better oil holding capacity and emulsifying ability than soy protein isolate. These results suggest that protein isolates and lipids can be simultaneously extracted by saline and acidic solutions, and pcRPIs and pcRLs can be used as functional materials in the food industry.

Liquid Metal-Mediated Mechanochemical Polymerization.

Mechanically controlled polymerization that employs the mechanical energy to fabricate novel synthetic materials has attracted considerable interest. However, only a few examples have been achieved so far, owing to the limited choices of materials and strategies. Herein, a versatile, liquid metal (LM)-mediated mechanochemical polymerization method (LMMMP) is developed for the air-compatible, robust preparation of polymers in an aqueous solution. This method involves the simultaneous disruption of bulk LMs into micro- and nanodroplets and the combination of monomers into polymers during ultrasonic irradiation. The pristine and reactive LM surface continuously generated by ultrasound endows this polymerization method with excellent oxygen tolerance, high reaction rate, and the ability to produce polymers with high molecular weight from a wide variety of water-soluble monomers. Besides, LM droplets are readily reclaimed and reused for polymerization. The authors envision that the LMMMP promotes the utilization of mechanical energy for the synthesis of functional polymers, constitutes a novel fabrication approach for polymer-LM nanocomposites, and provides new insight into the design of LM-based platforms for polymerization.

Fabrication of surface-active antioxidant biopolymers by using a grafted scallop (Patinopecten yessoensis) gonad protein isolate-epigallocatechin gallate (EGCG) conjugate: improving the stability of tuna oil-loaded emulsions.

The oxidation of unsaturated fats generally occurs at the oil-water interface of emulsions, so surface-active antioxidants are needed for inhibiting lipid oxidation. In this study, a scallop gonad protein isolate (SGPI)-epigallocatechin gallate (EGCG) conjugate was fabricated and characterized as an amphiphilic surface-active antioxidant in improving the physicochemical and oxidative stability of tuna oil-loaded emulsions via a free-radical grafting method. The covalent binding of EGCG to SGPIs was verified by using electrophoresis and gel permeation chromatography. Meanwhile, the structural, physical, thermal, as well as the in vitro antioxidant properties of the SGPI-EGCG conjugate were further characterized. The results indicated that the SGPI-EGCG conjugate contained more ß-sheet but less α-helix than SGPIs, leading to the changes of the secondary and tertiary conformation stability after conjugation. The radical scavenging and oxygen radical absorbance capacity of SGPIs were significantly increased by 4.9 times and 7.4 times, respectively, after the EGCG-grafting reaction. Compared with that stabilized by SGPIs, tuna oil emulsions emulsified by the SGPI-EGCG conjugate exhibited a smaller particle size and better storage stability. Furthermore, the SGPI-EGCG conjugate inhibited lipid and fatty acid oxidation during storage more significantly in tuna oil emulsions than SGPIs due to its higher interfacial accumulation and antioxidant activities. These results suggested that the SGPI-EGCG conjugate could be utilized as an efficient surface-active antioxidant and emulsifier for the encapsulation and protection of unsaturated lipids.

Quantitative Proteome Reveals Variation in the Condition Factor of Sea Urchin Strongylocentrotus nudus during the Fishing Season Using an iTRAQ-based Approach.

To investigate the variation in the condition factor of the sea urchin Strongylocentrotus nudus (S. nudus), gonads were collected in May (MAY), June (JUN), and July (JUL), at the beginning (AUG-b) and end of August (AUG-e). Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) detection of the gonads revealed an obvious enhancement of the band at about 37 kDa from July, which was identified as transforming growth factor-beta-induced protein ig-h3 (TGFBI) by nanoLC-ESI-MS/MS. Gonadal proteins were identified by isobaric tagging for relative and absolute quantitation (iTRAQ), and regulation of the identified proteins in pairs of the collected groups was observed. A total of 174 differentially expressed proteins (DEPs) were identified. Seven of the DEPs showed significant correlations with both the gonad index (GI) and protein content. These correlations included 6-phosphogluconate dehydrogenase, decarboxylating isoform X2 (6PGD), CAD protein, myoferlin isoform X8, ribosomal protein L36 (RL36), isocitrate dehydrogenase [NADP], mitochondrial isoform X2 (IDH), multifunctional protein ADE2 isoform X3, sperm-activating peptides (SAPs) and aldehyde dehydrogenase, and mitochondrial (ALDH). However, TGFBI had no correlation with gonad index (GI) or protein content. 6PGD, IDH, multifunctional protein ADE2 isoform X3, and ALDH were shown to interact with each other and might play key roles in changing the condition factor of S. nudus gonads.

Involvement of DNA in Gel Formation of Scallop (Patinopecten yessoensis) Male Gonad Hydrolysates and Corresponding Hybrid Gel with κ-Carrageenan.

Involvement of DNA in gelation and microstructural properties of scallop (Patinopecten yessoensis) male gonad hydrolysates (SMGHs) and corresponding hybrid gel with κ-carrageenan (SMGHs/κ-C) was studied using DNase pretreatment. Although DNase pretreatment significantly transformed SMGHs from weak gels to liquid, it made SMGHs have a superior synergistic effect on gel formation with κ-C by evidence of 2.7-fold G' and 1.1-fold melting temperature. However, the relaxation time (T21 and T23), functional groups, and flocculation behavior were comparable between SMGHs/κ-C and SMGHs/DNase/κ-C. Moreover, SMGHs/DNase/κ-C exhibited a denser network with more numerous patches and larger void spaces. These results suggest that DNA contributes to the gel formation of SMGHs whereas restricts more cationic peptides in SMGHs to bind sulfate groups in κ-C during gel formation.

Physiochemical Properties and Functional Characteristics of Protein Isolates from the Scallop (Patinopecten yessoensis) Gonad.

Protein isolates were recovered from scallop (Patinopecten yessoensis) gonads to develop a novel functional matrix by investigating their physiochemical and functional properties. Scallop gonad protein isolates (SGPIs) were prepared from degreased scallop gonads (DSGs) by an alkali extraction and isoelectric solubilization/precipitation (ISP) process. The protein compositions of the SGPIs were mainly vitellogenin and beta-actin with molecular weights of 266 and 42 kDa, respectively, as determined using Nano-liquid chromatography-mass/mass (Nano-LC-MS/MS). After the ISP process, the protein solubility of the SGPIs was significantly improved, and the surface hydrophobicity of SGPIs intensely increased by 1.1-fold, which were attributed to the exposure of aromatic residues such as phenylalanine, tyrosine, and tryptophan. However, the content of total/reactive sulfhydryl in SGPIs was decreased compared with that of DSGs. Meanwhile, the ISP process caused partial protein unfolding, as indicated by circular dichroism analysis, which exhibited a remarkable rise in the ß-sheet content with a parallel decline in the α-helix and random coil contents (P < 0.05). SGPIs exhibited a better oil absorption capacity and foaming property than both DSGs and soybean protein isolates (SPIs). Moreover, the emulsifying capacity of SGPIs was greatly enhanced by the ISP process, which was superior to the effect of commercial SPIs and was ascribed to its favorable solubility as well as surface characteristics. PRACTICAL APPLICATION: During the processing of scallop (Patinopecten yessoensis) adductors, scallop gonad, a high-protein part, is usually discarded as processing by-products despite its edibility. In recent years, scallop gonads are regarded as good sources to develop protein matrices due to their high protein content and numerous nutrients. In this study, scallop gonad protein isolates (SGPIs) were isolated by isoelectric solubilization/precipitation (ISP) process. The preferable solubility, foaming property coupled with high emulsifying property of SGPIs indicated that the SGPIs could be potentially utilized as a good protein emulsifier and additives in production of kamaboko gels, hamburger patties, sausages, and pet foods.

Light-Induced Shape Morphing of Liquid Metal Nanodroplets Enabled by Polydopamine Coating.

Shape morphing nanosystems have recently attracted much attention and a number of applications are developed, spanning from autonomous robotics to drug delivery. However, the fabrication of such nanosystems remains at an early stage owing to limited choices of strategies and materials. This work reports a facile method to fabricate liquid metal (LM) nanodroplets by sonication of bulk LM in an aqueous dopamine hydrochloride solution and their application in light-induced shape morphing at the nanoscale. In this method, dopamine acts as a surfactant, which stabilizes the LM nanodroplets dispersion during the sonication, and results in downsizing of the nanodroplets. Furthermore, by adding 2-amino-2-(hydroxymethyl)-1,3-propanediol to the suspension, self-polymerization of dopamine molecules occurs, resulting in the formation of polydopamine (PDA)-coated LM nanodroplets. Owing to the high photothermal conversion of the PDA, PDA-coated LM nanodroplets are transformed from spherical shapes to ellipsoids by NIR laser irradiation. This study paves a simple and reliable pathway for the preparation of functional LM nanodroplets and their application as shape-morphing nanosystems.

Bioaccessibility and cellular uptake of ß-carotene in emulsion-based delivery systems using scallop (Patinopecten yessoensis) gonad protein isolates: effects of carrier oil.

Emulsion-based delivery systems were structured by using scallop gonad protein isolates (SGPIs) as novel food-grade emulsifiers. The effects of carrier oil, including the long chain triglycerides (LCT) and medium chain triglycerides (MCT), on the bioaccessibility and cellular uptake of ß-carotene (BC) were investigated. Both LCT and MCT delivery systems remained stable at pH 7-8 but aggregated at lower pH values (3-6) according to the results of light scattering and microscopy measurements. LCT droplets fabricated within SGPIs were digested and released more slowly than MCT droplets during the simulated gastrointestinal tract digestion. The LCT emulsion showed higher BC bioaccessibility (65.5%) than the MCT emulsion (23.1%) as a result of the greater solubilization of BC in mixed micelles fabricated from long-chain fatty acids. Moreover, the LCT emulsion produced higher cellular uptake of BC as compared with the MCT emulsion in intestinal epithelial cells. These results demonstrated that SGPIs could be used as novel food-grade emulsifiers to protect lipophilic bioactive compounds in emulsion-based delivery systems, in which LCT is more suitable to encapsulate and deliver BC than MCT.

In silico assessment and structural characterization of antioxidant peptides from major yolk protein of sea urchin Strongylocentrotus nudus.

Sea urchin gonads have been demonstrated to contain major yolk protein (MYP), which can be hydrolyzed by enzymes to release biologically active peptides. The in silico analysis of the MYP sequence in the BIOPEP database showed the presence of fragments with antioxidant activity. The sequence was hydrolyzed by 21 kinds of proteases and 23 antioxidant peptides were obtained. Eight peptides, including Leu-Trp (LW), Arg-Trp (RW), Ala-Trp (AW), Thr-Trp (TW), Ala-Asp-Phe (ADF), Leu-Trp-Lys (LWK), Ser-Asp-Phe (SDF) and Leu-Tyr (LY), were screened and a score over 0.5 was obtained using PeptideRanker. The peptides LW, TW and LWK showed a stronger antioxidant capacity with IC50 values of 8.85, 9.59 and 9.62 mmol L-1, respectively, compared to that of glutathione (10.81 mmol L-1). Furthermore, AW, LW and LY showed Trolox equivalent antioxidant capacity (TEAC) values of 3.07, 1.87 and 1.52 mmol TE per mmol peptide, respectively. These results suggest that the MYP from sea urchin (S. nudus) gonads is a good source of antioxidant peptides with abundant tryptophan.

Palladium-catalyzed heck-type cascade cyclization of (Z)-1-iodo-1,6-dienes with N-tosyl hydrazones.

A palladium-catalyzed heck-type cascade cyclization of (Z)-1-iodo-1,6-dienes with N-tosyl hydrazones is reported. The alkylpalladium intermediate coupled with the diazo compound, generating the second alkylpalladium species bearing two ß-H, which generated a terminal alkene as the major products in the anti-Zaitsev way via the highly regioselective ß-H elimination. It provided a new way to synthesize tetrahydropyridine derivatives bearing a terminal alkene.

Methylation Signature Genes Identification of the Lung Squamous Cell Carcinoma Occurrence and Recognition Research.

DNA methylation (DNAm) is one of the most important epigenetic event effecting gene expression, and aberrant DNAm has been implicated in the initiation and progression of human cancers. To identify methylation (ME) signature genes for the pathogenesis of lung squamous cell carcinoma (LUSC), the pattern recognition method was used to analyze the genome-wide gene ME data, which were collected from the LUSC normal and cancer stage I samples in The Cancer Genome Atlas project database. A total of 102 ME signature genes were identified by means of a combination of statistical methods such as correlation, analysis of variance, and Elastic Net. The accuracy and specificity are all above 99%, sensitivity is 100%, and Matthews correlation coefficient is higher than 0.99 through the machine learning method modeling, which are higher than the previous study. The Kyoto Encyclopedia of Genes and Genomes pathway analysis and Gene Ontology enrichment analysis indicated the highly related relationship among these genes. They also indicated the immediate relationship between our signature genes and the occurrence of LUSC, which is very important to the understanding of its mechanism and to the development of new targeted therapy.

Characteristic antioxidant activity and comprehensive flavor compound profile of scallop (Chlamys farreri) mantle hydrolysates-ribose Maillard reaction products.

The objective of the present study was to improve the utilization of scallop (Chlamys farreri) byproducts by using Maillard reaction. Scallop mantle hydrolysates (SMHs) were prepared using neutrase then reacted with ribose. Thirty-four peptides were identified from SMHs by UPLC-Q-TOF-MS, and the abundance of Asp and Lys suggested the strong Maillard reactivity. The formation of Schiff's base as well as modification of amide I, II and III bands in Maillard reaction products (MRPs) was confirmed by ultraviolet-visible, fluorescence, and Fourier transform infrared spectroscopy. Thirty volatile compounds were produced by the reaction of SMHs with ribose. Moreover, MRPs with enhanced radical scavenging and anti-linoleic acid peroxidation activities over SMHs promoted the survival and reduced the DNA damage of HepG2 cells treated with hydrogen peroxide. These results suggest that SMHs-ribose MRPs can be potentially used as food antioxidant for suppressing of lipid oxidation or protecting of cell from oxidative damage.