A novel seawater hydrothermal-deep eutectic solvent pretreatment enhances the production of fermentable sugars and tailored lignin nanospheres from Pinus massoniana.

Lignocellulose biorefinery depended on effective pretreatment strategies is of great significance for solving the current global crisis of ecosystem and energy security. This study proposes a novel approach combining seawater hydrothermal pretreatment (SHP) and microwave-assisted deep eutectic solvent (MD) pretreatment to achieve an effective fractionation of Pinus massoniana into high value-added products. The results indicated that complex ions (Mg2+, Ca2+, and Cl-) in natural seawater served as Lewis acids and dramatically promoted the depolymerization of mannose and xylan into oligosaccharides with 40.17 % and 75.43 % yields, respectively. Subsequent MD treatment realized a rapid and effective lignin fractionation (~90 %) while retaining cellulose. As a result, the integrated pretreatment yielded ~85 % of enzymatic glucose, indicating an eightfold increase compared with untreated pine. Because of the increased hydrophobicity induced by the formation of acyl groups during MD treatment, uniform lignin nanospheres were successfully recovered from the DES. It exhibited low dispersibility (PDI = 2.23), small molecular weight (1889 g/mol), and excellent oxidation resistance (RSI = 5.94), demonstrating promising applications in functional materials. The mechanism of lignin depolymerization was comprehensively elucidated via FTIR, 2D-HSQC NMR, and GPC analyses. Overall, this study provides a novel and environmentally friendly strategy for lignocellulose biorefinery and lignin valorization.

Charge transport properties and mechanisms of bacterial cellulose (BC)-Zinc complexes.

Most current flexible electronic devices are based on petroleum materials that are difficult to degrade. The exploration of sustainable and eco-friendly materials has become a major focus in both the scientific and industrial communities. In this study, BC-Zn-BIM (bacterial cellulose-Zn-benzimidazole), a novel composite electrode material based on biodegradable BC was developed. Here, BC acted as a conductive medium involved in the conductive behavior of the composite material. We've explored the charge transport mechanisms of BC-Zn-BIM by density functional theory (DFT) calculations, and applied it in the electrochemical detection of Bisphenol A (BPA). The results indicated that the oxygen-containing groups in BC and the nitrogen-containing heterocycles in BIM have a tendency to lose electrons, whereas zinc ions actively acquire electrons from these groups. This process promoted charge transfer within BC-Zn-BIM and endowed it with semiconductor-like properties, enhancing the electrocatalytic reaction of BPA. The detection limit of the electrochemical biosensor was 12 nM, and the sample recovery was 95.1%105.6%. This study clarified the mechanism of the higher electrical properties achieved in Zn-BIM complex grown in-situ on dielectric BC. This will further promote the development of low-cost, environmentally friendly flexible electronic devices.

Insights into the poplar cell wall deconstruction following deep eutectic solvent pretreatment for enhanced enzymatic saccharification and lignin valorization.

In this study, a combination of microcosmic and chemical analysis methods was used to investigate deep eutectic solvent (DES) pretreatment effects on cell wall's micromorphology and lignin's dissolution regular, in order to achieve high-performance biorefinery. The atomic force microscope observed that DES pretreatment peeled off non-cellulose components to reduced "anti-degradation barrier", resulting to improve the enzymatic saccharification from 12.36 % to 90.56 %. In addition, DES pretreatment can break the ß-O-4 bond between the lignin units resulting in a decline in molecular weight from 3187 g/mol to 1112 g/mol (0-6 h). However, long pretreatment time resulted regenerated lignin samples repolymerization. Finally, DES has good recoverability which showed saccharification still can reach 51.51 % at 6 h following four recycling rounds and regenerated lignin also had a typical and well-preserved structure. In general, this work offers important information for industrial biorefinery technologies and lignin valorization.

Seeing Is Not Necessarily Believing: Is the Surface-Enhanced Raman Spectroscopy Signal Really from the Target?

Reagent purity is crucial to experimental research, considering that the ignorance of ultratrace impurities may induce wrong conclusions in either revealing the reaction nature or qualifying the target. Specifically, in the field of surface science, the strong interaction between the impurity and the surface will bring a non-negligible negative effect. Surface-enhanced Raman spectroscopy (SERS) is a highly surface-sensitive technique, providing fingerprint identification and near-single molecule sensitivity. In the SERS analysis of trace chloromethyl diethyl phosphate (DECMP), we figured out that the SERS performance of DECMP is significantly distorted by the trace impurities from DECMP. With the aid of gas chromatography-based techniques, one strongly interfering impurity (2,2-dichloro-N,N-dimethylacetamide), the byproduct during the synthesis of DECMP, was confirmed. Furthermore, the nonignorable interference of impurities on the SERS measurement of NaBr, NaI, or sulfadiazine was also observed. The generality ignited us to refresh and consolidate the guideline for the reliable SERS qualitative analysis, by which the potential misleading brought by ultratrace impurities, especially those strongly adsorbed on Au or Ag surfaces, could be well excluded.

Development of starch-based amorphous CoOx self-supporting carbon aerogel electrocatalyst for hydrogen evolution.

Hydrogen energy is turning into a major research topic in this complex and changing world. In recent years, more and more research has been done on transition metal oxides and biomass composites. In this study, potato starch and amorphous cobalt oxide were assembled into carbon aerogel by sol-gel method and high-temperature annealing (CoOx/PSCA). The connected porous structure of the carbon aerogel is conducive to HER mass transfer, and its structure can avoid the agglomeration of transition metals. It also has great mechanical properties and can be directly used as a self-supporting catalyst for electrolysis with 1 M KOH for hydrogen evolution, which showed excellent HER activity and yielded the effective current density of 10 mA cm-2 at 100 mV overpotential. Electrocatalytic experiments further showed that the better performance of CoOx/PSCA for HER can be attributed to the high electrical conductivity of carbon and the synergistic effect of unsaturated catalytic sites on the amorphous CoOx cluster. The catalyst comes from a wide range of sources, is easy to produce, and has good long-term stability, so it can be used in large-scale production. This paper provides a simple and easy method to make biomass-based transition metal oxide composites for electrolyzing water to produce hydrogen.

Preparation and Characterization of Degradable Cellulose-Based Paper with Superhydrophobic, Antibacterial, and Barrier Properties for Food Packaging.

A great paradigm for foremost food packaging is to use renewable and biodegradable lignocellulose-based materials instead of plastic. Novel packages were successfully prepared from the cellulose paper by coating a mixture of polylactic acid (PLA) with cinnamaldehyde (CIN) as a barrier screen and nano silica-modified stearic acid (SA/SiO2) as a superhydrophobic layer. As comprehensively investigated by various tests, results showed that the as-prepared packages possessed excellent thermal stability attributed to inorganic SiO2 incorporation. The excellent film-forming characteristics of PLA improved the tensile strength of the manufactured papers (104.3 MPa) as compared to the original cellulose papers (70.50 MPa), enhanced by 47.94%. Benefiting from the rough nanostructure which was surface-modified by low surface energy SA, the contact angle of the composite papers attained 156.3°, owning superhydrophobic performance for various liquids. Moreover, the composite papers showed excellent gas, moisture, and oil bacteria barrier property as a result of the reinforcement by the functional coatings. The Cobb300s and WVP of the composite papers were reduced by 100% and 88.56%, respectively, and their antibacterial efficiency was about 100%. As the novel composite papers have remarkable thermal stability, tensile strength, and barrier property, they can be exploited as a potential candidate for eco-friendly, renewable, and biodegradable cellulose paper-based composites for the substitute of petroleum-derived packages.

Decarboxylative Selective Phosphorylation of Aliphatic Acids: A Transition-Metal- and Photocatalyst-Free Avenue to Dialkyl and Trialkyl Phosphine Oxides from White Phosphorus.

Developing practical and mild strategies for the direct functionalization of white phosphorus (P4 ) without chlorination is an appealing but formidable challenge. To this end, we report a breakthrough in the preparation of structurally diverse dialkylphosphines and trialkylphosphines that rely on the successive generation of carbon-centered radicals from N-hydroxyphthalimide (NHPI) esters and the controllable alkylation of the P4 molecule under transition-metal- and photocatalyst-free conditions. To facilitate separation and prevent product losses during purification, the corresponding oxidation products dialkylphosphine oxides (DAPOs) and trialkylphosphine oxides (TAPOs) were isolated. This photoinduced phosphorylation reaction features one-pot operation, high product selectivity, and tolerates a broad range of alkyl NHPI esters, including derivatives of complex natural products and pharmaceuticals. Further diversified transformation of DAPOs to construct P-F, P-C, P-N, and P-O bonds was also demonstrated.

Biomimetic Robust Starch Composite Films with Super-Hydrophobicity and Vivid Structural Colors.

The starch composite films (SCFs) will be one of the best alternative packaging materials to petroleum based plastic films, which mitigates white pollution and energy consumption. However, weak mechanical stability, water resistance, and dyeability has hindered the application of SCFs. Herein, a bioinspired robust SCFs with super-hydrophobicity and excellent structural colors were prepared by fiber-reinforcement and assembling SiO2/Polydimethylsiloxane (PDMS) amorphous arrays on the surface of SCFs. The properties of the designed SCFs were investigated by various methods including scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), a tensile test, contact angle (CA) test, and an optical test. The results showed that the obtained SCFs possessed a higher tensile strength (55.17 MPa) attributed to the formed abundant hydrogen bonds between the molecular chains of the starch, cellulose fiber, and polyvinyl alcohol. Benefiting from the nanostructure with rough surface which were modified by materials with low surface free energy, the contact angle and sliding angle of the film reached up to 154° and 2°, respectively. The colors which were produced by the constructive interference of the coherent scattered light could cover all of the visible regions by tuning the diameters of the SiO2 nanoparticles. The strategy in the present study not only reinforces the mechanical strength and water resistance of SCFs but also provides an environmentally friendly way to color the them, which shows unprecedented application potential in packaging materials of the starch composite films.

Promising seawater hydrothermal combining electro-assisted pretreatment for corn stover valorization within a biorefinery concept.

In this study, for the first time, seawater hydrothermal (SH) pretreatment combining subsequent electrogenerated alkaline hydrogen peroxide (EAHP) pretreatment was proposed to achieve an effective fractionation of corn stover into high value-added products. During SH pretreatment, complex ions in natural seawater (Mg2+, Ca2+ and Cl-) were used to promote depolymerization of xylan into xylo-oligosaccharides with 49.37% yield (190 °C,40 min), 18.52% higher than that of deionized water. Subsequent EAHP treatment not only provided a green and economical way to produce hydrogen peroxide but also synchronously realized satisfied delignification (94.91%). The integrated pretreatment resulted in 91.16% of glucose yield, which was about 5.6 times more than that of unpretreated corn stover. In addition, the recovered lignin fraction which has a potential application in functional materials were investigated by FTIR, 2D-HSQC NMR and GPC. In short, this work provided a novel and environmentally-friendly strategy for biorefinery-based fractionation of corn stover.

Physicochemical Properties of the Soluble Dietary Fiber from Laminaria japonica and Its Role in the Regulation of Type 2 Diabetes Mice.

Laminaria japonica is a large marine brown alga that is annually highly productive. However, due to its underutilization, its potential value is substantially wasted. For example, a lot of Laminaria japonica cellulose remains unused during production of algin. The soluble dietary fiber (SDF) was prepared from the byproducts of Laminaria japonica, and its physicochemical properties were explored. SDF exhibits good water-holding, oil-holding, water-absorbing swelling, glucose and cholesterol absorption capacity, and inhibitory activity of α-amylase and α-glucosidase. In addition, the beneficial effects of SDF in diabetic mice include reduced body weight, lower blood glucose, and relieved insulin resistance. Finally, the intestinal flora and metabolomic products were analyzed from feces using 16S amplicon and LC-MS/MS, respectively. SDF not only significantly changed the composition and structure of intestinal flora and intestinal metabolites, but also significantly increased the abundance of beneficial bacteria Akkermansia, Odoribacter and Bacteroides, decreased the abundance of harmful bacteria Staphylococcus, and increased the content of bioactive substances in intestinal tract, such as harmine, magnolol, arachidonic acid, prostaglandin E2, urimorelin and azelaic acid. Taken together, these findings suggest that dietary intake of SDF alleviates type 2 diabetes mellitus disease, and provides an important theoretical basis for SDF to be used as a functional food.

Complete genome sequence of Pseudoalteromonas sp. Xi13 capable of degrading κ-selenocarrageenan isolated from the floating ice of Southern Ocean.

κ-Selenocarrageenan, a type of selenized carrageenan polysaccharide, can be degraded by bacteria into oligosaccharides, which has a lower molecular weight and a higher bioavailability. However, research on the microbial degradation of κ-selenocarrageenan is less. In this article, we show that Pseudoalteromonas sp. Xi13, a possibly novel Antarctic bacterium isolated from the floating ice of Southern Ocean, can degrade κ-selenocarrageenan into selenium-oligosaccharides. To gain insights into these biological activities, this bacterium was focused on screening, identification and optimization of submerged fermentation conditions by single-factor experiment. Furthermore, Selenium-oligosaccharides, mainly disaccharides and tetrasaccharides, had a certain inhibitory effect on HeLa cervical cancer cells. Whole genome sequencing and data analysis revealed a plethora of glycoside hydrolase might be involved in κ-selenocarrageenan degradation simultaneously. All told, the recent analysis of above experiment may provide a detailed insight into the characterization, function and catalytic mechanism of Pse sp. Xi13.

A diguanylate cyclase regulates biofilm formation in Rhodococcus sp. NJ-530 from Antarctica.

Biofilms represent a protective survival mode in which bacteria adapt themselves to the natural environment for survival purposes. Biofilm formation is regulated by 3,5-cyclic diguanylic acid (c-di-GMP), which is a universal second messenger molecule in bacteria. Diguanylate cyclase (DGC) catalyses c-di-GMP intracellular synthesis, which plays important roles in bacterial adaptation to the natural environment. In this study, the DGC gene was first cloned from Antarctic Rhodococcus sp. NJ-530. DGC contained 948 nucleotides and encoded 315 amino acids with a molecular weight of 34.6 KDa and an isoelectric point of 5.58. qRT-PCR demonstrated that the DGC expression level was significantly affected by lower salinity and temperature. Consistently, more biofilm formation occurred under the same stress. It has been shown that Rhodococcus sp. NJ-530 can adapt to the extreme environment in Antarctica, which is closely related to biofilm formation. These results provide an important reference for studying the adaptive mechanism of Antarctic microorganisms to this extreme environment. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s13205-021-03093-z.

Iron Phthalocyanine/Two-Dimensional Metal-Organic Framework Composite Nanosheets for Enhanced Alkaline Hydrogen Evolution.

Hydrogen evolution reaction (HER) in alkaline medium is currently under scientific spotlight for generating clean H2 fuel from electrochemical water splitting. However, alkaline HER suffers from sluggish reaction kinetics because of the additional energy required for water dissociation from catalysts in contrast to acidic HER. Herein, we report the development of two-dimensional metal-organic framework (2D MOF) Ni-1,4-benzenedicarboxylic acid-based composite nanosheets for superior performance in HER electrocatalysis. Iron phthalocyanine (FePc) molecules are uniformly anchored on the ultrathin 2D Ni-MOF, showing a substantially increased current density, improved activity, and enhanced durability in alkaline HER. On account of the ultralarge specific surface of Ni-MOF and the coupling effects between FePc and 2D MOFs, the resultant nanosheet catalyst FePc@Ni-MOF exhibits a low overpotential (334 mV) and satisfactory long-term stability (10 h) at a current density of 10 mA·cm-2, which outperform those of pristine FePc, Ni-MOF, and the counterpart FePc@bulk-MOF. This study provides new insights into the synthesis of robust MOF-based nanosheet composites with high performance in catalysis.

An azine-based polymer derived hierarchically porous N-doped carbon for hydrophilic dyes removal.

In this study, a novel hierarchically porous N-doped carbon (HPNC) material was successfully prepared by soft-templating method. The commercial triblock copolymer of Pluronic F127 and a polyazine derived from hydrazine hydrate & glyoxal were used as soft template and precursor, respectively. The obtained materials were fully characterized and tested as a sorbent for the removal of hydrophilic dyes of Methylene blue (MB), Basic Fuchsin (BF), Eosin Y (EY) and Rhodamine B (RB) from their aqueous effluents. According to the characterization results, the synthesized material of HPNC-1000 presented thick fibrous morphology with micron size in diameter, hierarchically porous structure with surface area of 1853 m2/g, pore volume of 1.59 cm3/g and nitrogen content of 4.5 wt%. Adsorption-desorption investigation reveals that synergistic effect of hydrophobic interaction and hydrogen-bonding formation of the dye molecules with the sorbent was most pronounced in the adsorptions. The maximum adsorption capacities for MB, BF, EY and RB reached 0.83, 0.92, 1.23 and 1.83 mmol g-1, respectively. The adsorption processes well fitted by the pseudo first-order kinetic model and the Liu's isotherm. The sorbent can be regenerated by above 90% of the initial adsorption efficiency after six regeneration cycles.

High-performance electrocatalyst based on polyazine derived mesoporous nitrogen-doped carbon for oxygen reduction reaction.

Nitrogen-doped porous carbon materials have high potential in metal-free electrocatalysts, which is essential for several renewable energy conversion systems. Herein, we report a convenient and environment-friendly method to fabricate a nitrogen doped mesoporous carbon (NMC) using a nonionic surfactant of Pluronic F127 micelles as the template and a Schiff-base polymer (polyazine) as the precursor. The synthesized NMCs were of spheric morphology and mesoporous structures with surface area up to 1174 m2 g-1 and high level of nitrogen (2.9-19 at%) and oxygen (4.9-7.4 at%) simultaneously doped. The electrochemical data of NMCs were analyzed in the context of the BET and XPS information. A correlation between ORR activity and the pyridinic-N was found. The NMC-700 demonstrate the highest electrocatalytic activity for ORR among the studied materials, which can be ascribed to the reasonable surface area and mesoporous structure, as well as the most abundant touchable pyridinic-N, thus providing more effective active sites for the oxygen reduction. In comparsion to the control sample, the NMC-700 provides the ORR electrocatalytic activity approximate to that of commercial Pt/C catalyst with a highly long-term stability.

Identification of the 14-3-3 ß/α-A protein as a novel maternal peptidoglycan-binding protein that protects embryos of zebrafish against bacterial infections.

14-3-3 proteins are widespread in animals, but their functions and mechanisms remain poorly defined. Here we clearly demonstrate that 14-3-3 ß/α-A is a newly identified PGN-binding protein present abundantly in the eggs/embryos of zebrafish. We also show that recombinant 14-3-3 ß/α-A acts as a pattern recognition receptor capable of identifying the bacterial signature molecule PGN, binding the bacteria, and functions as an antibacterial effector molecule directly killing the bacteria. Importantly, microinjection of r14-3-3 ß/α-A into early embryos significantly enhanced the resistance of the embryos against pathogenic A. hydrophila challenge, and this enhanced bacterial resistance was markedly reduced by co-injection of anti-14-3-3 ß/α-A antibody. Collectively, these results indicate that 14-3-3 ß/α-A is a maternal PGN-binding protein that can protect the early embryos of zebrafish against pathogenic attacks, a novel role assigned to 14-3-3 ß/α-A proteins. This work also provides new insights into 14-3-3 proteins that are widely distributed in various animals.

Effects of late-onset dietary intake of salidroside on insulin/insulin-like growth factor-1 (IGF-1) signaling pathway of the annual fish Nothobranchius guentheri.

Salidroside (SDS) is the main active ingredient of Rhodiola which has many biological functions including anti-fatigue, anti-tumor, and immune regulation activities. Our last paper demonstrated that SDS prolonged longevity of the annual fish Nothobranchius guentheri, a promising vertebrate model for anti-aging research. However, little is known about its effect on insulin/insulin-like growth factor-1 (IGF-1) signaling pathway (IIS pathway). In this study, we show that SDS is able to decrease accumulation of SA-ß-Gal. We also show that SDS administraton could reduce the expression levels of Igf-1 and Igf-1R, downregulate the expressions of p-PI3K and p-Akt and upregulate the expression levels of Sirt1 and Foxo3a, both of which are the downstream regulators of the IIS pathway. We also find that SDS could alleviate DNA damage, which could result in increased expression of transcription factor Foxo3a. Collectively, these data indicate that SDS may take part in the IIS pathway.

Ti-Mesh supported porous CoS2 nanosheet self-interconnected networks with high oxidation states for efficient hydrogen production via urea electrolysis.

The urea oxidation reaction (UOR) is an ideal alternative to the oxygen evolution reaction (OER) towards energy efficient hydrogen production. However developing Earth-abundant electrocatalysts for urea oxidation and hydrogen generation still remains a big challenge. Herein, porous CoS2 nanosheet self-interconnected networks with high oxidation states located on a Ti-mesh (P-CoS2/Ti) are synthesized and can act as a high activity catalyst for both the hydrogen evolution reaction (HER) and urea oxidation reaction (UOR). In this literature, we report a very interesting phenomenon that cobalt hydroxide with different chemical compositions and crystal structures can be synthesized by adjusting the concentration of NaOH during the etching process. Moreover, porous CoS2 nanosheets with different crystallite sizes can be synthesized by adjusting the sulfuration temperature. P-CoS2/Ti presents outstanding catalytic performance with an overpotential of 91 mV to deliver a current density of 10 mA cm-2 for the HER, and it gives an anode potential of 1.243 V vs. RHE at 10 mA cm-2 for the UOR. A two-electrode electrolyser is used to validate the catalyst performance, and the P-CoS2/Ti||P-CoS2/Ti electrode is capable of producing a current density of 10 mA cm-2 at a cell potential of only 1.375 V, demonstrating its potential feasibility in the practical application of efficient hydrogen production.

Copper-Catalyzed Direct Twofold C-P Cross-Coupling of Unprotected Propargylic 1,4-Diols: Access to 2,3-Bis(diarylphosphynyl)-1,3-butadienes.

The first facile and efficient Cu-catalyzed direct coupling of unprotected propargylic diols with H-phosphine oxides was developed, providing a practical approach to access structurally diverse 2,3-bis(diarylphosphynyl)-1,3-butadienes along with the formation of two new P-Csp2 and two new C═C bonds under ligand- and base-free conditions.

Preparation and characterization of chitosan membranes.

The present study investigates a new solvent system for the dissolution of chitosan and a new method for preparing chitosan membranes. First, aqueous tartaric acid was used to pretreat chitosan. Then, the chitosan was precipitated with ethanol or other regenerating agents, and 1.5 mL of 1-ethyl-3-methylimidazolium acetate ([EMIM]AC) was added to obtain translucent suspensions. The chitosan membranes were prepared by casting the suspensions on glass plates and allowing solvent evaporation. The structure and properties of the films were investigated by SEM, FT-IR, XRD and TGA. Also, the mechanical properties, as well as physical and chemical characteristics, of the chitosan films were evaluated. The results indicated that the optimum dissolution time was 10 min and the most suitable drying temperature was 60 °C. The thus-prepared film was moderately thick (about 0.02 mm) and had a smooth surface, without curling. The chitosan film prepared by ethanol regeneration had a tensile strength of up to 24 MPa, a minimum swelling degree of 78%, and a water vapor transmission rate of 270 g m-2 d-1 without the addition of plasticizer.