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In this study, hierarchically porous ZSM-5 catalysts were fabricated by one-pot assembling ZSM-5 particles onto diverse biomass templates (e.g., rice husk, tea seed husk, tung shell, and coconut shell), wherein the biomass template was transformed into bio-SiO 2 or biochar depending on the calcination conditions. The biotemplated ZSM-5 variants, including ZSM-5(RH), ZSM-5(TSH), ZSM-5(TS), and ZSM-5(CS), exhibited significantly improved deoxygenation performance, achieving ∼100.0% deoxygenation efficiency as compared to the untemplated ZSM-5 catalyst (85.3%). Among them, the ZSM-5(TSH) catalyst exhibited the best performance, accompanied by 100% conversion, 99.6% deoxygenation rate, and 82.3% olefin selectivity. Interestingly, the product distribution over biotemplated ZSM-5 was dominant C 4 = -C 8 = (selectivity of ∼100% in total olefins), while long-chain olefins (C 9 = -C 17 = ) was the major product (selectivity of 57.3%) over the untemplated ZSM-5. Moreover, molecular dynamics (MD) simulations revealed that biotemplated ZSM-5 exhibited superior diffusion coefficients of stearic acid (reaction substrate) and anthracene (coke precursor) compared to the untemplated ZSM-5, indicating higher self-diffusion rates and consequently superior activity and stability in the catalytic pyrolysis reactions. Furthermore, in situ DRIFTS results showed stearic acid over ZSM-5(TSH) primarily was converted to the C 17 H 36 intermediate mainly via the decarboxylation route, followed by dehydrogenation pyrolysis and C-C breaking reactions into C 4 = -C 8 = products. Overall, this work developed an effective strategy for manufacturing hierarchically porous zeolite catalysts using biomass-derived bio-SiO 2 or biochar as the platform.

Lead-chloride perovskites are promising candidates for optoelectronic applications, such as visible-blind UV photodetection. It remains unclear how the deep defects in this wide-bandgap material impact the carrier recombination dynamics. In this work, we study the defect properties of MAPbCl 3 (MA = CH 3 NH 3 ) based on photoluminescence (PL) measurements. Our investigations show that apart from the intrinsic emission, four sub-bandgap emissions emerge, which are very likely to originate from the radiative recombination of excitons bound to several intrinsic vacancy and interstitial defects. The intensity of various emission features can be tuned by adjusting the type and ratio of precursors used during synthesis. Our study not only provides important insights into the defect property and carrier recombination mechanism in this class of material but also demonstrates efficient strategies for defect passivation and engineering, paving the way for further development of lead-chloride perovskite-based optoelectronic devices.

The efficient and economic conversion of CO 2 and renewable H 2 into methanol has received intensive attention due to growing concern for anthropogenic CO 2 emissions, particularly from fossil fuel combustion. Herein, we have developed a novel method for preparing Ni/In 2 O 3 nanocatalysts by using porous MIL-68(In) and nickel(II) acetylacetonate (Ni(acac) 2 ) as the dual precursors of In 2 O 3 and Ni components, respectively. Combined with in-depth characterization analysis, it was revealed that the utilization of MIL-68(In) as precursors favored the good distribution of Ni nanoparticles (∼6.2 nm) on the porous In 2 O 3 support and inhibited the metal sintering at high temperatures. The varied catalyst fabrication parameters were explored, indicating that the designed Ni/In 2 O 3 catalyst (Ni content of 5 wt %) exhibited better catalytic performance than the compared catalyst prepared using In(OH) 3 as a precursor of In 2 O 3 . The obtained Ni/In 2 O 3 catalyst also showed excellent durability in long-term tests (120 h). However, a high Ni loading (31 wt %) would result in the formation of the Ni-In alloy phase during the CO 2 hydrogenation which favored CO formation with selectivity as high as 69%. This phenomenon is more obvious if Ni and In 2 O 3 had a strong interaction, depending on the catalyst fabrication methods. In addition, with the aid of in situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory (DFT) calculations, the Ni/In 2 O 3 catalyst predominantly follows the formate pathway in the CO 2 hydrogenation to methanol, with HCOO* and *H 3 CO as the major intermediates, while the small size of Ni particles is beneficial to the formation of formate species based on DFT calculation. This study suggests that the Ni/In 2 O 3 nanocatalyst fabricated using metal-organic frameworks as precursors can effectively promote CO 2 thermal hydrogenation to methanol.

Cross-linking with functional molecular species in polymeric carbon nitride (PCN) could offer a positive strategy that tunes its molecular structure with excellent conductivity to improve photocatalytic activity. Herein, the benzene ring-cross-linked photocatalyst is obtained via the polymerization of urea, melamine, and trimesic acid. Benzene ring-cross-linked PCN narrows the band gap and augments the push-pull effect of carriers, thus enhancing visible light harvesting and transfer easiness of photogenerated electron/hole pairs. Notably, the amount of trimesic acid was optimized during the benzene ring-cross-linked photocatalyst preparation (marked as 01T/A-CN, 02T/A-CN, and 03T/A-CN). Among them, 02T/A-CN photocatalyst achieved an excellent hydrogen production rate of 1931 μmol/h·g, which is higher than that of CN under visible light and beyond most reported. Theoretical calculations further confirmed that the introduction of benzene ring significantly reduces the band gap of PCN, bringing the delocalized electron, a longer intramolecular electron transition distance, and molecular bending. All those factors made benzene ring-cross-linked PCN with improved photocatalytic hydrogen production under visible light irradiation.

The commercialization of alloy-type anodes has been hindered by rapid capacity degradation due to volume fluctuations. To address this issue, stress-relief engineering is proposed for Si anodes that combines hierarchical nanoporous structures and modified layers, inspired by the phenomenon in which structures with continuous changes in curvature can reduce stress concentration. The N-doped C-modified hierarchical nanoporous Si anode with a microcurved pore wall (N-C@m-HNP Si) is prepared from inexpensive Mg-55Si alloys using a simple chemical etching and heat treatment process. When used as the anode for lithium-ion batteries, the N-C@m-HNP Si anode exhibits initial charge/discharge specific capacities of 1092.93 and 2636.32 mAh g -1 at 0.1 C (1 C = 3579 mA g -1 ), respectively, and a stable reversible specific capacity of 1071.84 mAh g -1 after 200 cycles. The synergy of the hierarchical porous structure with a microcurved pore wall and the N-doped C-modified layer effectively improves the electrochemical performance of N-C@m-HNP Si, and the effectiveness of stress-relief engineering is quantitatively analyzed through the theory of elastic bending of thin plates. Moreover, the formation process of Li 15 Si 4 crystals, which causes substantial mechanical stress, is investigated using first-principles molecular dynamic simulations to reveal their tendency to occur at different scales. The results demonstrate that the hierarchical nanoporous structure helps to inhibit the transformation of amorphous Li x Si into metastable Li 15 Si 4 crystals during lithiation.

Herein, we present a novel method for the N -arylation of amino acid esters using α-bromoacetaldehyde acetal and acetoacetate via an I 2 -mediated metal-free benzannulation strategy, which disclosed the first synthetic application of N -arylation of amino acids using nonaromatic building blocks. The synthesized N -arylated amino acid derivatives were found to possess promising selective inhibition against human hepatocellular liver carcinoma cells, human melanoma cells, and human normal liver cells, with an IC 50 value as low as 16.79 μg·mL -1 .

Designing stimulus-switch viscoelastic solutions and Pickering emulsions with reversible CO 2 -responsive behavior remains a challenge. A rosin-based CO 2 -responsive surfactant, N-cetyl-maleimidepimaric acid N,N-dimethylenediamide (C 16 MPAN), was synthesized and used to prepare CO 2 -triggered viscoelastic solutions and Pickering emulsions. This surfactant exhibited excellent CO 2 -responsive performance in water and formed a viscoelastic solution. This viscoelastic system was investigated by dynamic light scattering (DLS), rheology, and cryogenic transmission electron microscopy (Cory-TEM). The shear viscosity of the system increased by 3-4 orders of magnitude after bubbling with CO 2 and a large number of elongated, flexible, tubular wormlike micelles were observed. Further, Pickering emulsions were prepared by C 16 MPAN + synergistically with cellulose nanocrystals (CNCs), whose stability and switchability were investigated via adsorption isotherm, droplet size, contact angle, and macroscopic photographs. C 16 MPAN + was adsorbed with CNCs to form mechanical barriers at the oil-water interface, making the emulsion stable for at least three months, and desorption from CNCs enabled emulsion breaking. The cycle could be switched reversibly multiple times and the particle size distribution of emulsion was basically the same. This work enriches the application of biomass resources in intelligent responsive materials.

Metal-organic frameworks (MOFs) have become promising host materials for enzyme immobilization and protection. Herein, ZIF-8 nanocubes were successfully self-assembled onto yeast as a biological template to obtain hybrid Y@ZIF-8. The size, morphology, and loading efficiency of ZIF-8 nanoparticles assembled on yeast templates can be well-regulated by adjusting the various synthetic parameters. Particularly, the amount of water significantly affected the particle size of ZIF-8 assembled on yeast. Through using a cross-linking agent, the relative enzyme activity of Y@ZIF-8@t-CAT could be greatly enhanced and remained the highest even after seven consecutive cycles, with improved cycling stability, as compared to that of Y@ZIF-8@CAT. In addition to the effect of the physicochemical properties of Y@ZIF-8 on the loading efficiency, the temperature tolerance, pH tolerance, and storage stability of Y@ZIF-8@t-CAT were also systematically investigated. Importantly, the catalytic activity of free catalase was decreased to 72% by 45 days, while the activity of the immobilized catalase remained above 99%, suggesting good storage stability. The present work demonstrates that yeast-templated ZIF-8 nanoparticles have a high potential to be used as biocompatible immobilization materials and are promising candidates for the preparation of effective biocatalysts in biomedicine applications.

Water pollution is one of the major problems that need to be solved in modern society, and there is a need to develop an effective adsorbent to purify the polluted water. In this article, three supramolecular metallohydrogels containing a three-dimensional network structure have been prepared from rosin derivatives. The supramolecular metallohydrogels have good thermal stability and maintain mechanical strength at high temperatures. Interestingly, the sodium N -(dehydroabiety1)maleamate/Ca 2+ supramolecular metallohydrogels exhibit rare multi-stimulus responsiveness (mechanical vibration, temperature, pH, EDTA, etc.), especially to mechanical vibration with over 10 cycles, indicating ultra-mechanical response properties. More importantly, the unique three-dimensional network structure of the metallohydrogels can effectively adsorb cationic dyes in the wastewater. The adsorption amount and adsorption rate of this supramolecular metallohydrogels for rhodamine 6G after 48 h were at least 160.6 mg/g and 97%, respectively. The adsorption kinetic process of this metallohydrogel follows a quasi-secondary kinetic model, where the adsorption process is mainly electrostatic and weak π-π interactions. And the metallohydrogels can also be recovered by 0.5 mol/L hydrochloric acid solution desorption after adsorption of the dye. This is the first supramolecular metallohydrogel system prepared from the natural product rosin and applied to dye adsorption. This broadens the application of rosin in the field of supramolecular gel and dye adsorption and recycling.

Asymmetric addition of terminal alkynes catalyzed by a transition metal to isatins obviously is an efficient and economic method for the synthesis of 3-alkynyl-3-hydroxy-2-oxindoles. The new dimeric chiral quaternary ammoniums derived from a natural chiral alkaloid, quinine, can be used as cationic inducers of the enantioselectivity for the Ag(I)-catalyzed alkynylation of isatin derivatives under mild conditions. The desired chiral 3-alkynyl-3-hydroxy-2-oxindoles can be obtained in good to high yields with high to excellent enantioselectivites (≤99% ee). A variety of aryl-substituted terminal alkynes and substituted isatins are tolerated in this reaction.

The emerged strategy of manipulating the rhombohedral crystal structure provides another new degree of freedom for optimizing the thermoelectric properties of GeTe-based compounds. However, the concept is difficult to be effectively measured and often depends on heavy doping that scatters carriers severely. Herein, we synergistically manipulate lattice distortion and vacancy concentration to promote the excellent electrical transport of GeTe-Cu 2 Te alloys and quantify the interaxial angle-dependent density of state effective mass. Distinct from the conventional electronic coupling effect, about 2% substitution of Zr 4+ significantly increases the interaxial angle, thereby enhancing the band convergence effect and improving the Seebeck coefficient. In addition, Ge-compensation attenuates the mobility deterioration, leading to improved power factor over the whole temperature range, especially exceeding ∼22 μW cm -1 K -2 at 300 K. Furthermore, the Debye-Callaway model elucidates low lattice thermal conductivity due to strong phonon scattering from Zr/Ge substitutional defects. As a result, the highest figure of merit zT of ∼1.6 (at 650 K) and average zT ave of ∼0.9 (300-750 K) are obtained in (Ge 1.01 Zr 0.02 Te) 0.985 (Cu 2 Te) 0.015 . This work demonstrates the effective band modulation of Zr on GeTe-based materials, indicating that the modification of the interaxial angle is a deep pathway to improve thermoelectrics.

Although much progress has been made in developing botanical fungicides to combat fungal diseases in crops, there remains a great need to improve the efficiency and long-term safety of these fungicides. This study proposes a novel strategy for designing citral-thiourea derivatives that feature such desirable properties. The motivation of the work herein was to enhance the antifungal activity of citral against C. gloeosprioides by exploiting the synergistic effect that arises from combining citral and thiourea compounds, thereby producing citral-thiourea derivatives that exhibit good long-term safety. The results revealed that the generated compounds e1 , e3 , e6 , e18 , and g showed remarkable antifungal activities against C. gloeosprioides , with corresponding EC 50 values reaching 0.16, 1.66, 1.37, 4.76, and 4.60 mg/L, respectively, showing that the compounds significantly outperformed both the positive control kresoxim-methyl and the commercially available fungicide carbendazim. Furthermore, compound g showed stronger protective efficacy against C. gloeosprioides than carbendazim on mango fruit at 25 mg/L. Investigating the preliminary structure-activity relationship (SAR) of the compounds also revealed that the citral-thiourea derivatives exhibited higher antifungal activities against C. gloeosprioides compared to citral and thiourea compounds. This reinforcement of antifungal activity observed in the derivatives was found to be attributable to the two characteristics of low molecular size and the presence of a fluorine atom in the meta-position of the benzene ring. Beyond this, it was determined from QSAR that two molecular descriptors (the Kier-Hall index (order 3) and Tot dipole of the molecules) were negatively related to the antifungal activity of the citral-thiourea derivatives, while one other (the maximum resonance energy of a C-H bond) was positively related to their antifungal activity. More importantly, the citral-thiourea derivatives with high antifungal activities ( i.e. , compounds e1 , e3 , e6 , e14 , e15 , e18 , and g ) exhibited negligible cytotoxicity to LO2 and HEK293T cell lines. The antifungal mechanism of the generated citral-thiourea derivatives was investigated by scanning electron microscopy (SEM) and relative conductivity. The derivatives were found to affect mycelial morphology and increase fungal cell membrane permeability, thereby resulting in the destruction of fungal cell membranes. These promising results provide novel insights into the study and potential application value of citral-thiourea derivatives as high-efficiency antifungal agents against C. gloeosprioides .

The utilization of thermoelectric devices that directly convert waste heat to electricity is an effective approach to alleviate the global energy crisis. However, the low efficiency of thermoelectric materials has puzzled the widespread applications. The CoSb 3 -based skutterudites are favored by device integration due to the excellent thermal stability, while the development of pristine CoSb 3 materials is limited by the ultra-high thermal conductivity and the poor Seebeck coefficient. In this work, we demonstrate that both structural improvement and strong phonon interaction are realized simultaneously in In-filled CoSb 3 coordinated with excessive Sb. The extra Sb compensates the deficiency on the Sb 4 ring, improving the Seebeck coefficient, and cooperates with In to further advance the carrier concentration. Therefore, the structure optimization and chemical potential regulation maximize the electrical properties. Thermally, the residual InSb nanoparticles and partial In/Sb-alloying, along with vibration of In in voids, jointly shorten the multi-frequency phonon relaxation time, leading to a dramatic decline in the lattice thermal conductivity. As a result, a maximum zT max of ∼1.27 at 650 K and an average zT avg of ∼0.9 from 300 to 750 K was obtained in In 1.4 Co 4 Sb 12 + 8%Sb, respectively. Our findings provide valuable guidance for the selection of CoSb 3 -based skutterudite dopants to achieve high-performance thermoelectric materials.

To develop new antifungal agents against phytopathogenic fungi, a series of citral-thiazolyl hydrazine derivatives were designed, synthesized, and characterized by FT-IR, 1 H NMR, 13 C NMR, and HRMS. Antifungal activity results showed that most synthetic compounds exhibited broad-spectrum antifungal activities against six phytopathogenic fungi in vitro . Notably, compounds b and c15 exhibited remarkable antifungal activity against Colletotrichum gloeosprioides , Rhizoctonia solani , Phytophthora nicotianae var. nicotianae , Diplodia pinea , Colletotrichum acutatum , and Fusarium oxysporum f. sp. niveum , which were all superior to the positive control tricyclazole. Structure-activity relationship (SAR) studies demonstrated that introducing electron-withdrawing groups such as F on the benzene ring exhibited outstanding antifungal activities against all the tested fungi. Furthermore, compound b could effectively control rice sheath blight and showed higher curative activities against R. solani than validamycin·bacillus in vivo . In addition, the in vitro cytotoxicity results indicated that compound b possessed moderate cytotoxicity activity, and all citral-thiazolyl hydrazine derivatives exhibited lower or no cytotoxicity to the LO2 and HEK293 cell lines. In addition, the acute oral toxicity test showed that compound b had moderate toxicity (level II) with an LD 50 value of 310 mg/kg bw (95% confidence limit: 175-550 mg/kg bw). Finally, a preliminary action mechanism study showed that causing obvious malformation of mycelium and increasing cell membrane permeability are two of the potential mechanisms by which compound b exerts antifungal activity. The present work indicates that some of these derivatives may serve as novel potential fungicides, and compound b is expected to be the leading structure for the development of new antifungal agents.

Using first-principles theory, this paper investigates the sensing behavior of the Ru-doped PtSe 2 (Ru-PtSe 2 ) monolayer for two dominant gases, namely, H 2 and C 2 H 2 , in the transformer oil to explore its potential as a gas sensor to evaluate the operation status of the electrical transformers. Ru-doping prefers to go through the S 1 site with the largest E b of -3.71 eV. Chemisorption is identified in the H 2 and C 2 H 2 systems with E ad obtained as -0.83 and - 2.09 eV, respectively, indicating the stronger performance of the Ru-PtSe 2 monolayer upon C 2 H 2 adsorption. Meanwhile, the obvious improvement of bandgap in the C 2 H 2 system suggests the potential of Ru-PtSe 2 monolayer as a resistance-type gas sensor for C 2 H 2 detection. Moreover, the applied biaxial strains ranging at 1-5% give rise to various Q T and E g in two systems, indicating the tunable sensing response of the Ru-PtSe 2 monolayer for gas detection with modulated strains. Our calculation proposes a novel 2D sensing material for H 2 and C 2 H 2 detection, which would be beneficial to stimulate more edge-cutting research in the gas sensing field as well., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

A novel pH-responsive wormlike micellar viscoelastic solution was constructed by a rosin-based anionic surfactant (Na-MPA-AZO-Na) in the presence of cetyltrimethylammonium bromide (CTAB). The viscoelasticity, aggregate morphology, and pH-responsiveness of the pH-responsive wormlike micelles have been investigated through the method of rheology and cryogenic-transmission electron microscopy. Its corresponding mechanism has been studied using 1 H NMR and 1 H- 1 H 2D NOESY HNMR. The zero-shear viscosity (η 0 ) of the wormlike micellar solution rapidly decreases by 3 orders of magnitude as the pH increases from 5.21 to 9.56. The viscoelastic fluids and water-like solutions can be converted by tuning the pH between 3.62 and 12.00, and the corresponding aggregates also transform between wormlike micelles and spherical micelles. In addition, the wormlike micellar cross-sectional diameter is approximately 10 nm, which is remarkably larger than that of the common wormlike micelles. The phenomenon can be attributed to the large steric volume of the rosin rigid skeleton. When the pH is 12.00, a "pseudo" Gemini surfactant is constructed by Na-MPA-AZO-Na and CTAB through the electrostatic interactions. Wormlike micelles also can be formed with the increasing concentrations. The η 0 of the wormlike micellar system shows strong dependence on concentration with an exponent of 9.6 (η 0 ∝ C 9.6 ). This work further promotes new applications of forest resources.

A kind of polymerizable dispersant based on natural rosin was used to disperse single-walled carbon nanotubes (SWNTs) in aqueous solution followed by in situ free-radical polymerization to achieve a controllable SWNTs dispersion, that not only can be controlled by CO 2 /N 2 , but can also be recycled and redispersed in CO 2 -saturated water after drying without sonication., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Pressure measurements are performed everyday with simple devices, and in the field of analytical chemistry the pressure-based signaling strategy offers two important advantages, signal amplification and particular applicability in point-of-care settings. Herein, by using vancomycin (Van)-functionalized platinum nanoparticles (PtNPs@Van) and aptamer-coated magnetic CuFe 2 O 4 nanoprobes dual-recognition units integrated with a catalyzed breakdown of H 2 O 2 for O 2 generation, we demonstrated that gas pressure can be used as a readout means for highly sensitive pathogenic bacteria identification and quantification. Using Staphylococcus aureus ( S. aureus) as a test case, integration of the molecular dual-recognition component with the catalyzed gas-generation reaction leads to a significant pressure change (Δ P), and the correlation between the concentration of S. aureus and the Δ P signal was found to be linear from 5.0 to 1.0 × 10 4 cfu/mL with a detection limit of 1.0 cfu/mL. Other nontarget bacteria show negative results, verifying the high specificity of the present strategy. When employed to assay S. aureus in saliva and milk samples, the approach shows recoveries from 93.3% to 107.1% with relative standard derivation (RSD) less than 8.8%. By the integration of catalyzed gas-generation reaction with the designed molecular recognition event, obviously the pressure-based signaling strategy could facilitate pathogenic bacteria identification and quantification not only in the laboratory but also in point-of-care settings, which could have great potential in the application of food safety and infectious disease diagnosis.

A novel CO 2 -responsive surfactant, maleopimaric acid glycidyl methacrylate ester 3-(dimethylamino)propylamine imide (MPAGN), based on sustainable resource of rosin was synthesized and used to prepare a kind of CO 2 -responsive Pickering emulsions with nanosilica. MPAGN can be reversibly responsive to CO 2 and N 2 between active cationic (MPAGNH + ) and inactive nonionic (MPAGN), leading to adsorb on or desorb from the surface of nanosilica, then stabilize or break emulsion. CO 2 -responsive behavior of MPAGN was verified by cycle change of pH and conductivity with bubbling CO 2 and N 2 alternately. The type of adsorption of MPAGNH + at the particle-water interface was explained according to the adsorption isotherms. The mechanisms of stabilization, destabilization, and restabilization of Pickering emulsion were analyzed according to zeta potentials and droplet size. This Pickering emulsion can be reversible between stable and unstable by bubbling CO 2 and N 2 alternately. Moreover, this emulsifier can be recycled when new oil was added after removing the initial oil. Therefore, it not only has economic benefits but also has an environmentally friendly property.

Many viruses often have closely related yet antigenically distinct serotypes. An ideal vaccine against viral infections should induce a multivalent and protective immune response against all serotypes. Inspired by bacterial membrane vesicles (MVs) that carry different protein components, we constructed an agr locus deletion mutant of the Staphylococcus aureus strain (RN4220-Δagr) to reduce potential toxicity. Nanoscale vesicles derived from this strain ( Δagr MVs) carry at least four major components that can deliver heterologous antigens. These components were each fused with a triple FLAG tag, and the tagged proteins could be incorporated into the Δagr MVs. The presentation levels were (3.43 ± 0.73)%, (5.07 ± 0.82)%, (2.64 ± 0.61)%, and (2.89 ± 0.74)% of the total Δagr MV proteins for Mntc-FLAG, PdhB-FLAG, PdhA-FLAG, and Eno-FLAG, respectively. With two DENV envelope E domain III proteins (EDIIIconA and EDIIIconB) as models, the DENV EDIIIconA and EDIIIconB delivered by two staphylococcal components were stably embedded in the Δagr MVs. Administration of such engineered Δagr MVs in mice induced antibodies against all four DENV serotypes. Sera from immunized mice protected Vero cells and suckling mice from a lethal challenge of DENV-2. This study will open up new insights into the preparation of multivalent nanosized viral vaccines against viral infections.

The production of chemicals and various materials from black liquor lignin will greatly improve the economics of biomass refining. In the present work, organosolv lignin residues (OLRs) from the organosolv pulping process were used to fabricate submicron lignin spheres using ethanol/water mixtures as an antisolvent, in conjunction with homogenization. Both the ethanol content in the ethanol/water mixture and the applications of homogenization were investigated as key factors affecting the agglomeration of OLRs. The results show that the solubility of the amphiphilic OLRs in ethanol was approximately 28 and 32 times greater than those of alkali lignin and kraft lignin, respectively. Using the optimal percentage of ethanol together with homogenization enhanced the nucleation of lignin macromolecules, such that the colloidal spheres of OLR were spontaneously assembled via gradual hydrophilic-lipophilic aggregation. The resulting OLR colloidal spheres had a yolk-shell structure and a mean particle diameter of around 200 nm, when the ethanol content was 50% and the homogenization time was 15 min or more. This study demonstrates a simple means of utilizing OLRs to produce lignin-based spheres. The lignin spheres generated in this work are thought to have potential applications in many fields as porous carbon precursors for energy storage, sensitive functional materials, and controlled-release fertilizer carriers., Competing Interests: The authors declare no competing financial interest.

Currently, anti-AD drug discovery using target-based approaches is extremely challenging due to unclear etiology of AD and absence of validated therapeutic protein targets. Neuronal death, regardless of causes, plays a key role in AD progression, and it is directly linked to neuroinflammation. Meanwhile, phenotypic screening is making a resurgence in drug discovery process as an alternative to target-focused approaches. Herein, we employed microglia-based phenotypic screenings to search for small molecules that modulate the release of detrimental proinflammatory cytokines. The identified novel pharmacological inhibitor of neuroinflammation (named GIBH-130) was validated to alter phenotypes of neuroinflammation in AD brains. Notably, this molecule exhibited comparable in vivo efficacy of cognitive impairment relief to donepezil and memantine respectively in both β amyloid-induced and APP/PS1 double transgenic Alzheimer's murine models at a substantially lower dose (0.25 mg/kg). Therefore, GIBH-130 constitutes a unique chemical probe for pathogenesis research and drug development of AD, and it also suggests microglia-based phenotypic screenings that target neuroinflammation as an effective and feasible strategy to identify novel anti-AD agents.

Recruitment of antibodies in human immune systems for targeted destruction of tumor cells has emerged as an exciting area of research due to its low occurrence of side effects, high efficacy, and high specificity. The presence of large amounts of anticarbohydrate natural antibodies in human sera has prompted research efforts to utilize carbohydrate epitopes for immune recruitment. Here, we have developed a general strategy for specific targeted destruction of tumor cells based on rhamnose-functionalized liposomes. Tumor cells artificially decorated with rhamnose epitopes were subjected to complement-mediated cytotoxicity in vitro and showed delayed tumor growth in vivo. This study highlights the therapeutic potential for activation of endogenous immune response through cell-surface glycan engineering.

An important result of research on mixed-lanthanide metal-organic frameworks (M'LnMOFs) is the realization of highly sensitive ratiometric luminescent thermometers. Here, we report the design and synthesis of the new M'LnMOF Tb0.80Eu0.20BPDA with high relative sensitivity in the physiological temperature regime (298-318 K). The emission intensity and luminescence lifetime were investigated and compared to those of existing materials. It was found that the temperature-dependent luminescence properties of Tb0.80Eu0.20BPDA are strongly associated with the distribution of the energy levels of the ligand. Such a property can be useful in the design of highly sensitive M'LnMOF thermometers.

Epoxidized soybean oil (ESO) grafted hydroxyethyl cellulose (HEC) was prepared via ring-opening polymerization, in which the hydroxyl groups of HEC acted as initiators and the polymeric ESO were covalently bonded to the HEC. Hydrolysis of ESO-grafted HEC (ESO-HEC) was performed with sodium hydroxide, and the hydrolyzed ESO-HEC (H-ESO-HEC) products were characterized via Fourier transform infrared (FT-IR) and (1)H and (13)C nuclear magnetic resonance (NMR) spectroscopies, high-temperature gel permeation chromatography (HT-GPC), and differential scanning calorimetry (DSC). The results indicated that ring-opening polymerization of ESO occurred with the hydroxyl groups of HEC as initiators. The molecular weights of the H-ESO-HEC products were varied by adjusting the mass ratio of HEC and ESO. Through neutralizing the carboxylic acid of H-ESO-HEC with sodium hydroxide, novel polymeric surfactants (H-ESO-HEC-Na) were obtained, and the effects of polymeric surfactants on the surface tension of water were investigated as a function of concentration of H-ESO-HEC-Na. The H-ESO-HEC-Na was effective at lowering the surface tension of water to 26.33 mN/m, and the critical micelle concentration (CMC) value decreased from 1.053 to 0.157 g/L with increases in molecular weights of the polymeric surfactants. Rheological measurements indicated that the H-ESO-HEC-Na solutions changed from pseudoplastic property to Newtonian with increasing shear rate.

SETD8/SET8/Pr-SET7/KMT5A is the sole protein lysine methyltransferase (PKMT) known to monomethylate lysine 20 of histone H4 in vivo. SETD8's methyltransferase activity has been implicated in many essential cellular processes including DNA replication, DNA damage response, transcription modulation, and cell cycle regulation. Developing SETD8 inhibitors with cellular activity is a key step toward elucidating the diverse roles of SETD8 via convenient pharmacological perturbation. From the hits of a prior high throughput screen (HTS), SPS8I1-3 (NSC663284, BVT948, and ryuvidine) were validated as potent SETD8 inhibitors. These compounds contain different structural motifs and inhibit SETD8 via distinct modes. More importantly, these compounds show cellular activity by suppressing the H4K20me1 mark of SETD8 and recapitulate characteristic S/G2/M-phase cell cycle defects as observed for RNAi-mediated SETD8 knockdown. The commonality of SPS8I1-3 against SETD8, together with their distinct structures and mechanisms for SETD8 inhibition, argues for the collective application of these compounds as SETD8 inhibitors.

A new mixed lanthanide metal-organic framework thermometer Tb0.9Eu0.1PIA with the significantly high sensitivity of 3.53% per K has been realized by making use of an organic ligand, 5-(pyridin-4-yl)isophthalate, with higher triplet state energy.

Targeting neuroinflammation may be a new strategy to combat Alzheimer's disease. An aminopyridazine 1b previously reported as a novel antineuroinflammatory agent was considered to have a potential therapeutic effect for Alzheimer's disease. In this study, we further explored the chemical space to identify more potent antineuroinflammatory agents and validate their in vivo efficacy in an animal model. Compound 14 was finally identified as an effective agent with comparable in vivo efficacy to the marketed drug donepezil in counteracting spatial learning and working memory impairment in an Aβ-induced Alzheimer's mouse model.