Molecular-caged metal-organic frameworks for energy management.

Metal-organic frameworks (MOFs) hold great promise for diverse applications when combined with polymers. However, a persistent challenge lies in the susceptibility of exposed MOF pores to molecule and polymer penetration, compromising the porosity and overall performance. Here, we design a molecular-caged MOF (MC-MOF) to achieve contracted window without sacrificing the MOF porosity by torsional conjugated ligands. These molecular cages effectively shield against the undesired molecule penetration during polymerization, thereby preserving the pristine porosity of MC-MOF and providing outstanding light and thermal management to the composites. The polymer containing 0.5 wt % MC-MOF achieves an 83% transmittance and an exceptional haze of 93% at 550 nanometers, coupled with remarkable thermal insulation. These MC-MOF/polymer composites offer the potential for more uniform daylighting and reduced energy consumption in sustainable buildings when compared to traditional glass materials. This work delivers a general method to uphold MOF porosity in polymers through molecular cage design, advancing MOF-polymer applications in energy and sustainability.

Quantifying sodium hypochlorite content in hypochlorite-based disinfectants via phase-conversion headspace technique.

In this work, a novel and efficient approach for sodium hypochlorite analysis is proposed via phase-conversion headspace technique, which is based on the gas chromatography (GC) detection of generated carbon dioxide (CO2) from the redox reaction of sodium hypochlorite with sodium oxalate. The data obtained by the proposed method suggest the high detecting precision and accuracy. In addition, the method has low detection limits (limit of quantification (LOQ) = 0.24 µg/mL), and the recoveries of added standard ranged from 98.33 to 101.27 %. The proposed phase-conversion headspace technique is efficient and automated, thereby offering an efficient strategy for highly efficient analysis of sodium hypochlorite and related products.

Establishing a new methodology for determining the water absorbability of cellulose-derived materials via a vapor-monitoring headspace strategy.

In this research, for the first time, we introduce a vapor-monitoring headspace strategy to establish a new methodology for determining the water absorbability of cellulose-derived materials. The method involves detecting the water in the gas phase from various cellulose-derived materials after achieving the equilibrium state. By utilizing the headspace technique to monitor the change in water vapor pressure from bound water to free water, a change point indicating the water absorbability can be identified through fitting procedures. The study showed that the newly-established method possesses high precision (relative standard deviation ≤2.92%) and accuracy (relative differences ≤5.74%) for water absorbability analysis. The present method emerges as a facile and reliable tool for measuring water absorbability, and the introduction of the vapor-monitoring headspace strategy is anticipated to inspire the development of a new type of analytical method.

Diatom Frustules Decorated with Co Nanoparticles for the Advanced Anode of Li-Ion Batteries.

Silica is regarded as a promising anode material for lithium-ion batteries (LIBs) because of its high theoretical capacity. However, large volume variation and poor electrical conductivity are limiting factors for the development of SiO2 anode materials. To solve this problem, combining SiO2 with a conductive phase and designing hollow porous structures are effective ways. In this work, The Co(II)-EDTA chelate on the surface of diatom biosilica (DBS) frustules and obtained DBS@C-Co composites decorated with Co nanoparticles by calcination without a reducing atmosphere is first precipitated. The unique three-dimensional structure of diatom frustules provides enough space for the volume change of silica during lithiation/delithiation. Co nanoparticles effectively improve the electrical conductivity and electrochemical activity of silica. Through the synergistic effect of the hollow porous structure, carbon layer and Co nanoparticles, the DBS@C-Co-60 composite delivers a high reversible capacity of >620 mAh g-1 at 100 mA g-1 after 270 cycles. This study provides a new method for the synthesis of metal/silica composites and an opportunity for the development of natural resources as advanced active materials for LIBs.

Design of Imide Oligomer-Mediated MOF Clusters for Solar Cell Encapsulation Systems by Interface Fusion Strategy.

Dielectric encapsulation materials are promising for solar cell areas, but the unsatisfactory light-management capability and relatively poor dielectric properties restrict their further applications in photovoltaic and microelectronic devices. Herein, an interface fusion strategy to engineer the interface of MOF (UiO-66-NH2 ) with anhydride terminated imide oligomer (6FDA-TFMB) is designed and a novel MOF cluster (UFT) with enhanced forward scattering and robust porosity is prepared. UFT is applied as an optical and dielectric modifier for bisphenol A epoxy resin (DGEBA), and UFT epoxy composites with high transmittance (>80%), tunable haze (45-58%) and excellent dielectric properties can be prepared at low UFT contents (0.5-1 wt%), which delivers an optimal design for dielectric encapsulation systems with efficient light management in solar cells. Additionally, UFT epoxy composites also show excellent UV blocking, and hydrophobic, thermal and mechanical properties. This work provides a template for the synthesis of covalent bond-mediated nanofillers and for the modulation of haze and dielectric properties of dielectric encapsulation materials for energy systems, semiconductors, microelectronics, and more.

A critical review on adsorption and recovery of fluoride from wastewater by metal-based adsorbents.

Rapid industrialization is deteriorating water quality, and fluoride pollution in water is one of the most serious environmental pollution problems. Adsorption technology is an efficient and selective process for removing fluoride from aqueous solutions using adsorbents. Metal-based adsorbents synergize the advantages of fast adsorption, high adsorption capacity, and excellent selectivity to effectively remove fluoride from water bodies, promising to satisfy environmental sustainability requirements. This paper reviews the metal-based adsorbents: iron-based, aluminum-based, lanthanum-based, cerium-based, titanium-based, zirconium-based, and multi-metal composite adsorbents, primarily focusing on the adsorption conditions and fluoride removal capacities and discusses prospects and challenges in the synthesis and application of metal-based adsorbents. This paper aims to stimulate new thinking and innovation in developing the next generation of sustainable adsorbents.

Cloning and identification of a new repressor of 3,17ß-Hydroxysteroid dehydrogenase of Comamonas testosteroni.

BACKGROUND: 3,17ß-hydroxysteroid dehydrogenase (3,17ß-HSD) is a key enzyme in the metabolic pathway for steroid compounds catabolism in Comamonas testosteroni. Tetracycline repressor (TetR) family, repressors existing in most microorganisms, may play key roles in regulating the expression of 3,17ß-HSD. Previous reports showed that three tetR genes are located in the contig58 of C. testosteroni ATCC 11996 (GenBank: AHIL01000049.1), among which the first tetR gene encoded a potential repressor of 3,17ß-HSD by sensing environmental signals. However, whether the other proposed tetR genes act as repressors of 3,17ß-HSD are still unknown. METHODS AND RESULTS: In the present study, we cloned the second tetR gene and analyzed the regulatory mechanism of the protein on 3,17ß-HSD using electrophoretic mobility shift assay (EMSA), gold nanoparticles (AuNPs)-based assay, and loss-of-function analysis. The results showed that the second tetR gene was 660-bp, encoding a 26 kD protein, which could regulate the expression of 3,17ß-HSD gene via binding to the conserved consensus sequences located 1100-bp upstream of the 3,17ß-HSD gene. Furthermore, the mutant strain of C. testosteroni with the second tetR gene knocked-out mutant expresses good biological genetic stability, and the expression of 3,17ß-HSD in the mutant strain is slightly higher than that in the wild type under testosterone induction. CONCLUSIONS: The second tetR gene acts as a negative regulator in 3,17ß-HSD expression, and the mutant has potential application in bioremediation of steroids contaminated environment.

Copper-coordinated cellulose ion conductors for solid-state batteries.

Although solid-state lithium (Li)-metal batteries promise both high energy density and safety, existing solid ion conductors fail to satisfy the rigorous requirements of battery operations. Inorganic ion conductors allow fast ion transport, but their rigid and brittle nature prevents good interfacial contact with electrodes. Conversely, polymer ion conductors that are Li-metal-stable usually provide better interfacial compatibility and mechanical tolerance, but typically suffer from inferior ionic conductivity owing to the coupling of the ion transport with the motion of the polymer chains1-3. Here we report a general strategy for achieving high-performance solid polymer ion conductors by engineering of molecular channels. Through the coordination of copper ions (Cu2+) with one-dimensional cellulose nanofibrils, we show that the opening of molecular channels within the normally ion-insulating cellulose enables rapid transport of Li+ ions along the polymer chains. In addition to high Li+ conductivity (1.5 × 10-3 siemens per centimetre at room temperature along the molecular chain direction), the Cu2+-coordinated cellulose ion conductor also exhibits a high transference number (0.78, compared with 0.2-0.5 in other polymers2) and a wide window of electrochemical stability (0-4.5 volts) that can accommodate both the Li-metal anode and high-voltage cathodes. This one-dimensional ion conductor also allows ion percolation in thick LiFePO4 solid-state cathodes for application in batteries with a high energy density. Furthermore, we have verified the universality of this molecular-channel engineering approach with other polymers and cations, achieving similarly high conductivities, with implications that could go beyond safe, high-performance solid-state batteries.

Mind Bomb 1 Promotes Pancreatic Cancer Proliferation by Activating ß-Catenin Signaling.

Mind bomb 1 (MIB1), an E3 ligase, plays a vital role in chemo-resistance and cancer metastasis. According to The Cancer Genome Atlas (TCGA), MIB1 gene is preferentially amplified in pancreatic cancer. Copy number alterations in MIB1 gene are associated with worse survival. Gene Expression Omnibus (GEO) also showed that pancreatic cancer with high mRNA level of MIB1 tend to be more resistant to gemcitabine and higher mRNA levels of MIB1 are found in pancreatic tumors compared with adjacent normal tissues. MIB1 knockdown (KD) in Panc-1 and HPAF2 cell lines significantly inhibit proliferation and colony formation of pancreatic cancer. The gene set enrichment analysis (GSEA) has also showed that ß-catenin is the downstream of MIB1. Western blot analysis showed that total and active ß-catenin levels are decreased in MIB1 KD cells. ß-catenin inhibitor also inhibits proliferation of Panc-1 and HPAF2 cells. We in this study implanted HPAF2 scramble and MIB1 KD cells orthotopically in athymic nude mice. Gemcitabine was used to treat the mice. Results revealed that after MIB1 KD HPAF2 cells were more sensitive to gemcitabine. In conclusion, we demonstrated that MIB1 promotes pancreatic cancer proliferation through activating ß-catenin signaling. MIB1 may thus be a therapeutic target in pancreatic cancer therapy.

MUC1 promotes glycolysis through inhibiting BRCA1 expression in pancreatic cancer.

Enhanced glucose metabolism is one of the hallmarks of pancreatic cancer. MUC1, a transmembrane protein, is a global regulator of glucose metabolism and essential for progression of pancreatic cancer. To clarify the role of MUC1 in glucose metabolism, we knocked out MUC1 in Capan-1 and CFPAC-1 cells. MUC1 knockout (KO) cells uptook less glucose and secreted less lactate with a much lower proliferating rate. The mRNA level of key enzymes in glycolysis also decreased significantly in MUC1 KO cells. We also observed increased expression of breast cancer type 1 susceptibility protein (BRCA1) in MUC1 KO cells. Since BRCA1 has a strong inhibitory effect on glycolysis, we want to know whether the decreased glucose metabolism in MUC1 KO cells is due to increased BRCA1 expression. We treated wild type (WT) and MUC1 KO cells with BRCA1 inhibitor. BRCA1 inhibition significantly enhanced glucose uptake and lactate secretion in both WT and MUC1 KO cells. Expression of key enzymes in glycolysis also elevated after BRCA1 inhibition. Elevated glucose metabolism is known to facilitate cancer cells to gain chemoresistance. We treated MUC1 KO cells with gemcitabine and FOLFIRINOX in vitro and in vivo. The results showed that MUC1 KO sensitized pancreatic cancer cells to chemotherapy both in vitro and in vivo. In conclusion, we demonstrated that MUC1 promotes glycolysis through inhibiting BRCA1 expression. MUC1 may be a therapeutic target in pancreatic cancer treatment.

PP2Acα inhibits PFKFB2-induced glycolysis to promote termination of liver regeneration.

The mechanisms underlying the initiation and proliferation of liver regeneration (LR) has been extensively studied using the partial hepatectomy (PHx) model, while little is known about the termination of LR. PP2Acα (protein phosphatase 2 A catalytic subunit α isoform) is the catalytic subunit of protein phosphatase 2 A (PP2A), accounting for most of intracellular serine/threonine phosphatase activity. We have previously observed that termination of LR delayed in PP2Acα liver-specific knockout (LKO) mice after PHx. In our study, we used phospho explorer antibody array analysis to screen the potential phosphorylation targets of PP2Acα, and PP2Acα had a great influence on the hepatic phosphoproteomic signaling in the termination of LR after PHx. We then tested the phosphorylation changes and metabolic function of 6-phosphofructo-2-kinase/fructose-2,6-bisphosphatase-2 (PFKFB2), an isoform of the key glycolytic enzyme PFKFB, which was significantly regulated by PP2Acα knockout. PP2Acα knockout enhanced glycolysis in vivo and in vitro, while adenoviral-mediated RNAi of PFKFB2 reversed the extension of postoperative liver regeneration in KO mice along with the downregulation of glycolysis. Therefore, we demonstrated that PP2Acα liver-specific knockout regulated the hepatocytes glycolysis via activating PFKFB2, thus enhancing liver regeneration during the termination stage.

A simple and rapid method for the determination of lead dioxide in minium by headspace gas chromatographic technique.

This paper demonstrated a simple and rapid approach for the determination of lead dioxide in minium using a headspace gas chromatographic (GC) technique. This new approach was based on the measurement of carbon dioxide from the redox reaction between lead dioxide and oxalic acid in a sealed headspace vial. The obtained results indicated that the new approach had good measurement accuracy (relative errors ≤8.71%) and precision (RSD ≤2.86%). Moreover, the limit of quantification (LOQ) and limit of detection (LOD) for this new approach were respectively 0.34% and 0.10%, and the recoveries ranged from 97.9 to 101.7%. The new approach is low-cost and reliable, which has potential for use in the analysis of lead dioxide in minium and related products.

Synthesis of a furfural-based DOPO-containing co-curing agent for fire-safe epoxy resins.

A furfural-based DOPO-containing flame retardant, 6,6'-(((methylenebis(4,1-phenylene))bis(azanediyl))bis(furan-2-ylmethylene))bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (MBF-DOPO), was synthesized and utilized as a co-curing agent of 4,4'-diaminodiphenyl methane (DDM) for fire-safe epoxy thermosets. For the cured epoxy resin containing 4.0% MBF-DOPO, the limiting oxygen index (LOI) reached 32.9% (with the V-0 rating in UL-94 test), and the peak heat release rate and total smoke production values were respectively decreased by 29.3% and 33.6%, compared to pure epoxy resin. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) results confirmed that the furfural-based flame retardant MBF-DOPO promoted the charring formation of the epoxy matrix, which effectively isolated the gas and heat transfer during combustion and thus enhanced the fire-safety performance of the epoxy thermosets. This work provides an effective route for synthesizing a furfural-based flame retardant, which possesses great potential for application in fire-safe epoxy thermosets.

Correction: Synthesis of a furfural-based DOPO-containing co-curing agent for fire-safe epoxy resins.

[This corrects the article DOI: 10.1039/C9RA06425G.].

An efficient headspace gas chromatographic technique for determining humic acid content in fertilizer.

A fast, convenient and commercially available approach for analyzing humic acid content in fertilizer using headspace gas chromatography (HS-GC) is presented in this paper. Humic acid is converted into carbon dioxide based on the oxidation of humic acid in strong acidic medium and can be measured via automatic HS-GC. Conditions for the alkaline extraction and the humic acid oxidation process are also optimized. The new technique proved to be precise (RSD ≤ 3.59%) and accurate (relative errors≤9.46% as compared with the spectrophotometric approach). The newly established technique presents a practical tool to routinely analyze humic acid content in fertilizer during the fertilizer production.

A fast and simple headspace gas chromatographic technique for quantitatively analyzing urea in human urine.

A fast and convenient headspace gas chromatographic (HS-GC) approach was described for the estimation of urea in human urine. The HS-GC could detect the generated carbon dioxide derived from the urease-catalyzed hydrolysis of urea. It was found that the hydrolysis of urea catalyzed by urease was completed within 40 min at 35 °C. The results proved the great accuracy (relative errors ≤ 8.48%) and precision (RSD ≤ 2.66%) of the HS-GC approach. Moreover, the recoveries ranged from 97.9% to 101.5%. The new approach is rapid and automated, which provides a new way to routinely analyze urea in urine for the control of metabolic disease.

Determination of iodate in iodized edible salt based on a headspace gas chromatographic technique.

This paper introduces a convenient approach for determining iodate in iodized salt by headspace gas chromatography (HS-GC). The analytical technique can measure the generated carbon dioxide from the redox reaction between iodate and sodium oxalate in the presence of strong acid. The formed carbon dioxide from this reaction in a closed vial is measured by GC. It was observed that the redox reaction in the vial was completed in 40 min at 95 °C. The results indicated that this analytical technique is precise (RSD ≤ 2.69%) and accurate (relative errors ≤ 7.21%). The present approach is fast and simple, providing a robust avenue to the routine estimation of iodate in iodized salt in a wide variety of applications from processing to quality monitoring.

A biobased Schiff base from protocatechualdehyde and its application in flame-retardant, low-smoke epoxy resin systems.

Herein, a new renewable Schiff base flame retardant 4,4'-((1E,1'E)-((oxybis(4,1-phenylene))bis(azanylylidene))bis(methanylylidene))bis(benzene-1,2-diol) (PH-ODA) was prepared by the reaction of protocatechualdehyde with 4,4'-diaminodiphenyl ether (ODA). PH-ODA (acting as a carbonization agent) combined with ammonium polyphosphate (APP) were used as intumescent flame retardants for commercial bisphenol A epoxy resin (DGEBA). For the cured epoxy resin containing 7.5% APP and 2.5% PH-ODA, the limiting oxygen index (LOI) reached 29.9% (with the V-0 rating in UL-94 test), and the peak heat release rate and total smoke production were respectively decreased by 88.1% and 68.3%, compared with pure epoxy resin. The enhancement of fire-safety performance was due to PH-ODA/APP promoting the formation of a compact intumescent char structure. It was also found that the synergism between PH-ODA and APP was helpful to enhance the fire resistance of the epoxy matrix. This work provides a facile and sustainable route for synthesizing Schiff base compounds from biomass-derived resources, possessing great potential for application in highly-effective intumescent flame retardants.

Utilizing two detectors in the measurement of trichloroacetic acid in human urine by reaction headspace gas chromatography.

A reaction headspace gas chromatography (HS-GC) technique was investigated for quantitatively analyzing trichloroacetic acid in human urine. This method is based on the decomposition reaction of trichloroacetic acid under high-temperature conditions. The carbon dioxide and chloroform formed from the decomposition reaction can be respectively detected by the thermal conductivity detection HS-GC and flame ionization detection HS-GC. The reaction can be completed in 60 min at 90°C. This method was used to quantify 25 different human urine samples, which had a range of trichloroacetic acid from 0.52 to 3.47 mg/L. It also utilized two different detectors, the thermal conductivity detector and the flame ionization detector. The present reaction HS-GC method is accurate, reliable and well suitable for batch detection of trichloroacetic acid in human urine.