Boron-doped reduced graphene oxide as an efficient cathode in microbial fuel cells for biological toxicity detection.

Electrodes with superior stability and sensitivity are highly desirable in advancing the toxicity detection efficiency of microbial fuel cells (MFCs). Herein, boron-doped reduced graphene oxide (B-rGO) was synthesized and utilized as an efficient cathode candidate in an MFCs system for sensitive sodium dodecylbenzene sulfonate (SDBS) detection. Boron doping introduces additional defects and improves the dispersibility and oxygen permeability, thereby enhancing the oxygen reduction reaction (ORR) efficiency. The B-rGO-based cathode has demonstrated significantly improved output voltage and power density, marking improvements of 75 % and 58 % over their undoped counterparts, respectively. Furthermore, it also exhibited remarkable linear sensitivity to SDBS concentrations across a broad range (0.2-15 mg/L). Notably, the cathode maintained excellent stability within the test range and showed significant reversibility for SDBS concentrations between 0.2 and 3 mg/L. The highly sensitive and stable B-rGO-based cathode is inspiring for developing more practical and cost-effective toxicant sensing devices.

A novel sponge composite of chitosan-sodium tripolyphosphate-melamine for anionic dye Orange II removal.

Since the potential carcinogenic, toxic and non-degradable dyes trigger serious environmental contamination by improper treatment, developing novel adsorbents remains a major challenge. A novel high efficiency and biopolymer-based environmental-friendly adsorbent, chitosan­sodium tripolyphosphate-melamine sponge (CTS-STPP-MS) composite, was prepared for Orange II removing with chitosan as raw material, sodium tripolyphosphate as cross-linking agent. The composite was carefully characterized by SEM, EDS, FT-IR and XPS. The influence of crosslinking conditions, dosage, pH, initial concentration, contacting time and temperature on adsorption were tested through batch adsorption experiments. CTS-STPP-MS adsorption process was exothermic, spontaneous and agreed with Sips isotherm model accompanying the maximum adsorption capacity as 948 mg∙g-1 (pH = 3). Notably, the adsorption performance was outstanding for high concentration solutions, with a removal rate of 97 % in up to 2000 mg∙L-1 OII solution (100 mg sorbent dosage, 50 mL OII solution, pH = 3, 289.15 K). In addition, the adsorption efficiency yet remained 97.85 % after 5 repeated adsorption-desorption cycles. The driving force of adsorption was attributed to electrostatic attraction and hydrogen bonds which was proved by adsorption results coupled with XPS. Owing to the excellent properties of high-effective, environmental-friendly, easy to separate and regenerable, CTS-STPP-MS composite turned out to be a promising adsorbent in contamination treatment.

A sensitive determination of Brilliant Blue FCF in some food samples using hydrophillic deep eutectic solvent-assisted magnetic nano gel-based dispersive solid phase microextraction prior to spectrophotometric analysis.

A new magnetic nano gel (MNG) was prepared from choline chloride/phenol deep eutectic solvent and magnetic amberlite XAD-7 nanocomposite. The dispersive solid phase micro extraction (dSPME) method was developed for seperation and preconcentration of Brilliant Blue FCF (BB) by the prepared MNG. In this study, firstly, the optimum DES type and mole ratio of DES were investigated before response surface methodology optimization. Then, the effect of the MNG-dSPME experimental parameters were optimized by response surface methodology using central composite design. Under the optimum microextraction conditions, limit of detection (LOD), limit of quantification (LOQ), preconcentration factor (PF), enhencament factor (EF) were found to be 1.15 µg L-1,3.80 µg L-1, 70, and 88, respectively. It was seen that the recovery of real samples were obtained from 95.5 to 103.6%. The pesent method was succesfully for extraction of BB in some food, personal care samples, to the best of our knowledge, this is the first study that is presented method on determination of BB by preconcentration with magnetic nano gel. The obtained results showed that the present procedure is effective, sensitive, and has high accuracy for the quantitative detection of BB.

Pseudo-water-soluble Fe2O3 as Nanozyme catalyzed chemiluminescent reaction for detection of brilliant blue in gelatin and beverages.

Converting solid iron oxide nanoparticles into a "pseudo-water-soluble" form before applying them to chemiluminescent reactions leads to enhance the chemiluminescence intensity. Using 8-hydroxyquinoline as a colloidal agent, a new, fast, and simple method of synthesizing pseudo-water-soluble Fe2O3 nanoparticles was developed. SEM, VSM, SAED, HRTEM, XRD, FTIR, and EDS techniques were used to characterize the synthesized Fe2O3 nanoparticles. Fe2O3 nanoparticles synthesized in this study have superior peroxidase-like activity (POD-like) and are stable under a wide range of pH and temperature. The chemiluminescence reaction of luminol-H2O2 is intensified and accelerated by a colloidal solution of Fe-nanoparticles/8-hydroxyquinoline. Reverse-flow injection analysis was employed to determine brilliant blue. A chemiluminescent sensing method based on iron oxide nanozymes was utilized for sensitive detection of the brilliant blue synthetic dye, achieving a limit of detection of 0.06 mg/L and a dynamic linear range of 0.1 to 50 mg/L. The recovery and relative standard deviations of real samples were found to be 97.83-99.93% and 0.09-3.07%, respectively. An analysis of a sample, from injection to obtaining the maximum peak, could be performed in less than one minute.

An artificial liquid-liquid phase separation-driven silk fibroin-based adhesive for rapid hemostasis and wound sealing.

The powerful adhesion systems of marine organisms have inspired the development of artificial protein-based bioadhesives. However, achieving robust wet adhesion using artificial bioadhesives remains technically challenging because the key element of liquid-liquid phase separation (LLPS)-driven complex coacervation in natural adhesion systems is often ignored. In this study, mimicking the complex coacervation phenomenon of marine organisms, an artificial protein-based adhesive hydrogel (SFG hydrogel) was developed by adopting the LLPS-mediated coacervation of the natural protein silk fibroin (SF) and the anionic surfactant sodium dodecylbenzene sulfonate (SDBS). The assembled SF/SDBS complex coacervate enabled precise spatial positioning and easy self-adjustable deposition on irregular substrate surfaces, allowing for tight contact. Spontaneous liquid-to-solid maturation promoted the phase transition of the SF/SDBS complex coacervate to form the SFG hydrogel in situ, enhancing its bulk cohesiveness and interfacial adhesion. The formed SFG hydrogel exhibited intrinsic advantages as a new type of artificial protein-based adhesive, including good biocompatibility, robust wet adhesion, rapid blood-clotting capacity, and easy operation. In vitro and in vivo experiments demonstrated that the SFG hydrogel not only achieved instant and effective hemostatic sealing of tissue injuries but also promoted wound healing and tissue regeneration, thus advancing its clinical applications. STATEMENT OF SIGNIFICANCE: Marine mussels utilize the liquid-liquid phase separation (LLPS) strategy to induce the supramolecular assembly of mussel foot proteins, which plays a critical role in strong underwater adhesion of mussel foot proteins. Herein, an artificial protein-based adhesive hydrogel (named SFG hydrogel) was reported by adopting the LLPS-mediated coacervation of natural protein silk fibroin (SF) and anionic surfactant sodium dodecylbenzene sulfonate (SDBS). The assembled SFG hydrogel enabled the precise spatial positioning and easy self-adjustable deposition on substrate surfaces with irregularities, allowing tight interfacial adhesion and cohesiveness. The SFG hydrogel not only achieved instant and effective hemostatic sealing of tissue injuries but also promoted wound healing and tissue regeneration, exhibiting intrinsic advantages as a new type of artificial protein-based bioadhesives.

Sustainable efficient utilization of magnetic porous biochar for adsorption of orange G and tetracycline: Inherent roles of adsorption and mechanisms.

Iron-doped biochar has been widely used as an adsorbent to remove contaminants due to the high adsorption performance, but it still suffers from complicated preparation methods, unstable iron loading, unsatisfactory specific surface area, and uneven distribution of active sites. Here, a novel magnetic porous biochar (FeCS800) with nanostructure on surface was synthesized by one-pot pyrolysis method of corn straw with K2FeO4, and used in orange G (OG) and tetracycline (TC) adsorption. FeCS800 exhibited outstanding adsorption capacities for OG and TC after K2FeO4 activation and the adsorption data were fitted satisfactorily to Langmuir isotherm and Pseudo-second-order kinetic model. The maximum adsorption capacities of FeCS800 for OG and TC were around 303.03 mg/g and 322.58 mg/g, respectively, at 25 °C and pH 7.0, which were 16.27 and 24.61 times higher than that before modification. Thermodynamic studies showed that the adsorption of OG/TC by FeCS800 were thermodynamically favorable and highly spontaneous. And the adsorption capacity of OG and TC by FeCS800 remained 77% and 81% after 5 cycles, respectively, indicating that FeCS800 had good stability. The outstanding adsorption properties and remarkable reusability of FeCS800 show its great potential to be an economic and environmental adsorbent in contaminants removal.

Modification of the phenyl ring B of phenyl 4-(2-oxoimidazolidin-1-yl)benzenesulfonates by pyridinyl moiety leads to novel antimitotics targeting the colchicine-binding site.

A series of 8 novel pyridinyl 4-(2-oxoimidazolidin-1-yl)benzenesulfonates (PYRIB-SOs) were designed, prepared and evaluated for their mechanism of action. PYRIB-SOs were found to have antiproliferative activity in the nanomolar to submicromolar range on several breast cancer cell lines. Moreover, subsequent biofunctional assays indicated that the most potent PYRIB-SOs 1-3 act as antimitotics binding to the colchicine-binding site (C-BS) of α, ß-tubulin and that they arrest the cell cycle progression in the G2/M phase. Microtubule immunofluorescence and tubulin polymerisation assay confirm that they disrupt the cytoskeleton through inhibition of tubulin polymerisation as observed with microtubule-destabilising agents. They also show good overall theoretical physicochemical, pharmacokinetic and druglike properties. Overall, these results show that PYRIB-SOs is a new family of promising antimitotics to be further studied in vivo for biopharmaceutical and pharmacodynamic evaluations.

Preparation of novel Fe-containing zeolite-A for KN-R decolorization by Fenton-like reaction.

Herein, novel catalysts of Fe-containing zeolite-A (Fe/zeolite-A) were synthesized by exchanging iron ions into zeolite-A framework, and short-chain organic acids (SCOAs) were employed as chelating agents. Reactive Brilliant Blue KN-R (KN-R) was used as a model pollutant to evaluate the performance of these catalysts based on the heterogeneous Fenton reaction. The results showed that Fe-OA/3A, which applied zeolite-3A as the supporter and oxalic as the chelating agent, presented the most prominent KN-R decolorization efficiency. Under the initial pH of 2.5, 0.4 mM KN-R could be totally decolorized within 20 min. However, the mineralization efficiency of KN-R was only 58.2%. Therefore, anthraquinone dyes were introduced to modify zeolite-3A. As a result, the mineralization efficiency of KN-R was elevated to 92.7% when using Alizarin Violet (AV) as the modifier. Moreover, the modified catalysts exhibited excellent stability, the KN-R decolorization efficiency could be maintained above 95.0% within 20 min after operating for nine cycles. The mechanism revealed that the Fe(II)/Fe(III) cycle was accelerated by AV-modified catalyst thus prompting the KN-R decolorization in Fenton-like system. These findings provide new insights for preparing catalysts with excellent activity and stability for dye wastewater treatment.

Multiplexed colorimetry collaborated with smartphone-based image analysis for simultaneous and fast visualization of dyes in both environmental and food samples.

In this work, a multiplexed colorimetric strategy was initiated for simultaneous and fast visualization of dyes using low-cost and easy-to-prepare indicator papers as sorbents. Response surface methodology (RSM) was employed to model statistically and optimize the process variables for dyes extraction and colorimetric assays. Multiplexed colorimetry was realized by virtue of synchronous color alignments from different dimensions of multiple dyes co-stained colorimetric cards under RSM-optimized conditions, and smartphone-based image analysis was subsequently performed from different modes to double-check the credibility of colorimetric assays. As concept-to-proof trials, simultaneous visualization of dyes in both beverages and simulated dye effluents was experimentally proved with results highly matched to HPLC or spiked amounts at RSM-predicted staining time as short as 50 s ∼3 min, giving LODs as low as 0.97 ± 0.22/0.18 ± 0.08 µg/mL (tartrazine/brilliant blue) for multiplexed colorimetry, which much lower than those obtained by single colorimetry. Since this is the first case to propose such a RSM-guided multiplexed colorimetric concept, it will provide a reference for engineering of other all-in-one devices which can realize synchronous visualization applications within limited experimental steps.

UV light and Fe2+ catalysed COD removal of AO 8 using NaOCl as oxidant.

The present study aims to establish NaOCl as a potential oxidant in the COD removal of Acid Orange 8 using UVC light (λ = 254 nm) and Fe2+ as catalysts. The different systems used in this study are NaOCl, Fe2+/NaOCl, UV/NaOCl, and Fe2+/NaOCl/UV. All these process were found to be operative in acidic, neutral and basic medium. The initial decolorisation and COD removal efficiency (CODeff) for different systems follow the order: Fe2+/NaOCl/UV > UV/NaOCl > Fe2+/NaOCl > NaOCl. Nevertheless, NaOCl can alone be used in the treatment process considering its CODeff to the extent of 95% in 90 min. The change in pH of the solutions after treatment is an important observation - for non-UV systems it remained around 11.0 and 7.0 in other systems. Thus, UV systems are environmental benign. The effect of various anions on CODeff was tested in Fe2+ systems. Presence of F- ions were found to accelerate CODeff in both the systems. However, the effect is more pronounced in Fe2+/ NaOCl/UV, where complete CODeff was observed in the presence of 9.0 gl-1 of F-. The COD removal kinetics for all systems was studied using zero-order, first-order, second-order, and BMG kinetic models. BMG model was found to be more suitable among all and is in good agreement with CODeff of all systems. It is, therefore, established that NaOCl can serve as a powerful oxidant in the advanced oxidation process.

Probing the interaction mechanism of SDBS with AtPrxQ from Arabidopsis thaliana: Insight into the molecular toxicity to plants.

As the most universally used anionic surfactant, ubiquitous existence and accumulation of sodium dodecyl benzene sulfonate (SDBS) in the environment has inevitably imposed the associated harmful impacts to plants due to producing excessive reactive oxygen species. However, the underlying hazardous mechanism of the SDBS-induced oxidative stress to plants at molecular level has never been reported. Here, the molecular interaction of AtPrxQ with SDBS was explored for the first time. The intrinsic fluorescence of AtPrxQ was quenched based on static quenching, and a single binding site of AtPrxQ towards SDBS and the potential interaction forces driven by hydrophobic interactions were predicted from thermodynamic parameters and molecular docking results. Besides, the interaction pattern of AtPrxQ and SDBS was also confirmed by the bio-layer interferometry with moderate binding affinity. Moreover, the structural changes of AtPrxQ along with the destructions of the protein framework and the hydrophobic enhancement around aromatic amino acids were observed upon binding with SDBS. At last, the toxic effects produced by SDBS on peroxidase activities and Arabidopsis seedlings growth were also characterized. Thus this work may provide insights on the molecular interactions of AtPrxQ with SDBS and assessments on the biological hazards of SDBS to plants even for the agriculture.

Homologation of the Alkyl Side Chain of Antimitotic Phenyl 4-(2-Oxo-3-alkylimidazolidin-1-yl)benzenesulfonate Prodrugs Selectively Targeting CYP1A1-Expressing Breast Cancers Improves Their Stability in Rodent Liver Microsomes.

Phenyl 4-(2-oxo-3-alkylimidazolidin-1-yl)benzenesulfonates (PAIB-SOs) are a new family of antimitotic prodrugs bioactivated in breast cancer cells expressing CYP1A1. In this study, we report that the 14C-labeled prototypical PAIB-SO [14C]CEU-818 and its antimitotic counterpart [14C]CEU-602 are distributed in whole mouse body and they show a short half-life in mice. To circumvent this limitation, we evaluated the effect of the homologation of the alkyl side chain of the imidazolidin-2-one moiety of PAIB-SOs. Our studies evidence that PAIB-SOs bearing an n-pentyl side chain exhibit antiproliferative activity in the nanomolar-to-low-micromolar range and a high selectivity toward CYP1A1-positive breast cancer cells. Moreover, the most potent n-pentyl PAIB-SOs were significantly more stable toward rodent liver microsomes. In addition, PAIB-SOs 10 and 14 show significant antitumor activity and low toxicity in chorioallantoic membrane (CAM) assay. Our study confirms that homologation is a suitable approach to improve the rodent hepatic stability of PAIB-SOs.

Study on the catalytic degradation of Acid Orange 7 and the potential mechanism by ferrous-percarbonate.

Factors affecting the degradation of Acid Orange 7 (AO7) were evaluated and optimized when ferrous was used to catalyze percarbonate in the present study. The optimized conditions included the initial pH values ranging from 3 to 11 for AO7 solution, the initial level of AO7, sodium percarbonate (SPC), and Fe2+ . Some ions and natural organic materials, which commonly exist in natural water, were also tested to evaluate their potential impacts on the degradation of AO7. The degradation efficiency of AO7 was up to 95% under the optimized test conditions, where the ferrous/percarbonate/AO7 molar ratio was 15/10/1 in the 0.285 mmol/l AO7 aqueous solution. The presence of Cl- , SO4 2- , NO3 - , Na+ , and Mg2+ did not affect the removal of AO7. The addition of HCO3 - significantly inhibited its removal, even when the concentration of HCO3 - was low to 0.6 mmol/l. A slight inhibition effect was observed when the added concentration of humic acid ranged from 0.5 to 5 mg/l, whereas the residue of AO7 was significantly enhanced when the level of humic acid was continually increased from 50 to 100 mg/l. Hydroxyl radicals (•OH) were the main reactive intermediates controlling the oxidation of AO7 in the present Fe2+ /SPC system. The produced intermediates through the degradation of AO7 were identified to include 2-coumaranone, 2-naphthol, phthalic acid, phthalimide, N-methylnaphthylamine, and 2-methylphenol. The proposed degradation pathways are consistent with the radical formation and the identified intermediates. PRACTITIONER POINTS: The ferrous/percarbonate system can remove 95% of AO7 under the optimized conditions. AO7 removal was inhibited by adding HCO3 - and humic acid, but not affected by Cl- , SO4 2- , NO3 - , Na+ , and Mg2+ . Hydroxylation, ring opening, and mineralization driven by the generated hydroxyl radicals were derived as the major processes for degrading AO7.

New 2-[(4-Amino-6-N-substituted-1,3,5-triazin-2-yl)methylthio]-N-(imidazolidin-2-ylidene)-4-chloro-5-methylbenzenesulfonamide Derivatives, Design, Synthesis and Anticancer Evaluation.

In the search for new compounds with antitumor activity, new potential anticancer agents were designed as molecular hybrids containing the structures of a triazine ring and a sulfonamide fragment. Applying the synthesis in solution, a base of new sulfonamide derivatives 20-162 was obtained by the reaction of the corresponding esters 11-19 with appropriate biguanide hydrochlorides. The structures of the compounds were confirmed by spectroscopy (IR, NMR), mass spectrometry (HRMS or MALDI-TOF/TOF), elemental analysis (C,H,N) and X-ray crystallography. The cytotoxic activity of the obtained compounds toward three tumor cell lines, HCT-116, MCF-7 and HeLa, was examined. The results showed that some of the most active compounds belonged to the R1 = 4-trifluoromethylbenzyl and R1 = 3,5-bis(trifluoromethyl)benzyl series and exhibited IC50 values ranging from 3.6 µM to 11.0 µM. The SAR relationships were described, indicating the key role of the R2 = 4-phenylpiperazin-1-yl substituent for the cytotoxic activity against the HCT-116 and MCF-7 lines. The studies regarding the mechanism of action of the active compounds included the assessment of the inhibition of MDM2-p53 interactions, cell cycle analysis and apoptosis induction examination. The results indicated that the studied compounds did not inhibit MDM2-p53 interactions but induced G0/G1 and G2/M cell cycle arrest in a p53-independent manner. Furthermore, the active compounds induced apoptosis in cells harboring wild-type and mutant p53. The compound design was conducted step by step and assisted by QSAR models that correlated the activity of the compounds against the HCT-116 cell line with molecular descriptors.

Efficient activation of peroxymonosulfate by nanotubular Co3O4 for degradation of Acid Orange 7: performance and mechanism.

Morphology optimization of catalysts has been considered as a viable strategy to improve the catalytic efficiency for peroxymonosulfate (PMS) activation by providing high surface area and abundant active sites. In this study, nanotubular Co3O4 (NT-Co3O4) was successfully synthesized as a PMS activator for the rapid removal of acid orange 7 (AO7) in aqueous solutions. Characterization results showed that NT-Co3O4 presented as aggregated nanotubes, with an average pore diameter of 10 nm. The specific surface area of NT-Co3O4 was as high as 41.8 m2 g-1. Catalytic experiments demonstrated that the degradation rate of AO7 in the NT-Co3O4/PMS system was 15 times greater than that in commercially available Co3O4/PMS system. The effects of various experimental parameters, including catalyst dose, PMS dose, pH, and temperature, were comprehensively investigated. The reactive species in the NT-Co3O4/PMS system were identified as sulfate radical (SO4•-) through both quenching tests and electron paramagnetic resonance (EPR) technology, and ≡CoOH+ played an important role in PMS activation. N atoms in the AO7 molecule were found to be preferentially attacked by SO4•-. Moreover, the good stability and reusability of NT-Co3O4 were confirmed by a five-cycle AO7 removal experiment. This study provides a broader view of the potential applications of nanotubular materials to achieve highly efficient PMS activation in treating dyes in wastewater.

Persulfate activation by ferrocene-based metal-organic framework microspheres for efficient oxidation of orange acid 7.

Ferrocene-based metal-organic framework with different transition metals (M-Fc-MOFs, M = Fe, Mn, Co) was synthesized by a simple hydrothermal method and used as a heterogeneous catalyst for persulfate activation. The samples were characterized by X-ray diffraction, transmission electron microscopy, X-ray electron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Meanwhile, the influences of factors such as catalyst dosage, persulfate concentration, and pH on the degradation of acid orange 7 (AO7) were studied in detail. The results showed that hollow cobalt-based ferrocenyl metal-organic framework microspheres (Co-Fc-MOFs) exhibited the best catalytic performance, which is closely related to the synergy of Fc/Fc+ and Co(II)/Co(III) cycles in persulfate activation. Free radical quenching studies indicated that both sulfate and hydroxyl appeared to contribute to the degradation of AO7.

Interaction of remimazolam benzenesulfonate and human serum albumin: a simulated physiological study.

Here, to elucidate the interaction mechanism and physicochemical properties of remimazolam and human serum albumin interactions, techniques such as fluorescence, circular dichroism (CD) spectroscopy, and isothermal titration calorimetry have been applied for study. The thermodynamic parameters at body temperature (ΔS = -207 J·mol-1 ·K-1 , ΔS = -9.76 × 104 J·mol-1 and ΔG = -3.34 × 104 J·mol-1 ; 310 K) manifests one strong binding site on the protein, which was modulated by van der Waals forces and hydrogen bonds. What is more, the results of CD, synchronous and three-dimensional fluorescence showed that remimazolam altered the microenvironment of the protein amino acid residues. A distance of 2.1 nm between the remimazolam and Trp shows the potential for resonance energy transfer. Furthermore, these results potentially provide information for illustrating the pharmacodynamics and toxicodynamics of remimazolam when it is applied clinically.

Branched alkyl of phenyl 4-(2-oxo-3-alkylimidazolidin-1-yl)benzenesulfonates as unique cytochrome P450 1A1-activated antimitotic prodrugs: Biological evaluation and mechanism of bioactivation.

We recently discovered a new family of prodrugs deriving from phenyl 4-(2-oxo-3-imidazolidin-1-yl)benzenesulfonates (PIB-SOs) bioactivatable by cytochrome P450 1A1 (CYP1A1) into potent antimitotics referred to as phenyl 4-(2-oxo-3-alkylimidazolidin-1-yl)benzenesulfonates (PAIB-SOs). PAIB-SOs display significant selectivity toward human breast cancer cells based on the N-dealkylation of PAIB-SOs into their corresponding PIB-SOs by CYP1A1. In this study, we have evaluated the molecular mechanism of the bioactivation of PAIB-SOs into PIB-SOs by branching the linear alkyl chain on the imidazolidin-2-one (IMZ) moiety of PAIB-SOs by branched alkyl groups such as isopropyl, isobutyl and sec-butyl. Our results show that PAIB-SOs bearing an isobutyl group on the IMZ moiety and either a methoxy, a chloro or a bromo group at positions 3, 3,5 or 3,4,5 on the aromatic ring B exhibit antiproliferative activity ranging from 0.13 to 6.9 µM and selectivity toward MCF7 and MDA-MB-468 mammary cancer cells comparatively to other cell lines tested. Moreover, the most potent and selective PAIB-SOs bearing an isobutyl group and either a 3,5-Cl (44), 3,5-Br (45) or a 3,4,5-OMe (46) on the IMZ moiety exhibit antiproliferative activity in the sub-micromolar range and high selectivity ratios toward mammary cancer cells. They stop the cell cycle of MCF7 cells in the G2/M phase and disrupt their cytoskeleton. Furthermore, our studies evidenced that PAIB-SOs bearing either an isopropyl, a sec-butyl or an isobutyl group are hydroxylated on the carbon atom adjacent to the IMZ (Cα-OH) but only PAIB-SOs bearing an isobutyl group are bioactivated into PIB-SOs. Finally, PAIB-SOs 45 and 46 exhibit low toxicity toward normal cells and chick embryos and are thus promising antimitotic prodrugs highly selective toward CYP1A1-expressing breast cancer cells.

Reusable TsOH-H2SO4 Mixed Catalysis for Tandem Synthesis of Biodiesel and Oxygenated Fuel Additives, tert-Butyl Glycerol Ethers.

A mixture of p-toluenesulfonic acid and sulfuric acid (TsOH-H2SO4) was used as a catalyst with a good performance in transesterification of palm oil (PO) with methanol and etherification of crude glycerol with isobutylene (tandem synthesis). For TsOH-H2SO4 catalyzed biodiesel production, the reaction noticeably ran faster in comparison with TsOH or H2SO4 alone and also gave up to 99.9% of the conversion using MeOH/PO molar ratio 9:1 at 80℃, in the period of 4 h. After the whole transesterification process, the crude glycerol phase was separated and then reacted with isobutylene in the etherification process using isobutylene/glycerol molar ratio 9:1 at 80℃, in the period of 5 h reaction time, to give DTBG and TTBG (91.14%). In the case of the etherification in biodiesel, higher selectivity of DTBG and TTBG (99.39%) was obtained in comparison with an absence of biodiesel as the solvent. Furthermore, the catalyst could be reused for 6 cycles of tandem synthesis (transesterification and etherification). The TsOH-H2SO4 catalyst showed a good catalytic performance in tandem synthesis similar to TsOH and it could be recovered for reuse while TsOH could not be recovered. This process offers an attractive route for reuse homogeneous catalyst of tandem synthesis, the main by-product of biodiesel, to tert-butyl glycerol ethers - a value-added in applications as a valuable fuel additive.

Photothermal-Enhanced Fenton-like Catalytic Activity of Oxygen-Deficient Nanotitania for Efficient and Safe Tooth Whitening.

The growing demand for charming smiles has led to the popularization of tooth bleaching procedures. Current tooth bleaching products with high-concentration hydrogen peroxide (HP, 30-40%) are effective but detrimental due to the increased risk of enamel destruction, tooth sensitivity, and gingival irritation. Herein, we reported a less-destructive and efficient tooth whitening strategy with a low-concentration HP, which was realized by the remarkably enhanced Fenton-like catalytic activity of oxygen-deficient TiO2 (TiO2-x). TiO2-x nanoparticles were synthesized with a modified solid-state chemical reduction approach with NaBH4. The Fenton-like activity of TiO2-x was optimized by manipulating oxygen vacancy (OV) concentration and further promoted by the near-infrared (NIR)-induced photothermal effect of TiO2-x. The TiO2-x sample named BT45 was chosen due to the highest methylene blue (MB) adsorption ability and Fenton-like activity among acquired samples. The photothermal property of BT45 under 808 nm NIR irradiation was verified and its enhancement on Fenton-like activity was also studied. The BT45/HP + NIR group performed significantly better in tooth whitening than the HP + NIR group on various discolored teeth (stained by Orange II, tea, or rhodamine B). Excitingly, the same tooth whitening performance as the Opalescence Boost, a tooth bleaching product containing 40% HP, was obtained by a self-produced bleaching gel based on this novel system containing 12% HP. Besides, negligible enamel destruction, safe temperature range, and good cytocompatibility of TiO2-x nanoparticles also demonstrated the safety of this tooth bleaching strategy. This work indicated that the photothermal-enhanced Fenton-like performance of the TiO2-x-based system is highly promising in tooth bleaching application and can also be extended to other biomedical applications.