Remarkable enantioselectivity enhancement of the extractors with nonaxial chirality in liquid-liquid extraction of underivatized amino acids by introducing t-butyl group.

A class of carbonyl extractors, (R)-3, (R)-4, and (R)-5, with nonaxial chirality containing asymmetric carbons has been synthesized and studied for their efficiencies in enantioselective liquid-liquid extraction for underivatized amino acids. The bulky t-butyl ketone extractors, (R)-4 and (R)-5, showed the stereoselectivities ranging 5.4-9.4 of l/d ratio much better than those of the aldehyde extractor, (R)-3, ranging 2.4-5.2. The imine formation rates and yields of the t-butyl ketones were not significantly affected by their bulkiness and even in the absence of resonance-assisted hydrogen bond. This work confirms that a bulky t-butyl ketone can be a good choice in the development of an extractor not only with axial chirality but also with nonaxial chirality for the enantioselective extraction of unprotected amino acids.

Optical and Fluorescent Dual Sensing of Aminoalcohols by in Situ Generation of BODIPY-like Chromophore.

A novel multifunctional aminophenylboronic acid connected to a diphenylketone gives both circular dichroism and fluorescence signals by in situ generation of a BODIPY-like chromophore in the presence of aminoalcohols. DFT calculations were used to understand the role of each functional group in the mechanism. This new sensor can distinguish different aminoalcohols and quantitatively indicate the concentration of the substrate, allowing for the convenient determination of the ee of racemic mixtures with a single probe.

Application of Antimicrobial Polymers in the Development of Dental Resin Composite.

Dental resin composites have been widely used in a variety of direct and indirect dental restorations due to their aesthetic properties compared to amalgams and similar metals. Despite the fact that dental resin composites can contribute similar mechanical properties, they are more likely to have microbial accumulations leading to secondary caries. Therefore, the effective and long-lasting antimicrobial properties of dental resin composites are of great significance to their clinical applications. The approaches of ascribing antimicrobial properties to the resin composites may be divided into two types: The filler-type and the resin-type. In this review, the resin-type approaches were highlighted. Focusing on the antimicrobial polymers used in dental resin composites, their chemical structures, mechanical properties, antimicrobial effectiveness, releasing profile, and biocompatibility were included, and challenges, as well as future perspectives, were also discussed.

A practical oxidative C-H functionalization of N-carbamoyl tetrahydro-ß-carbolines with diverse potassium trifluoroborates.

A practical and mild metal-free oxidative C-H functionalization of N-carbamoyl tetrahydro-ß-carbolines has been reported. This reaction has excellent functional group tolerance, and exhibits a broad range of potassium trifluoroborate components, allowing for the facile C-H functionalization of electronically varied N-carbamoyl THCs in high efficiency with excellent regioselectivity.

Highly enantioselective extraction of underivatized amino acids by the uryl-pendant hydroxyphenyl-binol ketone.

The hydroxyphenyl chiral ketone, (S)-3, reacts with D-amino acids bearing hydrophobic side chains exclusively over the L-amino acids in a two-phase liquid-liquid extraction, and thus acts as a highly stereoselective extractant. Calculations for the energy-minimized structures for the imine diastereomers and the comparison of the selectivities with other phenyl ketones, (S)-4 and (S)-5, demonstrate that the hydrogen bond between the carboxylate group and the phenolic hydroxyl group contributes to the remarkable enantioselectivities. The multiple hydrogen bonds present in the imine of (S)-3 reinforce the rigidity, and results in the difference between the stabilities of the imine diastereomers. The imine could be hydrolyzed in methanolic HCl solution, and the extraction of the evaporated residues revived the organic layer of (S)-3, which could enter into a new extractive cycle and leaves the D-amino acid with enantiomeric excess (ee) values of over 97 % in the aqueous layer.

Influence of substrate temperature on the properties of ZnTe:Cu films prepared by a magnetron co-sputtering method.

Copper-doped Zinc Tellurium (ZnTe:Cu) films were deposited on borosilicate glass using magnetron co-sputtering technique. The influence of the substrate temperature on the structural, morphological, optical and electrical properties of ZnTe:Cu films was investigated by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), UV-Vis spectrophotometer and Hall effect measurement system. The results indicate that substrate temperature significantly affects the properties of the ZnTe:Cu films. When the substrate temperature increases from room temperature to 600 °C, the (111)-preferred orientation of ZnTe:Cu films is gradually replaced by the (220)-preferred orientation. At high substrate temperatures (≥500 °C), the CuxTe phase appears in the ZnTe:Cu films, resulting in higher carrier concentration (>1019 cm-3) and lower resistivity (<10-2 Ω cm) of the prepared films.

Enantioselective liquid-liquid extractions of underivatized general amino acids with a chiral ketone extractant.

The chiral ketone (S)-3 shows high kinetic enantioselectivities toward the L form for general underivatized amino acids with hydrophobic side chains and a high thermodynamic enantioselectivity toward the D form for cysteine with its -SH polar side chain when used as an extractant in enantioselective liquid-liquid extractions in the presence of Aliquat 336. Consecutive extractions by imine formation and hydrolysis increase the enantiopurity of the amino acid, as both of these reactions are L-form-selective.

Carbon Quantum Dots Derived from Herbal Medicine as Therapeutic Nanoagents for Rheumatoid Arthritis with Ultrahigh Lubrication and Anti-inflammation.

As a typical chronic inflammatory joint disease with swelling and pain syndromes, rheumatoid arthritis (RA) is closely related to articular lubrication deficiency and excessive proinflammatory cytokines in its progression and pathogenesis. Herein, inspired by the dual effects of joint lubrication improvement and anti-inflammation to treat RA, two novel potential therapeutic nanoagents have been developed rationally by employing herbal medicine-derived carbon quantum dots (CQDs), i.e., safflower (Carthamus tinctorius L.) CQDs and Angelica sinensis CQDs, yielding ultrahigh lubrication and anti-inflammation bioefficacy. In vitro experimental results show that the two nanoagents display excellent friction reduction due to their good water solubility and spherical structure. Using RA rat models, it is indicated that the nanoagents significantly relieved swelling symptoms and inhibited the expression of related inflammatory cytokines, including IL-1, IL-6, and TNF-α, indicating their extraordinary anti-inflammation bioefficacy. Thus, combining the lubricating and anti-inflammation bioefficacy of CQDs derived from herbal medicine is an attractive strategy to develop new nanoagents for RA treatment.

A 3D-printed PCL/PEI/DNA bioactive scaffold for chemotherapy drug capture in vivo.

Systemic chemotherapy after surgery is necessary to control tumor recurrence, but the severe side effects caused by chemotherapeutic drugs pose a great threat to patients' health. In this study, we originally develop a porous scaffold used for chemotherapy drug capture by using 3D printing technology. The scaffold is mainly composed of poly (ε-caprolactone) (PCL) and polyetherimide (PEI) with a mass ratio of 5/1. Subsequently, the printed scaffold is modified with DNA through the strong electrostatic integration between DNA and PEI to endow the scaffold with the specific absorption to doxorubicin (DOX, a widely used chemotherapy drug). The results show that pore diameter has an important influence on DOX adsorption, and smaller pores will ensure a higher DOX absorption. In vitro, the printed scaffold can absorb about 45 % DOX. While in vivo, it remains a higher absorption ability to DOX when the scaffold is successfully implanted into the common jugular vein of rabbits. What's more, the scaffold has good hemocompatibility and biocompatibility, indicating its safety for in vivo application. Taken together, the 3D-printed scaffold with excellent capture of chemotherapy drugs will play an important role in reducing the toxic side effects of chemotherapy drugs and improving the life quality of patients.

Biomimetic chitosan nanoparticles with simultaneous water lubricant and anti-inflammatory.

Rheumatoid arthritis (RA) is a chronic inflammatory immune and lubrication dysfunction disease that causes great damage to the joints. Herein, inspired by the unique biochemistry structure and excellent hydration of chondroitin sulfate (CHI) existing in joint system, one kind of novel polysaccharide nanoparticle lubricant, that is chitosan nanoparticles (CS NPs) grafting CHI (CS-CHI), is synthesized by one-step surface chemistry reaction. CHI with negative charges can form hydration layers on the surface of CS NPs, thus improving the lubricity of nanoparticles. Simultaneously, CS-CHI NPs have effective loading and sustained drug release ability for anti-inflammatory drug diclofenac sodium (DS), along with good biocompatibility. Finally, based on a collagen-induced rat RA model, in vitro animals experimental results indicate that the as-synthesized CS-CHI@DS NPs has obvious inhibitory effects on inflammatory factors and can effectively prevent the damaged cartilage from further destruction.

Facile preparation of single-atom Ru catalysts via a two-dimensional interface directed synthesis technique for the NRR.

Through the catalysis system design of in situ Ru SACs (single atoms) anchored on a rGO/NC two-dimensional interface, we successfully realized the SA-Ru@rGO/NC electrocatalyst with high metal loading density at a relatively low temperature. The largest NH3 yield of 110.1 µg h-1 mgcat-1 and FE of 17.9% were achieved at -0.3 V under ambient conditions. The electronic environment of the catalyst was regulated by the electronic metal-support interaction, and the use of SACs had the advantages of inhibiting the hydrogen evolution reaction (HER) and enhancing N2 adsorption, which effectively improved the performance of electrocatalytic nitrogen fixation.

Applications of Antioxidants in Dental Procedures.

As people are paying more and more attention to dental health, various dental treatment procedures have emerged, such as tooth bleaching, dental implants, and dental restorations. However, a large number of free radicals are typically produced during the dental procedures. When the imbalance in distribution of reactive oxygen species (ROS) is induced, oxidative stress coupled with oxidative damage occurs. Oral inflammations such as those in periodontitis and pulpitis are also unavoidable. Therefore, the applications of exogenous antioxidants in oral environment have been proposed. In this article, the origin of ROS during dental procedures, the types of antioxidants, and their working mechanisms are reviewed. Additionally, antioxidants delivery in the complicated dental procedures and their feasibility for clinical applications are also covered. Finally, the importance of safety assessment of these materials and future work to take the challenge in antioxidants development are proposed for perspective.

Modified high-efficiency carbon material for deep degradation of phenol by activating persulfate.

A series of cobalt-nitrogen modified catalysts were prepared and applied to the degradation of phenol. The Mott Schottky catalyst (CoO/NGr@C) with high pyridine nitrogen content was designed to activate potassium peroxodisulfate (PDS) to generate active free radicals for phenol degradation. The structural properties of the materials are analyzed by XPS, TEM and then the charge density calculation is performed by DFT, which proves the existence of the highly active interface effect. Co-N-CMCM-41 can only degrade phenol into benzoquinone and it is difficult to achieve further degradation of benzoquinone, while the modified CoO/NGr@C can achieve deep mineralization of the intermediate benzoquinone through UV spectrum. EPR was used to prove that both hydroxyl radicals and sulfate radicals exist in the degradation process of phenol. Through the DFT simulation calculation of the material, it is proved that the existence of carbon activated by nitrogen and the electron rearrangement between cobalt and nitrogen-rich carbon lead to the catalytic activity of the material. The degradation conditions of phenol were optimized and the reaction kinetics of further phenol degradation were studied. The activation energy of phenol degradation on CoO/NGr@C is calculated to be 34.38 kJ mol-1.

An excellent antibacterial and high self-adhesive hydrogel can promote wound fully healing driven by its shrinkage under NIR.

The lacks of antibacterial properties, low adhesion and delayed wound healing of the hydrogel wound dressings limit their applications in wound treatment. To resolve these, a novel hydrogel composed of polydopamine (PDA), Ag and graphene oxide (GO) is fabricated for wound dressing via the chemical crosslinking of N-isopropylacrylamide (NIPAM) and N,N'-methylene bisacrylamide (BIS). The prepared hydrogel containing PDA@Ag5GO1 (Ag5GO1 denotes the mass ratio between Ag and GO is 5:1) exhibits effective antibacterial properties and high inhibition rate against E. coli and S. aureus. It shows high adhesion ability to various substrate materials, implying a simpler method to the wound obtained by self-fixing rather than suturing. More important, it can produce strong contractility under the irradiation of near-infrared light (NIR), exerting a centripetal force that helps accelerate wound healing. Thus, the hydrogel containing a high concentration PDA@Ag5GO1 irradiated by NIR can completely repair the wound defect (1.0 × 1.0 cm2) within 15 days, the wound healing rate can reach 100%, which was far higher than other groups. Taken together, the new hydrogel with excellent antibacterial, high adhesion and strong contractility will subvert the traditional treatment methods on wound defect, extending its new application range in wound dressing.

Converting Complex Sewage Containing Oil, Silt, and Bacteria into Clean Water by a 3D Printed Multiscale and Multifunctional Filter.

The exacerbating water pollution and water resource shortage pose a great danger to human health and make it imperative to recycle and treat the sewage. In this study, a direct-writing three-dimensional (3D) printing technology was adopted to prepare a 3D sodium alginate (SA)/graphene oxide (GO)/Ag nanoparticle (AgNP) aerogel (SGA), aiming to turn the complex sewage containing oil, silt, and bacteria into clean water depending only on gravity separation. The physicochemical properties and surface structure of the synthesized SGA were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The swelling rate, mechanical properties, antibacterial properties, oil and water separation effect, and durable stability of the filter membrane were also investigated to verify the versatility of the SGA filter. The results showed that GO helped improve the mechanical properties of the printed filter to withstand water impact during the filtration process. The printed filter had a well-designed and multiscale gradient pore structure, which can effectively intercept particles with different sizes to separate the silt from water, and the turbidity of the filtered water can be reduced from 60 to 1 nephelometric turbidity unit (NTU). The presence of SA endowed the printed filter with hydrophilic and oleophobic behaviors, which can effectively separate various kinds of oils from water. The uniform distribution of AgNPs in the filter produced via a facile and green reduction of SA facilitated the efficient bactericidal ability of the printed filter during the filtration process; meanwhile, the lower release concentration of Ag ions ensured drinking safety. What is more, the filter can be easily produced on a large scale and used for different sewage treatment situations with a durable stability of over 30 days. Taken together, the printed SGA filter has a broad application prospect in complex sewage treatment, providing a special solution for sewage treatment in poverty areas.

Near-Infrared Light-Triggered Unfolding Microneedle Patch for Minimally Invasive Treatment of Myocardial Ischemia.

It is hard to achieve safe, effective, and minimally invasive therapies on myocardial infarction (MI) via conventional treatments. To address this challenge, a vascular endothelial growth factor (VEGF)-loaded and near-infrared (NIR)-triggered self-unfolding graphene oxide (GO)-poly(vinyl alcohol) (PVA) microneedle (MN) patch was designed and fabricated to treat MI through a minimally invasive surgery (MIS). The folded MN patch can be easily placed into the chest cavity through a small cut (4 mm) and quickly recover to its original shape with 10 s of irradiation of NIR light (1.5 W/cm2, beam diameter = 0.5 cm), thanks to its excellent shape memory effect and fast shape recovery ability. Meanwhile, the unfolded MN patch can be readily punctured into the heart and wrap the heart tightly, thanks to its sufficient mechanical strength and adjustable morphological structure, thus ensuring a high fixation strength to withstand the high-frequency pulsation of the heart. In addition, the prepared MN patch has low cytotoxicity and controllable and sustainable release of VEGF. More importantly, the MN patch can effectively promote neovascularization, reduce myocardial fibrosis, and restore cardiac function, which indicates its promising application prospects in MIS.

Rheological and Mechanical Properties of Resin-Based Materials Applied in Dental Restorations.

Resin-based materials have been prevalent for dental restorations over the past few decades and have been widely used for a variety of direct and indirect procedures. Typically, resin-based dental materials are required to be flowable or moldable before setting and can provide adequate mechanical strength after setting. The setting method may include, but is not limited to, light-curing, self-curing or heating. In this review, based on different indications of resin-based dental materials (e.g., dental filling composite, dental bonding agent, resin luting cement), their rheological and mechanical properties were reviewed. Viscous and flexible properties were focused on for materials before setting, while elastic properties and mechanical strength were focused on for materials after setting. At the same time, the factors that may affect their rheological and mechanical properties were discussed. It is anticipated that the insightful information and prospections of this study will be useful to the future development and fabrication of resin-based dental restorative materials.

Oxidative esterification of renewable furfural on cobalt dispersed on ordered porous nitrogen-doped carbon.

A series of highly dispersed cobalt-based catalysts on N-doped ordered porous carbon (Co-NOPC) were synthesized using the sacrificial-template method. MCM-41, ZSM-5 and SBA-15 were employed as hard templates with 2,2'-bipyridine as the ligand. The physical and chemical properties of the Co-NOPC catalyst were characterized by Raman, XRD, SEM, TEM, EDX, ICP, BET, XPS. Co-NOPC had been proven to be a highly efficient catalyst for oxidative esterification of furfural (FUR) to methyl 2-furoate without alkaline additives. Catalytic performance was correlated to the dispersed cobalt, porous structure and specific surface area. The relationship between oxygen activation and the strong interaction of cobalt and pyridine nitrogen were confirmed by XPS. Catalytic performance enhancement mechanisms were correlated with the redistribution of electrons at the interface between carbon material and cobalt atoms through the molecular dynamics method and a reaction mechanism was also proposed. The optimized catalysts showed outstanding catalytic activity and stability and no obvious decrease in activity was found after 6 cycles with 99.6% FUR conversion and 96% methyl 2-furoate selectivity.

Au@polydopamine nanoparticles/tocilizumab composite as efficient scavengers of oxygen free radicals for improving the treatment of rheumatoid arthritis.

Rheumatoid arthritis (RA) is the most common chronic autoimmune disorder associated with high-cost, side effects, and low therapeutic effects. To improve the treatment of RA, we originally developed a novel anti-RA Au@polydopamine nanoparticles (PDANPs)/TCZ composite using PDANPs as the binding sites of gold nanoparticles (AuNPs) and the drug carries of tocilizumab (TCZ) through a facile and environmentally-friend method, aiming to effectively scavenge oxygen free radicals (OFR) and inhibit the formation of related inflammatory factors. Characterizations showed that AuNPs with the size of 11.4 ± 2.9 nm randomly distributed onto the surface of PDANPs (145.8 ± 31.9 nm), meanwhile TCZ was chemically cross-linked to PDANPs through Schiff base linkage. The synthesized composite had good biocompatibility that can promote the proliferation and growth of chondrocytes and fibroblasts. More importantly, Au@PDANPs/TCZ composite showed more excellent abilities to scavenge OFR and inhibit the related inflammatory factors in vitro and in vivo than that of AuNPs and PDANPs owing to the synergistic scavenging effect, ensuring its best therapeutic effect in RA therapy. This new composite will have application potential in the treatment of RA related disease.

Enantioselective extraction of unprotected amino acids coupled with racemization.

Scalable and economical methods for the production of optically pure amino acids, both natural and unnatural, are essential for their use as synthetic building blocks. Currently, enzymatic dynamic kinetic resolution (DKR) underpins some of the most effective processes. Here we report the development of enantioselective extraction coupled with racemization (EECR) for the chirality conversion of underivatized amino acids. In this process, the catalytic racemization of amino acids in a basic aqueous solution is coupled with the selective extraction of one enantiomer into an organic layer. Back-extraction from the organic layer to an acidic aqueous solution then completes the deracemization of the amino acid. The automation of the EECR process in a recycling flow reactor is also demonstrated. Continuous EECR is made possible by the sterically hindered chiral ketone extractant 5, which prevents the coextraction of the copper racemization catalyst because of its nonplanar geometry. Furthermore, the extractant 5 unexpectedly forms imines with amino acids faster and with greater enantioselectivity than less bulky derivatives, even though 5 cannot participate in intramolecular resonance-assisted hydrogen bonding. These features may allow EECR to challenge the preponderance of enzymatic DKR in the production of enantiomerically enriched amino acids.