Lipase‐catalyzed synthesis of aliphatic poly(β‐thioether ester) with various methylene group contents: thermal properties,crystallization and degradation

A series of novel aliphatic poly(β‐thioether ester)s with various methylene group contents were prepared by direct lipase‐catalyzed polycondensation of the monomer with an acid‐labile β‐thiopropionate group. The polycondensation reaction using immobilized lipase B from Candida antarctica was carried out in diphenyl ether at 90 °C. Poly(β‐thioether ester)s with high molecular weights of 20 500–57 000 Da and narrow polydispersities in the range 1.40–1.48 were obtained. Thermogravimetric analysis, differential scanning calorimetry and wide‐angle X‐ray diffraction were used to investigate the thermal properties and crystal structures of these polyesters. All the poly(β‐thioether ester)s were semicrystalline polymers and thermally stable up to at least 200 °C. In vitro degradation studies showed that they can rapidly degrade under acidic conditions by the hydrolysis of the β‐thiopropionate groups, suggesting their potential as acid‐degradable polymeric materials. © 2019 Society of Chemical Industry     

Photopolymerization synthesis of polyacrylic acid dispersant with methoxysilicon end groups and its application in a nano‐SiO2 aqueous system

In order to improve the dispersity and stability of the nano‐SiO₂ aqueous system with high solid content, a kind of polyacrylic acid dispersant with methoxysilicon end groups (KH590‐PAA) was synthesized by photopolymerization of acrylic acid (AA) initiated with (3‐mercaptopropyl)trimethoxysilane (KH590). After adding KH590‐PAA into the nano‐SiO₂ aqueous dispersion system (20 wt% solid content), the viscosity and the curing time of the system were measured with a rotational viscometer and the inverted bottle method. Moreover, the dispersion mechanism of KH590‐PAA for the nano‐SiO₂ aqueous system was researched by measuring the adsorption capacity, the particle size and the zeta potential of the nanoparticles with a conductivity meter, dynamic light scattering, SEM and TEM, respectively. The results showed that the methoxysilicon groups in KH590‐PAA could react with hydroxyl groups on the surface of nano‐SiO₂ in the process of stirring, which enhanced the adsorption capacity of the dispersant and then increased the surface charge of the particles. Therefore, electrostatic repulsion and steric hindrance effects between the SiO₂ nanoparticles could be further enhanced by adding the KH590‐PAA dispersant, and then the nano‐SiO₂ aqueous system exhibited better dispersity and stability. Besides, the dispersion properties of SiO₂ nanoparticles in water were closely related to the addition amount and the molecular weight of the KH590‐PAA dispersant. © 2018 Society of Chemical Industry     

Human responses to high levels of carbon dioxide and air temperature

In this study, 30 subjects were exposed to different combinations of air temperature (T_a: 24, 27, and 30°C) and CO₂ level (8000, 10 000, and 12 000 ppm) in a high-humidity (RH: 85%) underground climate chamber. Subjective assessments, physiological responses, and cognitive performance were investigated. The results showed that as compared with exposure to T_a = 24°C, exposure to 30°C at all CO₂ levels caused subjects to feel uncomfortably warm and experience stronger odor intensity, while increased mental effort and greater intensity of acute health symptoms were reported. However, no significant effects of T_a on task performance or physiological responses were found. This indicated that subjects had to exert more effort to maintain their performance in an uncomfortably warm environment. Increasing CO₂ from 8000 to 12 000 ppm at all T_a caused subjects to report higher rates of headache, fatigue, agitation, and feeling depressed, although the results were statistically significant only at 24 and 27°C. The text typing performance and systolic blood pressure (SBP) decreased significantly at this exposure, whereas diastolic blood pressure (DBP) and thermal discomfort increased significantly. These effects suggest higher arousal/stress. No significant interaction effect of T_a and CO₂ concentration on human responses was identified.     

Effect of Li2O on the crystallization behavior of CaO-Al2O3-SiO2-Li2O-Ce2O3 mold slags

The effect of Li₂O on the crystallization properties of CaO-Al₂O₃-SiO₂-Li₂O-Ce₂O₃ slags was investigated. With increasing the Li₂O content, LiAlO₂ and CaCeAlO₄ were the main crystalline phases. LiAlO₂ formed for the charge compensating of Li⁺ ions to [AlO₄^5?]-tetrahedrons, and CaCeAlO₄ formed as a result of the charge balance of Ce³⁺ ions, Ca²⁺ ions, and [AlO₆^9?]-octahedrons. Increasing the content of Li₂O to 10%, the crystallization temperature was the highest, and the incubation time was the shortest. The crystallization ability was strong due to the three factors of strengthening the interaction between ions and ion groups, decreasing the polymerization degree, and increasing the melting temperature. Further increasing the content of Li₂O, the crystallization performance was obviously suppressed, because the melting temperature and the force between the cations and the anion groups decreased.     

Electrospun fiber membranes from blends of poly(vinylidene fluoride) with fouling‐resistant zwitterionic copolymers

Nonwoven super‐hydrophobic fiber membranes have potential applications in oil–water separation and membrane distillation, but fouling negatively impacts both applications. Membranes were prepared from blends comprising poly(vinylidene fluoride) (PVDF) and random zwitterionic copolymers of poly(methyl methacrylate) (PMMA) with sulfobetaine methacrylate (SBMA) or with sulfobetaine‐2‐vinylpyridine (SB2VP). PVDF imparts mechanical strength to the membrane, while the copolymers enhance fouling resistance. Blend composition was varied by controlling the PVDF‐to‐copolymer ratio. Nonwoven fiber membranes were obtained by electrospinning solutions of PVDF and the copolymers in a mixed solvent of N,N‐dimethylacetamide and acetone. The PVDF crystal phases and crystallinities of the blends were studied using wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). PVDF crystallized preferentially into its polar β‐phase, though its degree of crystallinity was reduced with increased addition of the random copolymers. Thermogravimetry (TG) showed that the degradation temperatures varied systematically with blend composition. PVDF blends with either copolymer showed significant increase of fouling resistance. Membranes prepared from blends containing 10% P(MMA‐ran‐SB2VP) had the highest fouling resistance, with a fivefold decrease in protein adsorption on the surface, compared to homopolymer PVDF. They also exhibited higher pure water flux, and better oil removal in oil–water separation experiments. © 2018 Society of Chemical Industry     

Characterization,in vitro bioactivity and biological studies of sol-gel-derived TiO2 substituted 58S bioactive glass

Bioactive glasses (BGs) have been used for bone formation and bone repair processes in recent years. This study investigated the titanium substitution effect on 58S BGs (Ti-BGs) 60SiO₂-(36 − X)CaO-4P₂O₅-XTiO₂ (X = 0, 3, and 5 mol.%) prepared by the sol-gel technique, and the main goal was to find the optimum amount of titanium in Ti-BGs. Synthesized BGs, which were investigated after immersion in simulated body fluid (SBF), were tested by X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy. Moreover alkaline phosphate (ALP) activity, 3-(4,5dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, and antibacterial studies were employed to investigate the biological properties of Ti-BGs. According to the FTIR and XRD test results, hydroxyapatite (HA) formation on Ti-BGs surfaces was confirmed. Meanwhile, the presence of 5 mol.% compared to 3 mol.% increased the HA grain distribution and their size on the Ti-BGs surface. Additionally, MTT and ALP results confirmed that the optimal amount of titanium substitution in BG was 5 mol.%. Since 5 mol.% Ti incorporated BG (BG-5) had the highest biocompatibility level, antibacterial properties, maximum cell proliferation, and ALP activity among the synthesized Ti-BGs, it is presented as the best candidate for further in vivo investigations.     

Red-shift and improved afterglow of Sr3Al2-xBxO5Cl2:Eu2+, Dy3+ phosphors via a cation substitution strategy

Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ (x = 0, 0.2, 0.4) long persistent phosphors were prepared via solid-state process. The pristine Sr₃Al₂O₅Cl₂:Eu²⁺, Dy³⁺ phosphor exhibits orange/red broad band emission around 609 nm, which can be attributed to the electric radiation transitions 4f⁶5 d¹→4f⁷ of Eu²⁺. Upon the same excitation, the B³⁺-doped Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ phosphors display red-shift from 609 nm to 625 nm with increasing B³⁺ concentrations. The XRD patterns show that Al³⁺ can be replaced by B³⁺ in the host lattice at the tetrahedral site, which causes lattice contraction and crystal field enhancement, and thereafter achieves the red-shift on the emission spectrum. The XPS investigation provides direct evidence of the dominant 2-valent europium in the phosphor, which can be ascribed for the broad band emission of the prepared phosphors. The afterglow of all phosphors show standard double exponential decay behavior, and the afterglow of Sr₃Al₂O₅Cl₂:Eu²⁺, Dy³⁺is rather weak, while the sample co-doped with B³⁺shows longer and stronger afterglow, as confirmed after the curve simulation. The analysis of thermally stimulated luminescence showed that, when B³⁺ is introduced, a much deeper trap is created, and the density of the electron trap is also significantly increased. As a result, B³⁺ ions caused redshift and enhanced afterglow for the Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ phosphor.     

Growth,mechanical properties,and tribological performance of TiAlN/NbN and NbN/TiAlN bilayer coatings

Three different coatings, namely TiAlN, TiAlN (external)/NbN (internal) and NbN (external)/TiAlN (internal), were deposited on cemented carbides by arc ion plating. The comparative investigation conducted in this study elucidates the effect of the NbN layer and coating systems on the growth, mechanical properties, and tribological performance of the coatings. The results showed that the surface of the TiAlN and TiAlN/NbN coatings was smoother when TiAlN served as the external layer. The NbN/TiAlN coating, wherein NbN formed the external layer, had a much rougher but more symmetrical surface. With the introduction of the NbN layer, the increased micro stress induced a lower adhesion strength in the TiAlN/NbN and NbN/TiAlN coatings. The TiAlN/NbN and NbN/TiAlN coatings exhibited higher hardness and hardness/effective elastic modulus (H/E*). During the friction test, when the temperature was elevated to 700 °C, the tribological performance of the monolayer TiAlN coating was the lowest because of the TiO₂-induced breakage of the dense tribo-oxide film. The NbN layer participated in the formation of a NbO_x film at elevated temperatures, which was responsible for the high tribological performance of the two bilayer coatings. When the NbN layer was on the outermost layer and in direct contact with the elevated temperature atmosphere, the NbN/TiAlN coating generated a tribo-oxide film with high integrity, and its coefficient of friction decreased by 27% of that at room temperature. Therefore, the NbN/TiAlN coating exhibited the highest wear resistance at 700 °C.     

P-doped CoSe2 nanoparticles embedded in 3D honeycomb-like carbon network for long cycle-life Na-ion batteries

We report for the first time a Na-ion battery anode material composed of P-doped CoSe2 nanoparticles(P-CoSe2)with the size of 5-20 nm that are uniformly embed in a 3D porous honeycomb-like carbon network.High rate capability and cycling stability are achieved simultaneously.The honeycomb-like carbon network is rationally designed to support high electrical conductivity,rapid Na-ion diffusion as well as the accommodation of the volume expansion from the active P-CoSe2 nanoparticles.In particular,heteroatom P-doping within CoSe2 introduces stronger P-Co bonds and additional P-Se bonds that signif-icantly improve the structure stability of P-CoSe2 for highly stable sodiation/desodiation over long-term cycling.P-doping also improves the electrical conductivity of the CoSe2 nanoparticles,leading to highly elevated electrochemical kinetics to deliver high specific capacities at high current densities.Benefiting from the unique nanostructure and atomic-level P-doping,the P-CoSe2(2∶1)/C anode delivers an excel-lent cycle stability with a specific capacity of 206.9 mA h g-1 achieved at 2000 mA g-1 after 1000 cycles.In addition,this material can be synthesized using a facile pyrolysis and selenization/phosphorization approach.This study provides new opportunities of heteroatom doping as an effective method to improve the cycling stability of Na-ion anode materials.     

TiO2/MXene-Assisted LDI-MS for Urine Metabolic Profiling in Urinary Disease

Cancer remains an intractable medical problem. Rapid diagnosis and identification of cancer are critical to differentiate it from nonmalignant diseases. High-throughput biofluid metabolic analysis has potential for cancer diagnosis. Nevertheless, the present metabolite analysis method does not meet the demand for high-throughput screening of diseases. Herein, a high-throughput, cost-effective, and noninvasive urine metabolic profiling method based on TiO₂/MXene-assisted laser desorption/ionization mass spectrometry (LDI-MS) is presented for the efficient screening of bladder cancer (BC) and nonmalignant urinary disease. Combined with machine learning, TiO₂/MXene-assisted LDI-MS enables high diagnostic accuracy (96.8%) for the classification of patient groups (including 47 BC and 46 ureteral calculus (UC) patients) from healthy controls (113 cases). In addition, BC patients can also be identified from noncancerous UC individuals with an accuracy of 88.3% in the independent test cohort. Furthermore, metabolite variations between BC and UC individuals are investigated based on relative quantification, and related pathways are also discussed. These results suggest that this method, based on urine metabolic patterns, provides a potential tool for rapidly distinguishing urinary diseases and it may pave the way for precision medicine.