Computational studies on the radiative and nonradiative processes of luminescent N-heteroleptic platinum(II) complexes

Three N-heteroleptic Pt(II) complexes, [Pt(C^C)(O^O)] [O^O = acetylacetonate, C^C = 1-phenyl-1,2,4-triazol-5-ylidene (1), C^C = 4-phenyl-1,2,4-triazol-5-ylidene (2), C^C = 2-phenylpyrazine (3)] have been investigated with density functional theory (DFT) and time-dependent density functional theory (TDDFT). The radiative decay rate constants of complexes 1–3 have been discussed with the oscillator strength (f_n), the strength of spin–orbit coupling (SOC) interaction between the lowest energy triplet excited state (T₁) and singlet excited states (S_n), and the energy gaps between E(T₁) and E(S_n). To illustrate the nonradiative decay processes, the transition states between triplet metal-centered (³MC) and T₁ states have been optimized and were verified with the calculations of vibrational frequencies and intrinsic reaction coordinate (IRC). In addition, the minimum energy crossing points (MECPs) between ³MC and ground states (S₀) were optimized. At last, the potential energy curves relevant to the nonradiative decay pathways are simulated. The results show that complex 3 has the biggest photoluminescence quantum yield because the complex 3 has the biggest radiative decay rate constant and the smallest nonradiative decay rate constant in complexes 1–3.     

Fabrication of 3D structures via direct ink writing of kaolin/graphene oxide composite suspensions at ambient temperature

Kaolin/graphene oxide composite has been widely utilized in aero-space and architectural engineering applications due to its excellent mechanical property. Direct ink writing (DIW) is a freeform rapid prototyping technology that could be used to accurately fabricate the resulting size with complex shapes. In this study, we reported the DIW of kaolin/graphene oxide (GO) composite suspensions (KGCS) to assemble 3D structures at ambient temperature for the first time. The effects of GO on the chemical constitution and microstructure of kaolin suspensions were investigated. Rheology was characterized to ensure printability of KGCS. The addition of GO in kaolin suspensions quickened a flocculation structure, which dramatically changed their rheology properties. The DIW of 3D structures from the optimal KGCS sample maintained their initial shape without spreading. The flexural and compressive strengths of the dried optimal KGCS samples were obviously enhanced due to the improvement and reduction of the micro-defects compared from cured kaolin matrix.     

Role of Epithelial–Mesenchymal Plasticity in Pseudomyxoma Peritonei: Implications for Locoregional Treatments

The mechanisms by which neoplastic cells disseminate from the primary tumor to metastatic sites, so-called metastatic organotropism, remain poorly understood. Epithelial–mesenchymal transition (EMT) plays a role in cancer development and progression by converting static epithelial cells into the migratory and microenvironment-interacting mesenchymal cells, and by the modulation of chemoresistance and stemness of tumor cells. Several findings highlight that pathways involved in EMT and its reverse process (mesenchymal–epithelial transition, MET), now collectively called epithelial–mesenchymal plasticity (EMP), play a role in peritoneal metastases. So far, the relevance of factors linked to EMP in a unique peritoneal malignancy such as pseudomyxoma peritonei (PMP) has not been fully elucidated. In this review, we focus on the role of epithelial–mesenchymal dynamics in the metastatic process involving mucinous neoplastic dissemination in the peritoneum. In particular, we discuss the role of expression profiles and phenotypic transitions found in PMP in light of the recent concept of EMP. A better understanding of EMP-associated mechanisms driving peritoneal metastasis will help to provide a more targeted approach for PMP patients selected for locoregional interventions involving cytoreductive surgery and hyperthermic intraperitoneal chemotherapy.     

Burkholderia thailandensis E264/pBMTL3-tdpR发酵生产抗癌药物ThailandepsinA的研究

在伯克氏菌Bth264野生株产新型抗癌药物Thailandepsin A以及调节基因tdp R正向调控Thailandepsin A生物合成的基础上,利用基因工程菌Bth264/p BMTL3-tdp R发酵生产Thailandepsin A,以提高产量。以0.5%乳糖为诱导剂,确定最佳诱导条件:发酵15 h添加乳糖,诱导时间6 h;通过单因素实验,确定葡萄糖和胰蛋白胨作为碳氮源、装液量65/250 m L以及接种量1%;同时结合优化发酵培养基进行发酵,Thailandepsin A产量达到252.14 mg·L-1,比优化前的产量提高56%;另外在发酵过程中,添加大孔树脂HP-20原位吸附产物,Thailandepsin A产量可达283.75 mg·L-1,比不加树脂提高13.8%;最后,基于RT-PCR和比较Ct值法,基因工程菌和野生菌相比,Thailandepsin A生物合成基因tdp B、tdp C1的转录水平分别提高11.4倍和6.0倍,对应的产量增加4.6倍,从而在很大程度上说明调节基因tdp R的过表达促进生物合成基因转录水平的提高以及产量的增加。     

Fabrication of tungsten oxide photoanode by doctor blade technique and investigation on its photocatalytic operation mechanism

WO₃ is a potential material candidate for construction of photoanode for solar driven water splitting. In this work, μm-thick porous WO₃ photoanode is prepared by depositing a stable ink made of WO₃ nanoparticles and Aristoflex velvet polymer in water using the doctor blade technique, followed by a sintering in air. The nature of WO₃ nanoparticles, its loading mass on F-doped tin oxide electrode as well as sintering temperature are examined in order to optimize the photocatalytic activity of the resultant WO₃ photoanode. The operation of WO₃ photoanode is investigated by varying the light illumination direction and light incident intensity as well as changing the nature of the electrolyte. Dissolved tungsten in electrolyte is quantified by ICP-MS providing insights into the influences of electrolyte nature and operating conditions to the corrosion of WO₃. It is proposed that the H₂O₂ and OH^. radical generated as by-products of the photo-driven water oxidation on the photoanode surface are harmful species that accelerate the dissolution of WO₃.     

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.     

Raman and X-ray photoelectron spectroscopy study on the influence of La2O3 on the melt structure of SiO2–CaO–Al2O3–MgO

In order to gain more insights into the influence of rare earth elements on the melt structure of SiO₂–CaO–Al₂O₃–MgO glass ceramics, Raman and X-ray photoelectron spectroscopy techniques were used to study the influence of La₂O₃ on the Si–O/Al–O tetrahedron structure within SiO₂–CaO–Al₂O₃–MgO–quenched glass samples in this study. Results showed that some Raman peak shapes at low frequencies (200–840 cm^?1) changed significantly after the addition of La₂O₃, compared to the high frequency (840–1200 cm^?1) region that corresponds to the [SiO₄] structure, suggesting that the depolymerization of the low-frequency T–O–T (T=Si or Al) structure was more prevalent with La³⁺ addition. Besides, the depolymerization extent of the Si–O/Al–O tetrahedral network varied when the melt composition altered. Most notably, depolymerization is the most significant at a low CaO/SiO₂ ratio (0.25) and a high Al₂O₃ content (8%). Meanwhile, La³⁺ can promote the transformation of Si–O–Si and Al–O–Al bonds to the Si–O–Al ones, thereby forming a complex ionic cluster network interwoven with Si–O and Al–O tetrahedrons.     

Unique CNTs-chained Li4Ti5O12 nanoparticles as excellent high rate anode materials for Li-ion capacitors

Composite anode materials with a unique architecture of carbon nanotubes (CNTs)-chained spinel lithium titanate (Li₄Ti₅O₁₂, LTO) nanoparticles are prepared for lithium ion capacitors (LICs). The CNTs networks derived from commercial conductive slurry not only bring out a steric hindrance effect to restrict the growth of Li₄Ti₅O₁₂ particles but greatly enhance the electronic conductivity of the CNTs/LTO composites, both have contributed to the excellent rate capability and cycle stability. The capacity retention at 30 C (1 C = 175 mA g^?1) is as high as 89.7% of that at 0.2 C with a CNTs content of 11 wt%. Meanwhile, there is not any capacity degradation after 500 cycles at 5 C. The LIC assembled with activated carbon (AC) cathode and such a CNTs/LTO composite anode displays excellent energy storage properties, including a high energy density of 35 Wh kg^?1 at 7434 W kg^?1, and a high capacity retention of 87.8% after 2200 cycles at 1 A g^?1. These electrochemical performances outperform the reported data achieved on other LTO anode-based LICs. Considering the facile and scalable preparation process proposed herein, the CNTs/LTO composites can be very potential anode materials for hybrid capacitors towards high power-energy outputs.     

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.