Covalent organic frameworks (COFs) consist of monomers arranged in predictable structures with emergent properties. However, improved crystallinity, porosity, and solution processability remain major ...challenges. To this end, colloidal COF nanoparticles are useful for mechanistic studies of nucleation and growth and enable advanced spectroscopy and solution processing of thin films. Here we present a general approach to synthesize imine-linked 2D COF nanoparticles and control their size by favoring imine polymerization while preventing the nucleation of new particles. The method yields uniform, crystalline, and high-surface-area particles and is applicable to several imine-linked COFs.
X-ray scattering experiments reveal the nucleation of amorphous polymers, which crystallize
imine exchange processes during and after particle growth, consistent with previous mechanistic studies of imine-linked COF powders. The separation of particle formation and growth processes offers control of particle size and may enable further improvements in crystallinity in the future.
This work investigated the microstructure and tensile deformation behavior of Ti-6Al-4V alloy fabricated using a high-power laser solid forming (LSF) additive manufacturing. The results show that the ...post-fabricated heat-treated microstructure consists of coarse columnar prior-β grains (630–1000 μm wide) and α-laths (5–9 μm) under different scanning velocities (900 and 1500 mm/min), which caused large elongation (∼18%) superior to the conventional laser additive manufacturing Ti-6Al-4V alloy. The deformation behavior of the LSF Ti-6Al-4V alloy was investigated using in situ tensile test scanning electron microscopy. The results show that shear-bands appeared along the α/β interface and slip-bands occurred within the α-laths, which lead to cracks decaying in a zigzag-pattern in the LSF Ti-6Al-4V alloy with basket-weave microstructure. These results demonstrate that the small columnar prior-β grains and fine basket-weave microstructure exhibiting more α/β interfaces and α-laths can disperse the load and resist the deformation in the LSF Ti-6Al-4V components. In addition, a modified microstructure selection map of the LSF Ti-6Al-4V alloy was established, which can reasonably predict the microstructure evolution and relative grain size in the LSF process.
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Background
The aim of this study was to evaluate whether adjuvant chemotherapy is associated with improved survival in patients with resectable gastric neuroendocrine carcinomas (G‐NECs) or mixed ...adenoneuroendocrine carcinomas (G‐MANECs).
Methods
The study included patients with G‐NECs or G‐MANECs who underwent surgery in one of 21 centres in China between 2004 and 2016. Propensity score matching analysis was used to reduce selection bias, and overall survival (OS) in different treatment groups was estimated by the Kaplan–Meier method.
Results
In total, 804 patients with resectable G‐NECs or G‐MANECs were included, of whom 490 (60·9 per cent) received adjuvant chemotherapy. After propensity score matching, OS in the chemotherapy group was similar to that in the no‐chemotherapy group. Among patients with G‐NECs, survival in the fluorouracil (5‐FU)‐based chemotherapy group and the non‐5‐FU‐based chemotherapy group was similar to that in the no‐chemotherapy group. Similarly, etoposide plus cisplatin or irinotecan plus cisplatin was not associated with better OS in patients with G‐NECs. Among patients with G‐MANECs, OS in the non‐5‐FU‐based chemotherapy group was worse than that in the no‐chemotherapy group. Patients with G‐MANECs did not have better OS when platinum‐based chemotherapy was
used.
Conclusion
There was no survival benefit in patients who received adjuvant chemotherapy for G‐NECs or G‐MANECs.
Antecedentes
El objetivo de este estudio fue evaluar si la quimioterapia adyuvante mejoraba la supervivencia en pacientes con carcinomas gástricos resecables neuroendocrinos (gastric neuroendocrine carcinomas, G‐NECs) y carcinomas adenoneuroendocrinos mixtos (mixed adenoneuroendocrine carcinomas, G‐MANECs).
Métodos
Se incluyeron pacientes con G‐NECs y G‐MANECs tratados quirúrgicamente en 21 centros en China entre 2004 y 2016. Se utilizó un análisis de emparejamiento por puntaje de propensión para reducir el sesgo de selección y el método de Kaplan‐Meier para estimar la supervivencia global (overall survival, OS) de los pacientes en los diferentes grupos de tratamiento.
Resultados
En total, se incluyeron en el estudio 804 pacientes con G‐NECs y G‐MANECs resecables y 490 pacientes (60,9%) recibieron quimioterapia adyuvante. Después del emparejamiento por puntaje de propensión, la OS del grupo con quimioterapia fue similar a la del grupo sin quimioterapia. En los pacientes con G‐NECs, la supervivencia en los grupos con quimioterapia basada en 5‐FU (fluorouracilo) y de quimioterapia sin 5‐FU fue similar a la del grupo sin quimioterapia. Asimismo, la combinación de etopósido y cisplatino o de irinotecán y cisplatino no se asoció con una mejor OS en pacientes con G‐NECs. En pacientes con G‐MANECs, la OS del grupo con quimioterapia sin 5‐FU fue peor que la del grupo sin quimioterapia. Los pacientes con G‐MANECs no presentaron una mejor OS cuando se administró quimioterapia basada en platinos.
Conclusión
La administración de quimioterapia adyuvante en pacientes con G‐NECs y G‐MANECs no mejoró la supervivencia.
This multicentre study enrolled 804 patients with resectable gastric neuroendocrine carcinomas and gastric mixed adenoneuroendocrine carcinomas. In propensity score matching analysis, there were no associations between the use of adjuvant chemotherapy and improved overall survival. Similar results were obtained in stratified analysis according to different chemotherapy regimens.
No benefit
•Structural dynamics on the ultrafast time scale for CuI diimine complexes.•Key structural factors for optimal photoinduced electron transfer are identified.•Interplays of solvent accessibility to ...the copper center and behaviors of the excited state are characterized.•Structural design guidelines for CuI diimine complexes to be effective sensitizers and electron donors are outlined.•Listed recent applications of CuI diimine complexes in solar energy conversion systems.
Although they were discovered almost four decades ago, Cu(I) diimine complexes have emerged as a group of transition metal complexes that can play important roles in solar energy conversion and utilization, and have potential to replace the quintessential ruthenium polypyridyl complexes as light sensitizers, electron donors and catalytic centers. This review includes some recent photophysical studies and transient structural studies of Cu(I) diimine complexes using ultrafast optical transient absorption and emission as well as X-ray transient absorption spectroscopy. The main focus is on identifying the key structural factors that influence the excited-state properties, such as structural reorganization, intersystem crossing and solvent quenching, with these relatively new techniques on the ultrafast time scales. Ultimately, these structural factors can be used to rationally control the energetics and dynamics of the MLCT state during the light conversion processes. This insight will serve as guidance for material design using Cu(I) diimine complexes as building blocks.
2D hybrid halide perovskites with the formula (A′)2(A)n‐1PbnI3n+1 have remarkable stability and promising efficiency in photovoltaic and optoelectronic devices, yet fundamental understanding of film ...formation, key to optimizing these devices, is lacking. Here, in situ grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) is used to monitor film formation during spin‐coating. This elucidates the general film formation mechanism of 2D halide perovskites during one‐step spin‐coating. There are three stages of film formation: sol–gel, oriented 3D, and 2D. Three precursor phases form during the sol–gel stage and transform to perovskite, first giving a highly oriented 3D‐like phase at the air/liquid interface followed by subsequent nucleations forming slightly less oriented 2D perovskite. Furthermore, heating before crystallization leads to fewer nucleations and faster removal of the precursors, improving orientation. This outlines the primary causes of phase distribution and perpendicular orientation in 2D perovskite films and paves the way for rationally designed film fabrication techniques.
The mechanism of 2D halide perovskite film formation is resolved using in situ grazing‐incidence wide‐angle scattering (GIWAXS). The film begins as a sol–gel precursor before first forming a 3D MAPbI3‐like phase at the air/liquid interface. This acts as a template for the highly textured 2D phase with the layers perpendicular to the substrate, which grows closer to the substrate.
The recent explosive adoption of electric vehicles (EVs) and plug-in hybrid EVs (PHEVs) has sparked considerable interest in academia in developing efficient charging schemes. Supported by the ...advanced vehicle-to-grid network, vehicles and charging stations can, respectively, make better charging and pricing decisions via real-time information sharing. In this paper, we study the charging problem in an intelligent transportation system, which consists of smart-grid enabled charging stations and networked EVs. Each vehicle aims to select a station with the lowest charging cost by considering the charging prices and its location, while the objective of a charging station is to maximize its revenue, given the charging strategy of the vehicles. We employ a multi-leader multi-follower Stackelberg game to model the interplay between the vehicles and charging stations, in which the location factor plays an important role. We show that the equilibrium of the followers' subgame played by the vehicles exits, while the stations are able to reach an equilibrium of their subgame with respect to the charging prices. Therefore, the Nash equilibrium of the Stackelberg game is achievable using the proposed charging scheme. Finally, the performance of the proposed approach is demonstrated via extensive trace-driven simulations.
Epithelial-mesenchymal transition (EMT) has an established role in promoting tumor progression and the acquisition of therapeutic resistance. Here, the EMT phenotype was detected in ...cisplatin-resistant ovarian cancer tissues and cell lines, and correlated with decreased miR-186 expression, increased Twist1 expression, chemoresistance and poor prognosis in epithelial ovarian cancer (EOC) patients. Introducing miR-186 into EOC cells led to a reduction in twist family bHLH transcription factor 1 (Twist1) expression along with morphological, functional and molecular changes consistent with mesenchymal-to-epithelial transition, G1 cell-cycle arrest and enhanced cell apoptosis, which consequently rendered the cells more sensitive to cisplatin in vitro and in vivo. Furthermore, luciferase reporter and rescue assay results showed that the EMT and drug resistance reversal in response to miR-186 was mediated by Twist1. Collectively, these findings implicate miR-186 as an attractive candidate for overcoming chemoresistance in ovarian cancer therapy.
In this paper, cognitive routing coupled with spectrum sensing and sharing in a multi-channel multi-hop cognitive radio network (CRN) is investigated. Recognizing the spectrum dynamics in CRN, we ...propose an opportunistic cognitive routing (OCR) protocol that allows users to exploit the geographic location information and discover the local spectrum access opportunities to improve the transmission performance over each hop. Specifically, based on location information and channel usage statistics, a secondary user (SU) distributedly selects the next hop relay and adapts its transmission to the dynamic spectrum access opportunities in its neighborhood. In addition, we introduce a novel metric, namely, cognitive transport throughput (CTT), to capture the unique properties of CRN and evaluate the potential relay gain of each relay candidate. A heuristic algorithm is proposed to reduce the searching complexity of the optimal selection of channel and relay. Simulation results are given to demonstrate that our proposed OCR well adapts to the spectrum dynamics and outperforms existing routing protocols in CRN.
The chemical variety present in the organic electronics literature has motivated us to investigate potential nonbonding interactions often incorporated into conformational “locking” schemes. We ...examine a variety of potential interactions, including oxygen–sulfur, nitrogen–sulfur, and fluorine–sulfur, using accurate quantum-chemical wave function methods and noncovalent interaction (NCI) analysis on a selection of high-performing conjugated polymers and small molecules found in the literature. In addition, we evaluate a set of nonbonding interactions occurring between various heterocyclic and pendant atoms taken from a group of representative π-conjugated molecules. Together with our survey and set of interactions, it is determined that while many nonbonding interactions possess weak binding capabilities, nontraditional hydrogen-bonding interactions, oxygen–hydrogen (CH···O) and nitrogen–hydrogen (CH···N), are alone in inducing conformational control and enhanced planarity along a polymer or small molecule backbone at room temperature.