The hierarchical aggregation of molecular nanostructures from multiple components is a grand synthetic challenge, which requires highly selective linkage control. We demonstrate how two orthogonal ...linkage groups, that is, organotin and lanthanide cations, can be used to drive the aggregation of a giant molecular metal oxide superstructure. The title compound {(Sn(CH3)2)2O4{CeW5O18 TeW4O16CeSn(CH3)24TeW8O314}2}46− (1 a) features dimensions of ca. 2.2×2.3×3.4 nm3 and a molecular weight of ca. 25 kDa. Structural analysis shows the hierarchical aggregation from several independent subunits. Initial biomedical tests show that 1 features an inhibitory effect on the proliferation of HeLa cells based on an apoptosis pathway. In vivo experiments in mice reveal the antiproliferative activity of 1 and open new paths for further development of this new compound class.
Hierarchical assembly of a giant heterometallic polyoxotungstate supercluster with a molecular weight of ca. 25 kDa is reported. Geometrically unrestricted cerium(III) and geometrically restricted dimethyl tin cation linkers are used to gain access to a giant molecular species featuring three different polyoxometalate building units. The compound demonstrates in vitro and in vivo antiproliferative activity against HeLa cervical cancer cell lines.
Controlling the solution‐state aggregation of conjugated polymers for producing specific microstructures remains challenging. Herein, a practical approach is developed to finely tune the solid‐state ...microstructures through temperature‐controlled solution‐state aggregation and polymer crystallization. High temperature generates significant conformation fluctuation of conjugated backbones in solution, which facilitates the polymer crystallization from solvated aggregates to orderly packed structures. The polymer films deposited at high temperatures exhibit less structural disorders and higher electron mobilities (up to two orders of magnitude) in field‐effect transistors, compared to those deposited at low temperatures. This work provides an effective strategy to tune the solution‐state aggregation to reveal the relationship between solution‐state aggregation and solid‐state microstructures of conjugated polymers.
Using temperature‐controlled polymer aggregation, the solid‐state microstructures of conjugated polymers are finely tuned. The temperature‐controlled strategy enhances the molecular ordering in thin films and leads to efficient charge transport. A polymer transistor with tuned molecular ordering exhibited improved electron mobilities of up to 3.71 cm2 V−1 s−1, which is two orders of magnitude higher than the disordered samples.
The grey wolf optimizer (GWO) is a novel type of swarm intelligence optimization algorithm. An improved grey wolf optimizer (IGWO) with evolution and elimination mechanism was proposed so as to ...achieve the proper compromise between exploration and exploitation, further accelerate the convergence and increase the optimization accuracy of GWO. The biological evolution and the "survival of the fittest" (SOF) principle of biological updating of nature are added to the basic wolf algorithm. The differential evolution (DE) is adopted as the evolutionary pattern of wolves. The wolf pack is updated according to the SOF principle so as to make the algorithm not fall into the local optimum. That is, after each iteration of the algorithm sort the fitness value that corresponds to each wolf by ascending order, and then eliminate R wolves with worst fitness value, meanwhile randomly generate wolves equal to the number of eliminated wolves. Finally, 12 typical benchmark functions are used to carry out simulation experiments with GWO with differential evolution (DGWO), GWO algorithm with SOF mechanism (SGWO), IGWO, DE algorithm, particle swarm algorithm (PSO), artificial bee colony (ABC) algorithm and cuckoo search (CS) algorithm. Experimental results show that IGWO obtains the better convergence velocity and optimization accuracy.
Increased risk of colorectal cancer (CRC) is associated with altered intestinal microbiota as well as short‐chain fatty acids (SCFAs) reduction of output The energy source of colon cells relies ...mainly on three SCFAs, namely butyrate (BT), propionate, and acetate, while CRC transformed cells rely mainly on aerobic glycolysis to provide energy. This review summarizes recent research results for dysregulated glucose metabolism of SCFAs, which could be initiated by gut microbiome of CRC. Moreover, the relationship between SCFA transporters and glycolysis, which may correlate with the initiation and progression of CRC, are also discussed. Additionally, this review explores the linkage of BT to transport of SCFAs expressions between normal and cancerous colonocyte cell growth for tumorigenesis inhibition in CRC. Furthermore, the link between gut microbiota and SCFAs in the metabolism of CRC, in addition, the proteins and genes related to SCFAs‐mediated signaling pathways, coupled with their correlation with the initiation and progression of CRC are also discussed. Therefore, targeting the SCFA transporters to regulate lactate generation and export of BT, as well as applying SCFAs or gut microbiota and natural compounds for chemoprevention may be clinically useful for CRCs treatment. Future research should focus on the combination these therapeutic agents with metabolic inhibitors to effectively target the tumor SCFAs and regulate the bacterial ecology for activation of potent anticancer effect, which may provide more effective application prospect for CRC therapy.
Short‐chain fatty acids (SCFAs) produced in the human colon are the major products of bacterial fermentation of undigested dietary fiber and starch that escape absorption in the small intestine, and serve as a major source of energy for colonocytes. SCFAs are microbial‐derived metabolites, which are readily absorbed and used as an energy source by colonocytes. Several mechanisms have been proposed to underlie the anticancerous mechanisms of SCFAs. SCFAs reduce epithelial inflammation and trigger cancer cell apoptosis via p21 activity, providing an important defensive capacity against colorectal carcinogenesis.
The role of solution aggregates on the charge transport process of conjugated polymers in electronic devices has gained increasing attention; however, the correlation of the charge carrier mobilities ...between the solution aggregates and the solid‐state films remains elusive. Herein, three polymers, FBDOPV‐2T, FBDOPV‐2F2T, and FBDOPV‐4F2T, are designed and synthesized with distinct aggregation behavior in solution. By combining contact‐free ultrafast terahertz (THz) spectroscopy and field‐effect transistor measurements, we track the charge carrier mobility of the aggregates of these polymers from the solution to the thin‐film state. Remarkably, the mobility of these three polymers is found to follow nearly the same trend (FBDOPV‐2T>FBDOPV‐2F2T≫FBDOPV‐4F2T) in both solutions and thin‐film states. The quantitative mobility correlation indicates that the charge transport properties of solution aggregates play a critical role in determining the thin‐film charge transport properties and final device performance. Our results highlight the importance of investigating and controlling solution aggregation structures towards efficient organic electronic devices.
Different aggregation structures of three BDOPV‐based polymers in solution were obtained via subtle adjustment of the molecular structures. By employing contact‐free ultrafast terahertz (THz) spectroscopy, we directly reveal that the correlation of the charge carrier mobilities between the solution aggregates and the solid‐state films remains highly consistent.
Ultrasmall metal–organic frameworks (MOFs) may generate unique properties to expand the scope of applications. However, the synthesis is still a great challenge. Herein, we propose a strategy to ...synthesize ultrasmall MOFs by high gravity technology. With the aid of tremendous intensification of molecular mixing and mass transfer in high‐gravity field, six typical MOFs were obtained instantaneously in a continuous way. These samples are monodispersed with sub‐5 nm in size, smaller than the previously reported values and even close to the length of one crystal unit cell. As a proof‐of‐concept, catalytic activity for Knoevenagel reaction can be significantly enhanced using ultrasmall ZIF‐8. Conversion time of benzaldehyde was decreased by 94 % or 75 % compared to those using conventional or hierarchically porous ZIF‐8. More importantly, this approach is readily scalable with the highest space‐time yield for nano‐MOFs, which may promote the convenient synthesis and practical applications of ultrasmall MOFs in large‐scale.
A series of ultrasmall MOF nanoparticles could be instantaneously synthesized in a continuous way by a facile and universal strategy with the aid of high gravity intensification technology. This approach is readily scalable with the highest space‐time yield for nano‐MOFs. The as‐prepared ultrasmall ZIF‐8 exhibits extremely high catalytic activity for the Knoevenagel reaction.
Solution‐processable highly conductive polymers are of great interest in emerging electronic applications. For p‐doped polymers, conductivities as high a nearly 105 S cm−1 have been reported. In the ...case of n‐doped polymers, they often fall well short of the high values noted above, which might be achievable, if much higher charge‐carrier mobilities determined could be realized in combination with high charge‐carrier densities. This is in part due to inefficient doping and dopant ions disturbing the ordering of polymers, limiting efficient charge transport and ultimately the achievable conductivities. Here, n‐doped polymers that achieve a high conductivity of more than 90 S cm−1 by a simple solution‐based co‐deposition method are reported. Two conjugated polymers with rigid planar backbones, but with disordered crystalline structures, exhibit surprising structural tolerance to, and excellent miscibility with, commonly used n‐dopants. These properties allow both high concentrations and high mobility of the charge carriers to be realized simultaneously in n‐doped polymers, resulting in excellent electrical conductivity and thermoelectric performance.
Two conjugated polymers with rigid planar backbones, but with disordered crystalline structures, exhibit surprising structural tolerance to commonly used n‐dopants. These properties allow both high concentrations and high mobility of the charge carriers to be realized simultaneously in n‐doped polymers, resulting in excellent electrical conductivity of over 90 S cm−1 and thermoelectric performance up to 106 µW m−1 K−2.
The multi-level microstructure of conjugated polymers is the most critical parameter determining the charge transport property in field-effect transistors (FETs). However, controlling the ...hierarchical microstructures and the structural evolution remains a significant challenge. In this perspective, we discuss the key aspects of multi-level microstructures of conjugated polymers towards high-performance FETs. We highlight the recent progress in the molecular structures, solution-state aggregation, and polymer crystal structures, representing the multi-level microstructures of conjugated polymers. By tuning polymer hierarchical microstructures, we attempt to provide several guidelines for developing high-performance polymer FETs and polymer electronics.
The multi-level microstructures of conjugated polymers, including solution-state aggregation and crystal structures, are reviewed due to their influence on charge transport in polymer field-effect transistors.
Pure organic, heavy‐atom‐free room‐temperature phosphorescence (RTP) materials have attracted much attention and have potential applications in photoelectric and biochemical material fields owing to ...their rich excited state properties. They offer long luminescent lifetime, diversified design, and facile preparation. However, recent achievements of efficient phosphorescence under ambient conditions mainly focus on ordered crystal lattices or embedding into rigid matrices, which require strict growth conditions and have poor reproducibility. Herein, we developed a concise approach to give RTP with a decent quantum yield and ultralong phosphorescence lifetime in the amorphous state by radical binary copolymerization of acrylamide and different phosphors with oxygen‐containing functional groups. The cross‐linked hydrogen‐bonding networks between the polymeric chains immobilize phosphors to suppress non‐radiative transitions and provide a microenvironment to shield quenchers.
He ain't heavy: The radical binary copolymerization of acrylamide and different phosphors with oxygen‐containing functional groups allows efficient room‐temperature phosphorescence with ultralong lifetime in an amorphous polymer. The cross‐linked hydrogen‐bonding networks between the polymeric chains immobilize phosphors and suppress non‐radiative transitions.
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