Since polymers of cyclic topology have no main chain terminus, and the conformation is limited, they show physical and chemical properties different from those of linear polymers even the composition ...and molecular weight are the same. In order to pursue functions based on the topology of polymers, we have developed synthetic methods for cyclic polymers and constructed nanostructures by self-assembly. As a result, it was found that micelles and vesicles formed by cyclic polymers exhibit characteristics, which were greatly changed as compared with those of linear polymers. Based on cyclic-to-linear transformation, a gelling agent was developed, and furthermore, the reversible and repeatable topological conversion was achieved. Moreover, monolayer assemblies such as self-assembled monolayers on a gold surface and Langmuir–Blodgett films were constructed from cyclic macromolecules.
Nano-sized metal particles are attracting much interest in industrial and biomedical applications due to the recent progress and development of nanotechnology, and the surface-modifications by ...appropriate polymers are key techniques to stably express their characteristics. Herein, we applied cyclic poly(ethylene glycol) (c-PEG), having no chemical inhomogeneity, to provide a polymer topology-dependent stabilization for the surface-modification of gold nanoparticles (AuNPs) through physisorption. By simply mixing c-PEG, but not linear counterparts, enables AuNPs to maintain dispersibility through freezing, lyophilization, or heating. Surprisingly, c-PEG endowed AuNPs with even better dispersion stability than thiolated PEG (HS-PEG-OMe). The stronger affinity of c-PEG was confirmed by DLS, ζ-potential, and FT-IR. Furthermore, the c-PEG system exhibited prolonged blood circulation and enhanced tumor accumulation in mice. Our data suggests that c-PEG induces physisorption on AuNPs, supplying sufficient stability toward bio-medical applications, and would be an alternative approach to the gold-sulfur chemisorption.
A variety of single- and multicyclic polymers having programmed chemical structures with guaranteed purity have now become obtainable owing to a number of synthetic breakthroughs achieved in recent ...years. Accordingly, a broadening range of studies has been undertaken to gain updated insights on fundamental polymer properties of cyclic polymers in either solution or bulk, in either static or dynamic states, and in self-assemblies, leading to unusual properties and functions of polymer materials based on their cyclic topologies. In this article, we review recent studies aiming to achieve distinctive properties and functions by cyclic polymers unattainable by their linear or branched counterparts. We focus, in particular, on selected examples of unprecedented topology effects of cyclic polymers upon self-assemblies, dynamics and responses, to highlight current progress in
Topological Polymer Chemistry
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Unprecedented topology effects have been disclosed by new cyclic polymers upon their self-assemblies, dynamics and responses.
Human in vitro gametogenesis may transform reproductive medicine. Human pluripotent stem cells (hPSCs) have been induced into primordial germ cell-like cells (hPGCLCs); however, further ...differentiation to a mature germ cell has not been achieved. Here, we show that hPGCLCs differentiate progressively into oogonia-like cells during a long-term in vitro culture (approximately 4 months) in xenogeneic reconstituted ovaries with mouse embryonic ovarian somatic cells. The hPGCLC-derived oogonia display hallmarks of epigenetic reprogramming-genome-wide DNA demethylation, imprint erasure, and extinguishment of aberrant DNA methylation in hPSCs-and acquire an immediate precursory state for meiotic recombination. Furthermore, the inactive X chromosome shows a progressive demethylation and reactivation, albeit partially. These findings establish the germline competence of hPSCs and provide a critical step toward human in vitro gametogenesis.
Accumulating evidence suggests that cellular heterogeneity in organs and cell-cell and tissue-tissue interactions are crucial for maintaining physical homeostasis and disease progression. Endocrine ...organs also exhibit cellular heterogeneity and comprise multiple cell types. For instance, the pituitary gland comprises five types of pituitary hormone-producing cells as well as non-hormone-producing supporting cells, such as fibroblasts, endothelial cells, and folliculostellate cells. However, the functional roles of the interactions between hormone-producing and non-producing cells in the pituitary gland remain incompletely understood. Over the past decade, emerging technologies such as single-cell and spatial transcriptomics have provided excellent tools for studying cellular heterogeneity and their interactions; however, the application of these technologies in endocrine research remains limited. This review provides an overview of these technologies and discusses their strengths and limitations. Additionally, we also summarize the potential future applications of single-cell and spatial transcriptomics in the study of endocrine organs and their disorders.
•Investigations on acoustic flow and cavitation treatment are conducted using sonotrodes with various tips.•Conical tip yields quite different pattern of acoustic flow and higher efficiency of ...cavitation treatment.•A numerical model for simulating acoustic flow and predicting cavitation zone is developed.
Aiming at improving the efficiency of cavitation treatment, this work investigates characteristics of acoustic streaming and cavitation generated in water by dumbbell-shaped sonotrodes with plane, truncated and conical tips. The main emphasis was placed on elucidating the effects of tip shape and vibration amplitude ranged from 40 to 60 μm. The PIV technique and Weissler reaction were used to measure flow pattern and velocity of acoustic streaming, and cavitation efficiency, respectively. To provide a theoretical explanation to the experimental results, a self-developed mathematical model was used to simulate the acoustic streaming and predict the size of cavitation zone numerically.
Both the experimental and numerical results revealed that the sonotrode tip shape affects the acoustic streaming significantly, altering the flow magnitude and direction from fast and downward under the plane and truncated tips to relatively slow and upward near the conical tip. Besides, the conical tip provides a more efficient cavitation treatment in comparison with the plane and truncated tips. The simulation results showed that widening of cavitation zone and altering of acoustic streaming velocity and direction near the sonotrode tip are responsible for the enhancement of cavitation treatment efficiency.
Alkali metal carboxylates were discovered as efficient and simple catalysts for the ring-opening polymerization of cyclic esters that are alternatives to conventional metal-based catalysts and ...organocatalysts. In our system using an alcohol initiator and this simple catalyst, biodegradable and biocompatible aliphatic polyesters, such as poly(lactide), poly(ε-caprolactone), poly(δ-valerolactone), and poly(trimethylene carbonate), were obtained with predictive molecular weights ranging from 3500 to 22 600 and narrow dispersities. A kinetic experiment for the ROP of l-lactide confirmed the controlled/living nature of the present ROP system, which allowed the precise synthesis of end-functionalized polyesters as well as multihydroxyl-containing polyesters, including α,ω-hydroxy telechelic and star-shaped polyesters. Furthermore, a block copolymer containing the poly(l-lactide) segment was successfully synthesized using a macroinitiator possessing a hydroxyl group at the chain end. The tunability of the alkali metal carboxylates by the appropriate choice of the alkyl moiety and countercation enables not only control of the polymerization behavior but also expansion of the scope of the applicable monomers. Given the low cost, easy handling, and low toxicity of the alkali metal carboxylates, the present ROP system can be highly promising for both laboratory- and industrial-scale polyester productions.
Recent progress observed in Topological Polymer Chemistry is outlined with particular emphasis on single-cyclic (ring) and multi-cyclic polymers having programmed chemical structures, now becoming ...obtainable with guaranteed purity by newly developed synthetic protocols. By making use of these topological polymers, unprecedented opportunities have now been realized to provide new insights on fundamental polymer properties either in solution or bulk, in static or dynamic states, or in self-assemblies. Moreover, unusual properties and functions for polymer materials have now been revealed based on their cyclic topologies, i.e., topology effects, unattainable either by linear or branched counterparts.
Inhibitors of Mek1/2 and Gsk3β, known as 2i, enhance the derivation of embryonic stem (ES) cells and promote ground-state pluripotency in rodents. Here we show that the derivation of female mouse ES ...cells in the presence of 2i and leukaemia inhibitory factor (2i/L ES cells) results in a widespread loss of DNA methylation, including a massive erasure of genomic imprints. Despite this global loss of DNA methylation, early-passage 2i/L ES cells efficiently differentiate into somatic cells, and this process requires genome-wide de novo DNA methylation. However, the majority of imprinting control regions (ICRs) remain unmethylated in 2i/L-ES-cell-derived differentiated cells. Consistently, 2i/L ES cells exhibit impaired autonomous embryonic and placental development by tetraploid embryo complementation or nuclear transplantation. We identified the derivation conditions of female ES cells that display 2i/L-ES-cell-like transcriptional signatures while preserving gamete-derived DNA methylation and autonomous developmental potential. Upon prolonged culture, however, female ES cells exhibited ICR demethylation regardless of culture conditions. Our results provide insights into the derivation of female ES cells reminiscent of the inner cell mass of preimplantation embryos.
•Investigations on acoustic cavitation assisted plasma were conducted with a novel reactor.•Treatable range of solution electric conductivity has been remarkably expanded with acoustic ...cavitation.•Micro cavitation bubbles behave as “bridges” to help plasma propagate through water.•ACAP process shows good performance on Rhodamine B degradation with synergistic effects.
A novel wastewater treatment process, acoustic cavitation assisted plasma (ACAP) is proposed in this study aiming at expanding the treatable range of water pollutants due to a synergetic effect of ultrasound irradiation and high voltage plasma discharge. In this process, the role of acoustic cavitation is not only to provide generation of chemically active OH radicals, as for example in conventional ultrasonic wastewater treatment techniques, but also to ensure conditions for stable plasma generation in wastewater and, thus, to extend the treatable range of water pollutants. Rhodamine B (RhB) was used as a model pollutant in experiments examining effects of ultrasound amplitude, RhB initial concentration, output voltage, solution pH and electrical conductivity on the RhB degradation efficiency. The results revealed that the ultrasound-assisted plasma generation requires lower output voltages and allows to increase the acceptable range of electrical conductivity of treatable solutions up to 1000 μS/cm, that is about 24 times higher than in the case of conventional plasma discharge treatment. The alkaline and acid medium were found to be favorable for higher degradation efficiency. Additional measurements and results of recent investigations concerning underwater plasma showed that microbubbles presented in cavitation zone could serve as “bridges” making the pulse discharge propagation between the electrodes easier than in the conventional case. Besides, acoustic cavitation assists a faster transition of plasma discharge from ineffective streamer type to more effective spark type that further contributes to the improvement of the treatment performance.
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