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Empagliflozin (EMP) is known for its poor safety and efficacy profile due to its fast body distribution and poor solubility. Accordingly, an oral long-acting and floating/raft-forming nano gel was optimized to release coated EMP nanoparticles, and the released EMP nanoparticles showed enhanced dissolution compared to raw EMP particles. To repurpose EMP for cancer treatment, EMP shows anti-cancer and anti-inflammatory effects against cancer cells. EMP nanoparticles were characterized using FT-IR, PXRD, SEM, EMP encapsulation assay, and release studies. The raft-forming gel encapsulating the EMP was optimized and characterized. The EMP co-polymeric nanoparticles were studied to investigate EMP anti-cancer and anti-inflammatory activities against stomach cancer cells. The solubility of EMP nanoparticles was enhanced in 0.1 N HCl and pH 6.8 by 5 and 12 folds, respectively, compared to raw EMP powder. The particle size and zeta-potential values of improved EMP nanoparticles were 135.40 ± 18.60 nm, and -19.30 ± 0.80 mV, respectively. FT-IR, PXRD, SEM and TEM characterizations revealed polymeric coating of EMP particles. The study suggested that this optimized controlled-release raft-forming gel is a promising local oral approach against stomach cancer. The repurposing of EMP co-polymeric nanoparticles for stomach cancer and associated gastritis treatment was justified., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)

In the present research, we have synthesized new vinyl ketone monomers with mesogenic substituents, namely, 8-(3′-chloro-4′-pentyl-[1,1′-biphenyl-4-oxy)oct-1-en-3-one (BVK) and 8-[2′-chloro-4‴-octyl-[1,1′:4′,1″:4″,1‴-quaterphenyl-4-oxy]oct-1-en-3-one (QVK). The comparison of BVK, QVK, and previously synthesized 8-((4″-((1R,4S)-4-butylcyclohexyl)-2′-chloro-[1,1′,4′,1″-terphenyl]-4-yl)oxy)oct-1-en-3-one (TVK) has revealed that all of them are able to form crystals, while their ability to exhibit liquid crystalline behavior depends on the number of phenyl substituents attached to the para-position of the phenoxy group and is observed for TVK and QVK only. All of the monomers are able to achieve self-polymerization upon heating and free radical polymerization in bulk or in solution under the action of the common radical initiator AIBN. We have also succeeded in the RAFT polymerization of the synthesized vinyl ketones BVK and TVK using asymmetrical trithiocarbonates. The synthesized poly(vinyl ketones) exhibit LC behavior and are able to undergo photodegradation upon UV irradiation.

PolarFS is a distributed file system developed by Alibaba with ultra-low latency and high availability. It implements a variant of the Raft consensus protocol, called ParallelRaft. ParallelRaft breaks Raft's strict serialization restrictions in the commitment and execution of log entries and enables state machines to commit and execute log entries in an out-of-order way. However, ParallelRaft is not open-sourced. It has only a brief description, lacking formal specification. Moreover, the correctness of ParallelRaft has not been manually proven or formally checked. The purpose of the study is to provide a precise formal specification for ParallelRaft and to prove its correctness. Specifically, the following main contributions are accomplished. First, to clarify the relationship between Raft and ParallelRaft, ParallelRaft-SE (Sequential Execution) is proposed, which allows out-of-order commitment but prohibits out-of-order executions. Also, a refinement mapping from ParallelRaft-SE to Multi-Paxos is established. Second, it is discovered that ParallelRaft, according to its brief description in the literature, neglects the so-called "ghost log entries" phenomenon, which may violate the consistency among state machines. Therefore, based on ParallelRaft-SE, ParallelRaft-CE (Concurrent Execution) is proposed. ParallelRaft-CE avoids the "ghost log entries" phenomenon and ensures the consistency among state machines when executing concurrently by limiting parallelism in the commitment of log entries. The correctness of ParallelRaft-CE is proved manually. Finally, the formal specifications of ParallelRaft-SE and ParallelRaft-CE are provided by TLA+ (TLA stands for temporal logic of actions), and the refinement mapping from ParallelRaft-SE to Multi-Paxos and the correctness of ParallelRaft-CE are verified using the TLC model checker when the number of participants of the protocols is small. [ABSTRACT FROM AUTHOR]

In human body, alveoli are the primary sites for gas exchange which are formed by the dilation and protrusion of bronchioles at the end of the lung, and the rapid gas‐exchanging process in the alveoli ensures normal life activities. Based on the unique structures and functions of alveoli, it is necessary to study the regulation mechanism of its formation, respiration, and apoptosis. Herein, a class of reversible addition−fragmentation chain transfer (RAFT)‐derived amphiphilic triblock copolymers, PEO‐b‐P(DEAEMA‐co‐FMA)‐b‐PS is designed and synthesized. Due to the amphiphilic and gas‐responsive segments, these triblock copolymers can self‐assemble in aqueous solution and undergo the morphological transition from nanotubes to vesicles under gas stimulation; meanwhile, in the cycles of CO2/O2 stimulation, these vesicles can further realize the volume expansion and contraction, eventually rupture. The gas‐driven morphological transformations of these aggregates successfully imitate the formation, respiration, and apoptosis of alveoli, and provide an essential basis for revealing the life phenomena. [ABSTRACT FROM AUTHOR]

Fluorinated polymers are important materials that are widely used in many areas as taking the advantage of inertness to chemical corrosion, prominent weather resistance, low flammability, and good thermal stability. Poly(vinylidene fluoride) (PVDF) based fluoropolymers is the most common type of commercial fluoropolymer especially used as dielectric materials. However, there are always some shortcomings in practical applications, so it is necessary to modify PVDF-based fluoropolymers for better application. Controlled/living radical polymerization (CRP) and related techniques have become a powerful approach to tailoring the chemical and physical properties of materials and have given rise to great advances in modification of PVDF-based fluoropolymers. [ABSTRACT FROM AUTHOR]

Molecular oxygen is a radical scavenger in both conventional and controlled radical polymerization (CRP), resulting in many time-consuming methods for physically removing oxygen before the polymerization. Different approaches have been developed to have oxygen tolerance by chemically consuming or converting molecular oxygen into non-initiating species to address this issue. Recently, we propose another approach called oxygen initiation that directly transforms molecular oxygen into the initiating carbon radical in CRP. This feature article summarizes our recent developments in this direction. Oxygen-initiated reversible addition-fragmentation transfer (RAFT) polymerization has been successfully conducted using oxygen and trialkylborane as co-initiators under the ambient conditions and atmosphere without any prior degassed procedures. This gas-triggered initiation provides the opportunity for spatiotemporal control of the polymerization by molecular oxygen or air. Rationally synthesized alkylborane compounds could derive the predesigned structure of the initiating alkyl radical to minimize the side reactions and free polymer chains, achieving the synthesis of ultra-high molecular weight polymers. The challenges and perspectives are also discussed in the end. [ABSTRACT FROM AUTHOR]

Photoenzymatic reversible addition-fragmenatation chain transfer (RAFT) emulsion polymerization, surfactant-free or ab initio, of various monomers is reported with oxygen tolerance. In surfactant-free emulsion polymerizatoin, poly(N, N-dimethylacrylamide)s were used as stabilizer blocks for emulsion polymerization of methyl acrylate, n-butyl acrylate and styrene, producing well-defined amphiphilic block copolymers, including those with an ultrahigh molecular weight, at quantitative conversions. The controlled character of surfactant-free emulsion polymerization was confirmed by kinetic studies, chain extension studies and GPC analyses. Temporal control was demonstrated by light ON/OFF experiments. In ab initio emulsion polymerization of methyl acrylate and methyl methacrylate, low-dispersity hydrophobic polymers were synthesized with predictable molecular weights. This study extends the monomer scope suitable for photoenzymatic RAFT polymerization from hydrophilic to hydrophobic monomers and demonstrates that oxygen-tolerance can be equally achieved for emulsion polymerization with excellent RAFT control. [ABSTRACT FROM AUTHOR]

To address the problem of performance degradation caused by the blockchain backup mechanism as well as the high throughput and low latency requirements characteristic of blockchain applications, this paper optimizes the Raft consensus algorithm for the Hyperledger Fabric platform in terms of both log replication and leader election. In the log replication phase, the improvement of log replication based on apportionment idea aims to reduce the communication complexity of leader node by involving peer node in distributing log information. In the leader election phase, the improvement of leader election based on vote change mechanism changes the vote affiliation of peer node based on a comparison of votes from candidate nodes, aims to reach consensus in a round of election and reduces the election time. Through the performance test of the blockchain, it is demonstrated that the improved AdRaft algorithm improves 5.8% in throughput and reduces 1.3% in latency over the original Raft algorithm. [ABSTRACT FROM AUTHOR]

This study presents the successes in polystyrene (PS) synthesis through reversible additional fragmentation chain transfer (RAFT) polymerization. For RAFT polymerization of styrene, diethanolamine (DEA) RAFT agent was used. The PS synthesis has made significant progress in the control of the molecular weight distribution of polymeric products. The average molecular weight between 37113 and 43183 g mol–1 of PS determined by gel-permeation chromatography (GPC) was consistent with the accounted values. The controlled polymerization system also exhibited first-order linear kinetics and produced PS with slightly high dispersity (Mw/Mn = 1.42). The RAFT agents and polymers were characterized by NMR and Fourier transform-infrared (FTIR) spectroscopies, GPC), and differential scanning calorimetry (DSC). Besides, the structural and electronic properties for monomer, trimer and hexamer molecules on the DEA RAFT agent series were performed by density functional theory studies. Energy gap (Δ) values for monomer, trimer and hexamer were found to be 4.0396, 4.0943 and 4.0010 eV, respectively. These results show the chemical activity in the series and the charge transferability within the polymer. In the same series, the dipole moment values increased in parallel with the chain growth, as μ(D) = 0.9124, 1.9951 and 2.0918, respectively. [ABSTRACT FROM AUTHOR]

Atherosclerosis, the major cause of vascular disease, is an inflammatory process driven by entry of blood monocytes into the arterial wall. LDL normally enters the wall, and stimulates monocyte adhesion by forming oxidation products such as oxidised phospholipids (oxPLs) and malondialdehyde. Adhesion molecules that bind monocytes to the wall permit traffic of these cells. CD14 is a monocyte surface receptor, a cofactor with TLR4 forming a complex that binds oxidised phospholipids and induces inflammatory changes in the cells, but data have been limited for monocyte adhesion. Here, we show that under static conditions, CD14 and TLR4 are implicated in adhesion of monocytes to solid phase oxidised LDL (oxLDL), and also that oxPL and malondialdehyde (MDA) adducts are involved in adhesion to oxLDL. Similarly, monocytes bound to heat shock protein 60 (HSP60), but this could be through contaminating lipopolysaccharide. Immunohistochemistry on atherosclerotic human arteries demonstrated increased endothelial MDA adducts and HSP60, but endothelial oxPL was not detected. We propose that monocytes could bind to MDA in endothelial cells, inducing atherosclerosis. Monocytes and platelets synergized in binding to oxLDL, forming aggregates; if this occurs at the arterial surface, they could precipitate thrombosis. These interactions could be targeted by cyclodextrins and oxidised phospholipid analogues for therapy.

Raft formation is a frequently encountered problem during alumina feeding in the Hall-Héroult-process and will delay alumina from being dissolved into the melt. The mechanisms for the formation and disintegration of rafts are however not thoroughly understood yet. The current study investigates the dissolution behavior and raft structure from three different types of secondary alumina in a lab cell, with a particular attention to effect of fines, and involves both sampling of rafts and video recordings of the feeding. The mass loss rate was calculated to vary between −1.57 and −0.42 g min−1 for regular bulk alumina, and −1.15 and −0.06 g min−1 for fines. Rafts created from bulk alumina were flat with a distinct bulge or crater placed in the center of it, while rafts created from fines had a pellet-shaped structure and traces of undissolved alumina in the middle. The observed structure is due to the initial spreading of powder, confirmed by video recordings.

Herein, we report the preparation of temperature-responsive antibody–nanoparticles by the direct polymerization of N-isopropylacrylamide (NIPAAm) from immunoglobulin G (IgG). To this end, a chain transfer agent (CTA) was introduced into IgG, followed by the precipitation polymerization of NIPAAm in an aqueous medium via reversible addition–fragmentation chain transfer polymerization above the lower critical solution temperature (LCST). Consequently, antibody–polymer particles with diameters of approximately 100–200 nm were formed. Owing to the entanglement of the grafted polymers via partial chemical crosslinking, the antibody–nanoparticles maintained their stability even at temperatures below the LCST. Further, the dispersed nanoparticles could be collected by thermal precipitation above the LCST. Additionally, the antibody–nanoparticles formulation could maintain its binding constant and exhibited a good resistance against enzymatic treatment. Thus, the proposed antibody–nanoparticles can be useful for maximizing the therapeutic potential of antibody–drug conjugates or efficacies of immunoassays and antibody recovery and recycling.

In recent years, video stabilization has improved significantly in simple scenes, but is not as effective as it could be in complex scenes. In this study, we built an unsupervised video stabilization model. In order to improve the accurate distribution of key points in the full frame, a DNN-based key-point detector was introduced to generate rich key points and optimize the key points and the optical flow in the largest area of the untextured region. Furthermore, for complex scenes with moving foreground targets, we used a foreground and background separation-based approach to obtain unstable motion trajectories, which were then smoothed. For the generated frames, adaptive cropping was conducted to completely remove the black edges while maintaining the maximum detail of the original frame. The results of public benchmark tests showed that this method resulted in less visual distortion than current state-of-the-art video stabilization methods, while retaining greater detail in the original stable frames and completely removing black edges. It also outperformed current stabilization models in terms of both quantitative and operational speed.

In this paper, we report a more simple and efficient way to a maleimide-structural copolymer superplasticizer(SP) that was synthesized by aqueous reversible addition-fragmentation chain transfer(RAFT) polymerization of methylallyl sulfonate (SMAS), N-carbamoyl maleimide (NCM), and N-methoxy polyethylene glycols-N'-carbamoyl maleimide (MPNCM). The structure was manifested by FTIR, 1H NMR, TGA and GPC. The comonomers content of the SP were changed by the proportion of SMAS, NCM, and MPNCM in the synthesis recipes. The effects on fluidity, adsorption, zeta potential, compressive strength, scanning electron microscopy (SEM), and Isothermal calorimetry in cement mortars were investigated. The experimental result showed that the SP2 with the certain monomer ratio of SMAS, NCM, and MPNCM had excellent workability of concrete, dispersion, and retention capability. The positive and negative charges of the SP2 interacted with the charges of the surface of cement pastes were largely responsible for enhancing the flocculation of cement particles with the effects of repulsion of stereo hindrance forming. The saturated adsorption amount changes with the various proportions of SMAS, NCM, and MPNCM on account of the different ratios of the negative and positive charges on the cement particles. The proper ratio of comonomers of SP2 was benefiting the adsorption. [ABSTRACT FROM AUTHOR]

A series of thermoresponsive polyacrylamides containing sulfide, sulfone, or sulfoxide was successfully prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization. The thermal properties of polyacrylamides with sulfone or sulfoxide, which have not been studied before, were investigated for the first time. While poly[N‐(2‐(propylsulfonyl)ethyl)acrylamide] (P2SO2) with sulfone groups was water insoluble, poly[N‐(2‐(propylsulfinyl)ethyl)acrylamide] (P2SO) with sulfoxide groups was water soluble, indicating that the sulfoxide moiety is more hydrophilic than sulfone. By controlling the end of the polymer chain, we synthesized poly[N‐(2‐(ethylsulfonyl)ethyl)acrylamide] (P1SO2) and poly[N‐(2‐(butylsulfinyl)ethyl)acrylamide] (P3SO), which exhibit an lower critical solution temperature (LCST) in water around 24–26°C. For adjusting a wide range of LCST, we synthesized the random copolymers by controlling the initial feed ratio of hydrophobic M2SO2 and hydrophilic M2SO. The amphiphilic block copolymers were also synthesized and assembled in water to yield the micelles. After adding H2O2 to this micellar solution, the hydrophobic block was oxidized and converted to a hydrophilic block, leading to the transformation of micelles to unimers. [ABSTRACT FROM AUTHOR]

The integration of multi-access edge computing (MEC) and RAFT consensus makes it feasible to deploy blockchain on trustful base stations and gateways to provide efficient and tamper-proof edge data services for Internet of Things (IoT) applications. However, reducing the latency of storing data on blockchain remains a challenge, especially when an anomaly-triggered data flow in a certain area exceeds the block generation speed. This letter proposes an intelligent transaction migration scheme for RAFT-based private blockchain in IoT applications to migrate transactions in busy areas to idle regions intelligently. Simulation results show that the proposed scheme can apparently reduce the latency in high data flow circumstances. [ABSTRACT FROM AUTHOR]

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One of the efficient methods for enhancement of the heavy metal adsorption of nano graphene oxide (GO) is the surface modification through functional polymer. In this study, cross-linked polymethacrylamide (CPMAM) as hydrogel network was synthesized via reversible addition-fragmentation chain transfer (RAFT) technique to graft on the surface of GO activated phenylalanine (GO-Ph). The proposed mechanism for the grafting and chemically crosslinking reactions was proved with various techniques. The modified GO was employed as an excellent adsorbent for the removing of Cd(II) ions from aqueous solutions. The results indicated that ion adsorption basically relies on adsorbing time, solution pH, temperature, and initial Cd(II) concentration. In the optimized condition adsorption capacity was calculated to be 41.14 mg/g. Moreover, the adsorption kinetics and isotherm analysis demonstrated that the adsorption model was fitted with the pseudo-second-order and Freundlich isotherm models, respectively. The thermodynamic study showed that the ion adsorption process was endothermic and spontaneous. Based on the obtained results, the surface-modified GO with CPMAM has the potential to be used in sensitive environment that needs to completely remove Cd(II) ions. [ABSTRACT FROM AUTHOR]

Adsorption of proteins on biological surfaces is a detrimental phenomenon that reduces the work‐life of the implants in various biomedical applications. Here, we synthesized a new class of thermoresponsive zwitterionic poly(phosphobetaine) (PMPC) microgel with excellent surface antifouling property by macro‐RAFT mediated thiol‐epoxy click reaction. End‐group modified zwitterionic PMPC homopolymers with well‐defined molecular weight and narrow dispersity were grafted onto poly(N‐vinylcaprolactam‐co‐glycidyl methacrylate) (PVG) copolymer backbone followed by addition of a cross‐linker, leading to microgel formation. While no upper critical solution temperature (UCST) was found in poly(N‐vinylcaprolactam‐co‐glycidyl methacrylate‐g‐2‐methacryloyloxyethyl phosphorylcholine) (PVGP) graft copolymers, the corresponding microgels exhibited both UCST and lower critical solution temperature (LCST) transitions, related to the swelling and collapse of PMPC and poly (N‐vinylcaprolactam) (PVCL) components respectively. An increase in the molecular chain length of the PMPC increased the shifting of UCST and LCST of the microgels to higher temperatures, due to the ability of zwitterionic groups to coordinate a large number of water molecules. The effect of the variation in the molecular weights of amphiphilic poly(ethylene glycol) diamine (PEG‐NH2) cross‐linker was also reflected in both temperature and salt responsiveness of the microgels. The efficacy of the microgels as potential antifouling materials was further studied by fluorescence microscopy and XPS analysis on microgel coatings treated with FITC‐BSA solution and pure BSA solution respectively. Lower protein adsorption was observed for microgels grafted with higher molecular chain length of PMPC, whereas, the microgels synthesized using higher molecular weight PEG‐NH2 diamine cross‐linker displayed greater protein adsorption on their surfaces. [ABSTRACT FROM AUTHOR]

In the plasma membranes of eukaryotic cells, relatively ordered lipid–protein domains can be formed. The characteristics of the interaction of domains can have a significant effect on the processes that require the co-localization of several membrane proteins. The ordered lipid bilayer is thicker than the surrounding disordered membrane. Therefore, it is expected that elastic deformations arise at the boundary of ordered domains, aiming at smoothing the jump in bilayer thickness. The typical length of the deformations equals several nanometers, and, as two domains approach each other, the deformations induced by their boundaries begin to overlap, thereby leading to the effective lateral interaction. In this work, we theoretically considered the influence of amphipathic peptides, adsorbed on the membrane, on the interaction energy of ordered domains. Amphipathic peptides can partially incorporate into the membrane, inducing elastic deformations therein. We used the theory of lipid membrane elasticity to analyze the deformation energy of various configurations of ordered domains and amphipathic peptides. In a membrane without peptides, it is necessary to overcome some energy barrier to bring two parallel boundaries of ordered domains into contact with each other. According to the results of our calculations, the presence of amphipathic peptides in a membrane leads to a severalfold increase in the height of this energy barrier. Thus, amphipathic peptides should significantly hinder the fusion of ordered domains and thereby contribute to the stabilization of the ensemble of nano-domains. [ABSTRACT FROM AUTHOR]

Magnetic nanocomposites are promising drug delivery systems for release and encapsulation of drugs because of the mild procedure of their fabrication from biopolymers, excellent chemical stability, their admissible magnetic properties and biocompatibility. The development of biocompatible carrier for hydrophobic drug delivery survives a longstanding issue in cancer therapy. We design and prepare a drug delivery system based on (β-Cyclodextrin)-star-poly(2-hydroxyethyl methacrylate)-graft-ε-Caprolactone β-CD-star-P(HEMA-g-CL) which was prepared by combining distinct polymerization techniques via ring open polymerization and reversible addition of fragmentation chain transfer polymerization. Then magnetic nanoparticles were functionalized with β-CD-star-P(HEMA-g-CL). The morphology and nanocomposite properties behaviors were investigated by field emission scanning electron microscopy, X-ray diffraction, dynamic light scattering and vibrating sample magnetometer (VSM) analysis. The model drug applied in this study is docetaxel (DTX). DTX-encapsulation efficacy was 91.7%. Release behaviors of DTX from the magnetic nanocomposite demonstrated that the rate of DTX release could be efficiently controlled through pH. [ABSTRACT FROM AUTHOR]

The high performance liquid chromatographic (HPLC) method was developed for the combined estimation of sodium alginate and pectin in raft forming pharmaceuticals on C18 column ZORBAX ODS (1.5 cm × 4.6 mm, 5 μm) with UV detection at 378 nm. The assay condition comprised of phosphate buffer pH 7.4 and methanol 60:40% v/v at a flow rate of 1.25 mL/min. The separation of sodium alginate and pectin with good resolution and a retention time less than 8 min was attained. The method was linear over a range of 200–800 μg/mL of sodium alginate and pectin. The regression values obtained from linearity curve of sodium alginate and pectin were 0.9993 and 0.9991, respectively. The retention time of sodium alginate and pectin was 3.931 and 7.470 min, respectively. The percent recovery of sodium alginate and pectin ranged from 94.2–98.5% and 92.1–98.4% respectively. The limit of detection (LOD) and limit of quantification (LOQ) of sodium alginate were found to be 2.443 and 3.129 μg/mL and the LOD and LOQ of pectin were 3.126 and 3.785 μg/mL, respectively. The resolution of sodium alginate and pectin was found in the range of 1.03–1.89 and 1.10–1.91, respectively. This method has been successfully applied to analyze the concentrations of sodium alginate and pectin in raft forming drug delivery systems. [ABSTRACT FROM AUTHOR]

Shellfish and algae aquaculture is widespread in marine waters with an extensive footprint that interacts in complex ways with the surrounding environment. Potential impacts include habitat alteration via modifications to flows, nutrients and sediment, and changes in the occurrence of parasites, disease, and other organisms in the food web. To quantify the impact of suspended aquaculture, understanding its scale and spatial arrangement is key. Using satellite imagery, we identified suspended aquaculture structures and assessed their density, type, and distance from shore in countries that produce >90% of global shellfish and algae (China, South Korea, Chile, Japan, and Vietnam). China and Vietnam contained the highest number of farms, with structure density greatest in South Korea and China. On average, longlines were 8 times more common than rafts, and were the dominant production type in all countries except Japan. Farms were located closest to shore in Vietnam (mean ± SE = 469 ± 458 m), and furthest from the coast in China (2010 ± 2157 m). Characterising cultivation techniques and the sprawl of infrastructure across major production regions informs farm placement, management, and regulation to mitigate risks and maximise the benefits associated with suspended aquaculture. • Satellite imagery revealed the spatial extent of suspended aquaculture. • Longlines dominated in China, South Korea, Chile and Vietnam, rafts in Japan. • Structures most abundant in China and most dense in South Korea and China. • On average, farms were closest to shore in Vietnam and furthest in China. • Implications for production, the environment and coastal spatial management. [ABSTRACT FROM AUTHOR]

[Display omitted] • Composite of py-pAMHS-NH 3 +-ph with rGO can be facilely prepared by π-π stacking interaction. • The rGO-py-pAMHS-NH 3 +-ph could efficiently eliminate HCHO via chemical reaction with the only by-product of water. • 206.41 mg HCHO could be effectively removed within 4 h by 1.0 g rGO-py-pAMHS-NH 3 +-ph. • Removal of HCl/H 2 S could be achieved by amine groups tethered rGO-py-pAMHS-NH 2 -ph via ion-bonding interactions. • The rGO-py-pAMHS-NH 3 +-ph shows a good cycle stability, thus has promising application prospect. In this paper, the contribution of self-assembled composite material of bifunctional polymer prepared by RAFT polymerization and rGO to the removal of low concentration HCHO and acids from air were systematically studied. Experimental results demonstrate that the condensation reaction between HCHO and the protonated amino group at the terminal of the rGO-py-pAMHS-NH 3 +-ph chain effectively can eliminate HCHO chemically, resulting in the release of H 2 O as the sole by-product following oxime bonds formation. rGO alone is incapable of chemically removing gaseous HCHO, but when combined with the py-pAMHS-NH 3 +-ph, efficient HCHO conversion can be achieved, well elucidating the remarkable HCHO removal capability via rGO-py-pAMHS-NH 3 +-ph. The HCHO chemical removal performance of composite is evaluated by a self-made device at the 1000 mL/min N 2 velocity under 25 °C and 50 % RH and it is found that 206.41 mg of HCHO can be removed in approximately 4 h by using 1.0 g of rGO-py-pAMHS-NH 3 +-ph. In addition, cycling experiments demonstrate the rGO-py-pAMHS-NH 3 +-ph possesses good durability. We also find that the rGO-py-pAMHS-NH 2 -ph has the ability to remove acids when the terminal protonated amino groups have been converted into amine functionalities. This green and zero-carbon emission methodology for chemical removal of HCHO degradation and acid pollutants could provide valuable reference for developing other efficient strategies to remove other pollutants such as VOCs etc. [ABSTRACT FROM AUTHOR]

[Display omitted] • Cu@A-HNT catalysts can effectively reduce the Cu residue in MBP-CTAs, meeting the requirements of RAFT polymerization. • This study demonstrates a potential method for constructing functional materials with multiblock copolymers. • This method could enable the facile adjustment of the skeleton of multiblock copolymers. Multiblock copolymer macrochain-transfer agents (MBP-CTAs) can be used to synthesize MBPs in one pot via reversible addition-fragmentation chain-transfer (RAFT) polymerization. MBP-CTAs can be efficiently synthesized via a copper-catalyzed azide-alkyne cycloaddition reaction. However, traditional purification methods cannot sufficiently purify MBP-CTAs, resulting in the failure of RAFT. In this study, it was discovered that using a supported catalytic system, namely, Cu@A-HNTs, inhibited the connection between Cu and S. The residual Cu content in the MBP-CTA was successfully reduced to a low level (7.88 µg/mg). Then, hydrophilic and hydrophobic MBPs were synthesized through RAFT polymerization using the MBP-CTAs. Subsequently, multiblock copoly(methyl methacrylate-b-butyl methacrylate-CTA)s (PMMA-b-PBMA-c-CTA)s were successfully prepared. The MBP-CTAs and MBPs were characterized using ultraviolet–visible spectroscopy, 1H nuclear magnetic resonance, size-exclusion chromatography, matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry, differential scanning calorimetry measurements and uniaxial tensile tests. The results of performance testing of PMMA-b-PBMA-c-CTAs demonstrated that their fracture stress and strain significantly increased comparing with that of PMMA-b-CTAs. [ABSTRACT FROM AUTHOR]

[Display omitted] • Carboxylated trithiocarbonate mediates RAFT polymerization of a bisphosphonic acrylate. • Two RAFT methodologies lead to phosphonated double hydrophilic block copolymers. • DHBCs interact with lanthanide ions (Gd, Eu) to form polyionic complexes. • Bisphosphonated polyionic complexes enhance the stability of MRI contrast agents. The synthesis of double hydrophilic block copolymers (DHBCs) with one block containing bisphosphonic acid groups was performed by aqueous RAFT polymerization with two approaches, either starting from a PEO-based macro-chain transfer agent (macro-CTA) or by chain extension of a RAFT-capped bisphosphonic acrylate homopolymer with oligo(ethylene glycol) methyl ether acrylate (OEGA). By complexation with gadolinium and europium ions, these polymers are prone to form hybrid polyionic complexes (HPICs) as evidenced by mono- and multi-angle DLS, TEM and luminescence measurements. The obtained HPICs showed better chemical stability at low pH values compared to previously reported counterparts based on carboxylic and monophosphonic acid groups (i.e., PEO- b -PAA and PEO- b -PVPA respectively). Due to their high relaxivity values, the proposed HPICs show potential as contrast agents for magnetic resonance imaging (MRI). [ABSTRACT FROM AUTHOR]

[Display omitted] • The novel block copolymer PMAA-b-PGGMA with abundant hydroxyl groups was synthesized by RAFT polymerization. • The block copolymer can effectively disperse SiO 2 particles in water with broad pH values (3–13). • The SiO 2 particles was well disoersed by spatial site-blocking effect and electrostatic repulsive effect. • Sub-micron and micron sized SiO 2 particles with high solid content (35 wt%) are effective dispersed by block copolymers in water. The dispersion of silicon dioxide (SiO 2) by a block copolymer under highly acidic or strongly alkaline conditions in water is still a challenge. In this study, block copolymers containing repeating units of methacrylic acid (MAA) and glycidyl methacrylate (GMA) were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. Subsequently, the epoxide groups underwent ring-opening reaction and the polymer chain end dithioester groups were removed through one-step hydrolysis, leading to the formation of a block copolymer named PMAA- b -PGGMA, which contained abundant hydroxyl groups. Hydroxyl groups act as anchoring groups and interact with the silanol groups on the surface of SiO 2 particles simultaneously, resulting in a steric site-blocking effect. Besides, the electrostatic repulsion effect of PMAA as a stable group with a negative charge on SiO 2. The block copolymer PMAA 43 - b -PGGMA 50 can effectively disperse sub-micron- and micron-sized SiO 2 even at high SiO 2 content (35 wt%) and broad pH values (3–13) in water. [ABSTRACT FROM AUTHOR]

[Display omitted] • Synthesis of novel amphiphilic block copolymers. • Study of the thermal stability of the amphiphilic block copolymers. • Effect of the nature of the selective solvent on the micellization properties of amphiphilic copolymers. • Effect of the macromolecular architecture on the micellization properties of amphiphilic copolymers. • Encapsulation of the hydrophobic compound curcumin into the micellar structures. Block copolymers of N-vinyl pyrrolidone (NVP) and isobornyl methacrylate (IBMA), PIBMA- b -PNVP, were prepared employing the RAFT polymerization technique. IBMA was polymerized first followed by the polymerization of NVP in the presence of a suitable fluoroalcohol to accelerate the crossover reaction. The copolymers were characterized by Size Exclusion Chromatography (SEC) and NMR spectroscopy. The thermal stability of these copolymers was studied via Thermogravimetric Analysis (TGA) and Differential Thermogravimetry (DTG), showing unique characteristics compared to the respective PIBMA and PNVP homopolymers. The micellization behavior was studied in THF, which is a selective solvent for the PIBMA blocks. The corresponding statistical copolymers, PNVP- stat -PIBMA were also examined to elucidate the effect of the macromolecular architecture on the micellar properties. Furthermore, the self-assembly behavior in aqueous solutions was studied for the PIBMA- b -PNVP block copolymers. Water is a selective solvent for the PNVP blocks. Static (SLS) and dynamic light scattering (DLS) were employed to study the micellar assemblies. The encapsulation of the hydrophobic compound curcumin within the micellar core of the micellar structures in aqueous solutions was investigated by UV–Vis spectroscopy and DLS measurements. [ABSTRACT FROM AUTHOR]

Original distributed consensus algorithms are typically engineered with wired communication networks in mind. However, when these algorithms are applied in wireless networks, the unique characteristics of wireless communication among nodes, including high error rates, variable latency, and dynamic network topology, present novel challenges that necessitate the development of adaptive protocols. This article aims to address these challenges by designing an adaptive protocol specifically for the implementation of the Raft consensus algorithm within wireless environments. We first outline the key stages of this adaptive protocol, focusing on enhancing robustness and efficiency in the state synchronization and routing processes, which are demonstrated through extensive simulations. The proposed adaptive protocol intends to ensure consistent states across nodes in wireless networks, which promote reliable and effective distributed systems for a variety of applications in autonomous wireless networks, including Vehicle-to-everything (V2X), Internet of Things (IoT), and edge computing. [ABSTRACT FROM AUTHOR]

Fatemeh Farjadian,1 Somayeh Rezaeifard,2 Mahsa Naeimi,1 Sahar Ghasemi,1 Soliman Mohammadi-Samani,1,3 Mark E Welland,4 Lobat Tayebi51Pharmaceutical Sciences Research Center, Shiraz University of Medical Sciences, Shiraz, Iran; 2Institute for Cancer Research, Shiraz University of Medical Sciences, Shiraz, Iran; 3Department of Pharmaceutics, Faculty of Pharmacy, Shiraz University of Medical Sciences, Shiraz, Iran; 4The Nanoscience Centre, Department of Engineering, University of Cambridge, Cambridge, United Kingdom; 5Marquette University, School of Dentistry, Milwaukee, WI, USACorrespondence: Fatemeh FarjadianPharmaceutical Sciences Research Center, Shiraz University of Medical Sciences, P.C. 71348-14336, Shiraz, IranTel +987132424127(302)Fax +9871132424126Email farjadian_f@sums.ac.irLobat TayebiMarquette University, School of Dentistry, Milwaukee, WI 53233, USATel +1 414 288 8383Fax +2708971179Email lobat.tayebi@marquette.eduWebsitetayebigroup.mu.eduBackground: Smart materials capable of responding to external stimuli are noteworthy candidates in designing drug delivery systems. In many of the recent research, temperature and pH have been recognized as the main stimulating factors in designing systems for anti-cancer drugs delivery systems.Purpose: In this study, thermo and pH-responsive character of a nano-carrier drug delivery platform based on lysine modified poly (vinylcaprolactam) hydrogel conjugated with doxorubicin was assessed.Methods: Poly (vinylcaprolactam) cross-linked with poly (ethyleneglycol) diacrylate was prepared via RAFT polymerization, and the prepared structure was linked with lysine through ring-opening. The anti-cancer drug doxorubicin, was linked to lysine moiety of the prepared structure via Schiff-base reaction. The prepared platform was characterized by 1,HNMR and FT-IR, while molecular weight characterization was performed by size exclusion chromatography. The temperature-responsive activity was evaluated using differential scanning calorimetry and dynamic light scattering. In vitro release pattern in simulated physiologic pH at 37°C was compared with acidic pH attributed to tumor site and elevated temperature. The anticancer efficiency of the drug-conjugated structure was evaluated in breast cancer cell line MCF-7 in 24 and 48 h, and cell uptake assay was performed on the same cell line.Conclusion: According to the results, well-structure defined smart pH and temperature responsive nano-hydrogel was prepared. The enhanced release rates are observed at acidic pH and elevated temperature. We have concluded that the doxorubicin-conjugated nanoparticle results in higher cellular uptakes and more cytotoxicity.Keywords: drug delivery, DOX, RAFT, PVCL, lysine, cancer

Thermo-responsive hydrophilic polymers, including those showing tuneable lower critical solution temperature (LCST), represent a continuous subject of exploration for a variety of applications, but particularly in nanomedicine. Since biological pH changes can inform the organism about the presence of disequilibrium or diseases, the development of dual LCST/pH-responsive hydrophilic polymers with biological potential is an attractive subject in polymer science. Here, we present a novel polymer featuring LCST/pH double responsiveness. The monomer ethylthiomorpholine oxide methacrylate (THOXMA) can be polymerised via the RAFT process to obtain well-defined polymers. Copolymers with hydroxyethyl methacrylate (HEMA) were prepared, which allowed the tuning of the LCST behaviour of the polymers. Both, the LCST behaviour and pH responsiveness of hydrophilic PTHOXMA were tested by following the evolution of particle size by dynamic light scattering (DLS). In weak and strong alkaline conditions, cloud points ranged between 40–60 °C, while in acidic medium no LCST was found due to the protonation of the amine of the THOX moieties. Additional cytotoxicity assays confirmed a high biocompatibility of PTHOXMA and haemolysis and aggregation assays proved that the thiomorpholine oxide-derived polymers did not cause aggregation or lysis of red blood cells. These preliminary results bode well for the use of PTHOXMA as smart material in biological applications.

A novel method is demonstrated to encapsulate titanium dioxide pigment using directed polymerization‐induced self‐assembly (PISA) with reversible addition‐fragmentation chain‐transfer (RAFT) controlled emulsion polymerization. The polymerization is carried out in a batch process in which both styrene (Sty) and the pigment are emulsified using triblock amphiphilic macro‐RAFT copolymers as stabilizers. RAFT‐controlled chain growth leads to directed lamellar self‐assembly, forming polystyrene (PS) shells' encapsulating pigment particles with 100% efficiency. The pigment resides either at centers of single‐void vesicles or within the interior of multivoid vesiculated particles. The presence of complex morphologies such as spherical particles, nanofibers, nanoplatelets, and polymer vesicles confirms the PISA pathway. The process is optimized to preferably produce polymer‐vesiculated pigment for use as an enhanced opacifier in water‐based paint. [ABSTRACT FROM AUTHOR]

The effect of the hydrophobicity of block copolymer macro-RAFT agents on the controllability of RAFT surfactant-free cationic emulsion polymerization of styrene was investigated. Three different copolymers, poly(dimethyl aminoethyl acrylate) (PDMAEA), poly(dimethyl aminoethyl acrylate-co-styrene)-b-(butyl acrylate) (P(DMAEA-co-St)-b-PBA) and poly(dimethyl aminoethyl acrylate-co-styrene)-b-(hexafluorobutyl acrylate) (P(DMAEA-co-St)-b-PHFBA), which had different hydrophobicity in their hydrophobic segments, were synthesized and used as the macro-RAFT agents. When P(DMAEA-co-St)-b-PHFBA and P(DMAEA-co-St)-b-PBA were used as macro-RAFT agents, the RAFT surfactant-free cationic emulsion polymerization of styrene underwent very fast. But when the PDMAEA was used as the macro-RAFT agent, no polymerization of styrene was observed. The controllability of styrene polymerization with P(DMAEA-co-St)-b-PHFBA as the RAFT agent showed much better than that with P(DMAEA-co-St)-b-PBA as the macro RAFT agent. This was ascribed to hydrophobicity difference of the hydrophobic segment between P(DMAEA-co-St)-b-PHFBA and P(DMAEA-co-St)-b-PBA macro-RAFT agents. A mechanism explanation for the controllability of emulsion polymerization was proposed. The location of the active trithiocarbonate group of the macro-RAFT agent in micelle was supposed to be a key factor affecting the controllability of RAFT surfactant-free cationic emulsion polymerization of styrene. The hydrophobicity of the RAFT agent and nature of medium had impact on the location of the active trithiocarbonate group of the macro-RAFT agent in micelle and affected the polymerization controllability. [ABSTRACT FROM AUTHOR]

Zwitterionic microspheres of poly2-(dimethylamino) ethyl methacrylate (PDMAEMA) block polymethacrylic acid (MAA) were prepared by RAFT dispersion polymerization in alcohols. 4-Cyano-4-(phenylcarbonothioylthio) pentanoic acid (CPDB) was used as the RAFT agent. 2,2′-Azobis(2,4-dimethyl) valeronitrile (V65) was used as the initiator, and PDMAEMA-CPDB was used as the macro-chain transfer agent (CTA). 1HNMR was applied to determine the polymerization degrees of both PDMAEMA-CTA and PDMAEMA-b-PMAA. SEM, dynamic light scattering (DLS), and small-angle X-ray diffraction (SAX) were employed to characterize the microspheres. It was observed that the polarity of alcohols impacted the partition of MAA and V65 between the mini-droplets of PDMAEMA-CTA/MAA complexes and the continuous phase, thereby affected on the diameters of microspheres, the total conversion of MAA, and the polymerization degree of PMAA in the copolymers. For example, in methanol, the smallest diameter and polymerization degree of PMAA in the block copolymers were obtained, whereas the total conversion of MAA of the RAFT polymerization system was the highest. Most of RAFT polymerization of MAA occurred nearby PDMAEMA-CTA chains; thus, PDMAEMA-CTA acted as a template to regulate the length of PMAA in the copolymers. pH-sensitive characteristics of microspheres were dependent to the extra length of PDMAEMA-CTA, i.e., the difference of lengths between two blocks. When the length of PMAA was too short, e.g., PDMAEMA600-b-PMAA87, or the length of PMAA was closed to that of PDMAEMA, e.g., PDMAEMA79-b-PMAA93 and PDMAEMA102-b-PMAA131, the amphoteric characteristics of microspheres disappeared. The self-assembly behavior of diblock copolymers in KCl alcohol-water solution was also determined by the extra length of PDMAEMA. Microspheres turned into nanofibers or nano-ribbons, but for PDMAEMA600-b-PMAA87, the microspheres maintained their original spheric morphology. These results indicated that the charge-screening effects of salts played the key roles in the self-assembly. [ABSTRACT FROM AUTHOR]

The synthesis of hyperbranched aminobisphosphonic acid polymers via reversible addition‐fragmentation chain transfer (RAFT) self‐condensing vinyl polymerization is reported. A novel acrylamide‐functional chain transfer monomer is synthesized and characterized by 1H and 13C NMR spectroscopy, elemental analysis, and mass spectrometry. The monomer is subsequently copolymerized with an acrylamide monomer bearing a pendent amine group to create hyperbranched amine‐functional polymers with degrees of branching dictated by changing the reaction stoichiometry. The aminobisphosphonate functional group is introduced via a 3‐component Kabachnik‐Fields reaction. An alternate functionalization of the amine polymers to create acid‐degradable imine hydrogels is also employed. This work demonstrates the application of multicomponent reactions to RAFT‐derived hyperbranched polymers and provides a new route to previously inaccessible polymers. [ABSTRACT FROM AUTHOR]

Economic opportunities presented by large rivers, streams and lakes in vast steppes of Central Asia required rafts for shipment. The manufacturing of raft used by the Turkic peoples, who inhabited this region, consisted of the following: firstly sacks are prepared from animal skin, on which joists were laid on both right and left sides; over them thin pieces of wood were placed in gridiron form, and they are tightly fastened on the animal skin. This technique of construction of rafts has been transmitted among Turks for generations as a cultural object and these rafts became the most frequently used transportation vehicle on lakes and rivers. Therefore, raft became a commonly used vehicle by Turks in this territory. Although researchers argue that first water transportation vehicles were invented by Northern Sea tribes and Egyptians, Turks are also among the first boat makers. In this context, the merchants and envoys visiting Turkic geographies wrote about various types of boats and their usage. Raft has been developed by Turks as an art of handicraft to be used in bigger rivers for economic and political purposes and different types like boats without deck, wooden boats and small crafts were invented under different names, such as "bat" and "barka". The cultural value of the art of raft was not only found in written texts, but it is also described in tales, proverbs, poems, folk songs and epic poems, especially in the Old Turkic inscriptions. Turks applied a unique method in building two-winged ships known as "uchan", "târ", big "kemi" or "gemi". Consequently, Turks crossed over the rivers and lakes of Central Asia making them hegemonic nation of great steppes. The information about the construction of raft can be found in memoirs of travelers, in oral sources of folk literature and also among the Kyrgyz living along the Kyzyl-Suu River in Chon-Alai district in Kyrgyzstan and in Jerge-Tal district in Tajikistan as a handcraft transmitted, used and safeguarded. The knowledge and ability of building raft has been transmitted from generation to generation in this region and it kept its pure and authentic form. Thus, the transmission of traditional art of raft from generation to generation, which still can be found among the Kyrgyz and other Turkic peoples in the region, is a cultural heritage not to be ignored. Additionally, these information and artifacts should be evaluated and safeguarded as part of the intangible cultural heritage, because due to globalization, this element of cultural heritage is gradually losing its unique characteristics. Consequently, while the data about the art of raft, boat and ship building of Turks is presented in this study, it is concluded that the value of this heritage is related to its traces from previous forms. [ABSTRACT FROM AUTHOR]

Membrane rafts are dynamic, small (10–200 nm) domains enriched with cholesterol and sphingolipids that compartmentalize cellular processes. Rafts participate in roles essential to the lifecycle of different viral families including virus entry, assembly and/or budding events. Rafts seem to participate in virus attachment and recruitment to the cell surface, as well as the endocytic and non-endocytic mechanisms some viruses use to enter host cells. In this review, we will introduce the specific role of rafts in viral entry and define cellular factors implied in the choice of one entry pathway over the others. Finally, we will summarize the most relevant information about raft participation in the entry process of enveloped and non-enveloped viruses.

Raft is a fast, scalable, understandable consensus algorithm widely used in distributed systems. The Leader handles client requests and interacts with other servers to reach a consensus, so a stable, reliable, and powerful Leader is crucial for the cluster. We designed a policy-based voting mechanism to make the elected Leader as reliable as possible. In order to improve the asymmetric relationship between the Followers and Leader, we designed a mechanism to trigger a new round of the election actively so that the Leader node can actively transform into a Follower under certain conditions and enhance the symmetry between servers. Our proposed Raft-PLUS algorithm makes the elected Leader as reliable as possible through four election policies and designed three opposition policies to trigger a new round of the election. To verify the effectiveness of the Raft-PLUS algorithm, we configure different election and opposition policies on 12 servers to simulate the election and opposition process of the Leader and explain the process. To demonstrate the advantages of the Raft-PLUS algorithm, we built key-value stores based on Raft and Raft-PLUS, and we tested the performance of Raft-PLUS and the Raft algorithm in normal and abnormal states. Experimental results show that the Raft-PLUS algorithm has similar write throughput to the Raft algorithm under normal conditions. Regarding the quality of the Leader network changes, the average write throughput of the Raft-PLUS algorithm is 40% higher than that of the Raft algorithm. The Leader’s CPU usage fluctuated; the average write throughput of Raft-PLUS was 38% higher than Raft.

The Wallacean archipelago between the Indian and Pacific Oceans is a critical biogeographic boundary for all kinds of animals, from butterflies to birds. Humans are no exception, and in this paper we offer a three stage model for how our genus overcame this boundary. We review how Lower Palaeolithic hominins were able to colonize the larger islands of western Wallacea through incidental seagoing, and subsistence on the megaherbivores that also made these crossings. However, Lower Palaeolithic hominins were not able to maintain geneflow between islands, nor cross into eastern Wallacea and beyond into Sahul. This biogeographic threshold persisted for hundreds of thousands of years until the arrival of our own species, whose cognitive capacities for planning and abstraction likely allowed for the construction of composite material rafts, interdependent paddles, and multiple-day seafaring. With the sea-level rise of the terminal Pleistocene and early Holocene a greater connectivity is seen in the form obsidian exchange networks, inter-island bead and fishhook traditions, and the colonization of very small islands entirely depauperate in terrestrial fauna. We suggest that the appearance of shell adzes at this time reflects the production of dugout canoes to facilitate regular inter-island voyaging. Wallacea presents a key case study both in the limits of Lower Palaeolithic hominin dispersal and the capacities that allowed Homo sapiens to go beyond these, as well as the intensification response of our species to rapid benign environmental change. [ABSTRACT FROM AUTHOR]

Membrane rafts are dynamic, small (10–200 nm) domains enriched with cholesterol and sphingolipids that compartmentalize cellular processes. Rafts participate in roles essential to the lifecycle of different viral families including virus entry, assembly and/or budding events. Rafts seem to participate in virus attachment and recruitment to the cell surface, as well as the endocytic and non-endocytic mechanisms some viruses use to enter host cells. In this review, we will introduce the specific role of rafts in viral entry and define cellular factors implied in the choice of one entry pathway over the others. Finally, we will summarize the most relevant information about raft participation in the entry process of enveloped and non-enveloped viruses. [ABSTRACT FROM AUTHOR]