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Visualization of biomolecules, cells and tissues, as well as metabolic processes in vivo is significant for studying the associated biological activities. Fluorine magnetic resonance imaging (

Sonodynamic therapy (SDT) benefiting from its intrinsic merits, such as noninvasiveness and deep tissue penetrability, is receiving increasing considerable attention in reactive oxygen species (ROS)-based tumor treatment. However, current sonosensitizers usually suffer from low tumor lesion accumulation, insufficient ROS generation efficiency under ultrasound, and non-biodegradability, which seriously impede the therapeutic outcomes. Additionally, it is difficult that SDT alone can completely eradicate tumors because of the complex and immunosuppressive tumor microenvironment (TME). Herein, we simultaneously employ sonosensitive porphyrin building blocks and glutathione (GSH)-responsive disulfide bonds to construct a novel degradable multifunctional porphyrin-based hollow porous organic polymer (POP) nanosonosensitizer (H-Pys-HA@M/R), which combine SDT, "on-demand" chemotherapy, and immunotherapy. Taking the unique advantages of POPs with designable structures and high specific surface area, this H-Pys-HA@M/R nanosonosensitizer can achieve tumor target accumulation, GSH-triggered drug release, and low-frequency ultrasound-activating ROS generation with encouraging results. Furthermore, this multifunctional nanosonosensitizer can effectively evoke immunogenic cell death (ICD) response through the combination of SDT and chemotherapy for both primary and distal tumor growth suppression. Meanwhile, H-Pys-HA@M/R exhibits favorable biodegradation and biosafety. Therefore, this study provides a new strategy for reasonably designing and constructing POP-related sonosensitizers combining SDT/chemotherapy/immunotherapy triple treatment modalities to eradicate malignant tumors.

Gold nanostars (AuNS) are promising carriers for targeted delivery of therapeutic oligonucleotides, but their potential in fabricating an on-demand drug release system in a facile and robust way remains to be explored. In this paper, we used a model aptamer (HApt), acting not only as a target ligand but also as a natural thermal-responsive material, to decorate AuNS. The prepared gold nanoconstruct, HApt@AuNS, displayed stoichiometric loading capacity of the anthracycline drug doxorubicin (Dox). The on-demand drug release was realized by illuminating nanoconstructs with near-infrared (NIR) light. Furthermore, a higher degree of Dox release from the nanoconstructs was achieved in an acidic environment, compared to neutral conditions. The

Cell-derived vesicles retain the cytoplasm and much of the native cell membrane composition. Therefore, they are attractive for investigations of membrane biophysics, drug delivery systems, and complex molecular factories. However, their fragility and aggregation limit their applications. Here, the mechanical properties and stability of giant plasma membrane vesicles (GPMVs) are enhanced by decorating them with a specifically designed diblock copolymer, cholesteryl-poly[2-aminoethyl methacrylate-b-poly(ethylene glycol) methyl ether acrylate]. When cross-linked, this polymer brush enhances the stability of the GPMVs. Furthermore, the pH-responsiveness of the copolymer layer allows for a controlled cargo loading/release, which may enable various bioapplications. Importantly, the cross-linked-copolymer GPMVs are not cytotoxic and preserve in vitro membrane integrity and functionality. This effective strategy to equip the cell-derived vesicles with stimuli-responsive cross-linkable copolymers is expected to open a new route to the stabilization of natural membrane systems and overcome barriers to biomedical applications., Advanced Healthcare Materials, 11 (23), ISSN:2192-2640, ISSN:2192-2659

This paper reports a non-coplanar misalignment optical waveguide cantilever sensor realizing a monotonic response with a large operation range. A 1 × 2 Y-branch optical power splitter cantilever structure was designed, and one of the branches was reduced in thickness at the end, as a non-coplanar structure with respect to another. The misalignment coupling of the two branches due to the thickness of one branch leads to a monotonic response of an optical waveguide cantilever sensor. The simulation results showed a monotonic response with a sensitivity of 6 × 10 − 4 n m − 1 in a large operation range of − 1 to 1 µm.

In order to improve the efficiency of the small muzzle brake used in the anti-material rifle, the calculation model of the efficiency of the muzzle brake is established, and the main structural parameters of the small muzzle brake are optimized by using the MATLAB optimization toolbox. After optimization, the efficiency of the muzzle brake is improved by 38%. The test results show that the improved small muzzle brake can meet the requirements of anti-material rifle.

The influence law of a tracked vehicle grouser shape on the soil slide sinkage was investigated in this study via the numerical simulations and physical tests. A finite element model was built using the plastic incremental theory and generalized Hokker’s law, while constitutive soil parameters were obtained via triaxial test. The numerical simulation model was verified by physical test results. Based on the verified numerical simulation model, the influence law of the tracked vehicle grouser shape on the soil slide sinkage was determined. The results show that (1) shear displacement in the lateral direction can increase the soil sinkage in the vertical direction, which is referred to as the “slide sinkage”; (2) there is a linear relationship between the slide sinkage and the shear displacement; (3) the grouser width and height have a positive influence on the amount of slide sinkage. Under the same load, an increase in grouser width and height will cause an increase in the soil slide sinkage. Grouser thickness and pitch have a negative influence on the slide sinkage, and under the same load, increased grouser width and height cause a reduction in the soil slide sinkage. Grouser angle characteristics have no significant effect on the soil sinkage. The application of the slide sinkage in tracked vehicles traveling on soft roads was investigated in multibody system dynamics analysis software Recurdyn to confirm these observations. The results presented in this paper may provide a workable reference for the analysis of tracked vehicles in multibody system dynamics scenarios.

Pickering foams are foams stabilized by particles and are generally known to have good stability. A special subclass of particle-stabilized foams includes stimuli-responsive Pickering foams that can be formed or deconstructed by applying an external stimuli or changing the environmental conditions; such intelligent particles could find use in many practical applications. Here, we synthesized surfactant-free biocompatible poly[2(diethylamino)ethyl methacrylate] (PDEAEMA) hydrogel particles (HGPs) by emulsion polymerization. The morphology, structure, and surface charge of the HGPs were characterized by TEM, DLS, and the zeta potential, respectively. We have observed that the pH values of the aqueous solution have a strong influence on the formation of the Pickering foams in the presence of PDEAEMA HGPs. Namely, at pH values ≤4.0 no Pickering foams were produced, while at pH values >4.0 stable Pickering foams were formed. Moreover, the height, size and bubble size distribution of Pickering foams are strongly influenced by the pH values of aqueous solution and PDEAEMA HGPs concentration. The formed Pickering foams in basic aqueous solution can all be conveniently deconstructed by changing the pH values to below 4.0. Interestingly, the dried lamellas of the Pickering foams were constituted by either monolayers or multilayers of PDEAEMA HGPs as demonstrated by SEM.

Compartmentalization is fundamental in nature, where the spatial segregation of biochemical reactions within and between cells ensures optimal conditions for the regulation of cascade reactions. While the distance between compartments or their interaction are essential parameters supporting the efficiency of bio-reactions, so far they have not been exploited to regulate cascade reactions between bioinspired catalytic nanocompartments. Here, we generate individual catalytic nanocompartments (CNCs) by encapsulating within polymersomes or attaching to their surface enzymes involved in a cascade reaction and then, tether the polymersomes together into clusters. By conjugating complementary DNA strands to the polymersomes' surface, DNA hybridization drove the clusterization process of enzyme-loaded polymersomes and controlled the distance between the respective catalytic nanocompartments. Owing to the close proximity of CNCs within clusters and the overall stability of the cluster architecture, the cascade reaction between spatially segregated enzymes was significantly more efficient than when the catalytic nanocompartments were not linked together by DNA duplexes. Additionally, residual DNA single strands that were not engaged in clustering, allowed for an interaction of the clusters with the cell surface as evidenced by A549 cells, where clusters decorating the surface endowed the cells with a non-native enzymatic cascade. The self-organization into clusters of catalytic nanocompartments confining different enzymes of a cascade reaction allows for a distance control of the reaction spaces which opens new avenues for highly efficient applications in domains such as catalysis or nanomedicine., Compartmentalization is fundamental in nature, where the spatial segregation of biochemical reactions within and between cells ensures optimal conditions for the regulation of cascade reactions.

Nanotheranostics is an emerging field that brings together nanoscale-engineered materials with biological systems providing a combination of therapeutic and diagnostic strategies. However, current theranostic nanoplatforms have serious limitations, mainly due to a mismatch between the physical properties of the selected nanomaterials and their functionalization ease, loading ability, or overall compatibility with bioactive molecules. Herein, a nanotheranostic system is proposed based on nanocompartment clusters composed of two different polymersomes linked together by DNA. Careful design and procedure optimization result in clusters segregating the therapeutic enzyme human Dopa decarboxylase (DDC) and fluorescent probes for the detection unit in distinct but colocalized nanocompartments. The diagnostic compartment provides a twofold function: trackability via dye loading as the imaging component and the ability to attach the cluster construct to the surface of cells. The therapeutic compartment, loaded with active DDC, triggers the cellular expression of a secreted reporter enzyme via production of dopamine and activation of dopaminergic receptors implicated in atherosclerosis. This two-compartment nanotheranostic platform is expected to provide the basis of a new treatment strategy for atherosclerosis, to expand versatility and diversify the types of utilizable active molecules, and thus by extension expand the breadth of attainable applications.

Functionalization of hard or soft surfaces with, for example, ligands, enzymes or proteins, is an effective and practical methodology for the development of new applications. We report the assembly of two types of nanoreactors based upon poly(dimethylsiloxane)-block-poly(2-methyl-2-oxazoline) (PDMS-b-PMOXA) diblock copolymers as scaffold, uricase and lactoperoxidase as bio-catalysts located within the nanoreactors, and melittin as the biopores inserted into the hydrophobic shell. The nanoreactors were immobilized on poly(2-hydroxyethyl methacrylate)-co-poly(2-aminoethyl methacrylate hydrochloride) (PHEMA-co-P(2-AEMA·HCl) brushes-grafted wafer surfaces by utilizing the strong supramolecular interactions between biotin and streptavidin. The (PHEMA-co-P(2-AEMA·HCl) brushes on silicon surfaces were prepared by a surface initiating atom transfer radical polymerization (ATRP) "graft-from" technique. Cascade reactions between different surface-anchored nanoreactors were demonstrated by converting Amplex Red to the fluorescent probe resorufin by using the H2O2 produced from uric acid and H2O. The detailed properties of the nanoreactors on the functionalized surface including the binding behaviours and cascade reactions were investigated using emission spectroscopy, transmission electron microscopy (TEM), light scattering (LS), atomic force microscopy (AFM) and a quartz crystal microbalance (QCM-D). The results are proof-of-principle for the preparation of catalytically functional engineered surface materials and lay the foundation for applying this advanced functional surface material in biosensing, implanting and antimicrobial materials preparation.

DNA has been widely used as a key tether to promote self-organization of super-assemblies with emergent properties. However, control of this process is still challenging for compartment assemblies and to date the resulting assemblies have unstable membranes precluding in vitro and in vivo testing. Here we present our approach to overcome these limitations, by manipulating molecular factors such as compartment membrane composition and DNA surface density, thereby controlling the size and stability of the resulting DNA-linked compartment clusters. The soft, flexible character of the polymer membrane and low number of ssDNA remaining exposed after cluster formation determine the interaction of these clusters with the cell surface. These clusters exhibit in vivo stability and lack of toxicity in a zebrafish model. To display the breadth of therapeutic applications attainable with our system, we encapsulated the medically established enzyme laccase within the inner compartment and demonstrated its activity within the clustered compartments. Most importantly, these clusters can interact selectively with different cell lines, opening a new strategy to modify and expand cellular functions by attaching such pre-organized soft DNA-mediated compartment clusters on cell surfaces for cell engineering or therapeutic applications.

Melanin and polydopamine are potent biopolymers for the development of biomedical nanosystems. However, applications of melanin or polydopamine-based nanoparticles are limited by drawbacks related to a compromised colloidal stability over long time periods and associated cytotoxicity. To overcome these hurdles, a novel strategy is proposed that mimics the confinement of natural melanin in melanosomes. Melanosome mimics are developed by co-encapsulating the melanin/polydopamine precursors L-DOPA/dopamine with melanogenic enzyme Tyrosinase within polymersomes. The conditions of polymersome formation are optimized to obtain melanin/polydopamine polymerization within the cavity of the polymersomes. Similar to native melanosomes, polymersomes containing melanin/polydopamine show long-term colloidal stability, cell-compatibility, and potential for cell photoprotection. This novel kind of artificial melanogenesis is expected to inspire new applications of the confined melanin/polydopamine biopolymers.

Functionalized nanoparticles (NPs) are critical to a wide-ranging of applications. The more versatile use of the NPs hinges on the capability to readily modify them to perform different functions. For example functionalized polymeric nanomaterials bearing ligands can be employed in metal ion extraction and recovery. However, obtaining ion-imprinted particles via ligand copolymerization can be difficult to scale-up. We therefore present an alternative method to obtain ligand-carrying polymeric nanoparticles (LC-NPs) for metal ion absorption. Branched polyethyleneimine (b-PEI) was used to modify the negatively charged surfactant-free polystyrene (PS) NPs obtained via surfactant-free emulsion polymerization by employing “surfmers”. The obtained PEI-PS NPs were further cross-linked with phthaldialdehyde to form cross-linked PEI-PS (CPEI-PS). Both PEI-PS and CPEI-PS were capable of absorbing chromium, nickel, cobalt and copper ions, as evident in the color change upon absorption. Furthermore, the ion absorption capacity of both types of particles was comparable, but with a greater selectivity toward copper ions. The selectivity towards copper ions of CPEI-PS increased with the degree of dialdehyde cross-linking. Repeated absorption-desorption cycles showed no loss in the absorption capacity of CPEI-PS as compared to the non-crosslinked PEI-PS. Finally, both were further reacted with two different aldehydes, which ascertained that the primary amine groups were present for further reaction with aldehydes and thereby enabling further functionalization of these particles.

A targeted drug delivery nanosystem for glioblastoma multiforme (GBM) based on polymersomes (Ps) made of poly(dimethylsiloxane)-poly(2-methyloxazoline) (PDMS-PMOXA) diblock copolymers was developed to evaluate their potential to actively target brain cancer cells and deliver anticancer drugs. Angiopep2 was conjugated to the surface of preformed Ps to target the low density lipoprotein receptor-related protein 1 that are overexpressed in blood brain barrier (BBB) and glioma cells. The conjugation efficiency yield for angiopep2 was estimated to be 24%. The angiopep2-functionalized Ps showed no cellular toxicity after 24h and enhanced the cellular uptake around 5 times more in U87MG glioblastoma cells compared to the non-targeted Ps. The encapsulation efficiency of doxorubicin (DOX) in Ps was 13% by co-solvent method, compared to a film rehydration method (4%). The release profiles of the DOX from Ps showed a release of 42% at pH 5.5 and 40% at pH 7.4 after 24h, indicating that Ps can efficiently retain the DOX with a slow release rate. Furthermore, the in vitro antiproliferative activity of DOX-loaded Ps-Angiopep2 showed enhanced toxicity to U87MG glioblastoma cells, compared to non-targeted Ps. Overall, our in vitro results suggested that angiopep2-conjugated Ps can be used as nanocarriers for efficient targeted DOX delivery to glioblastoma cells.

To accurately predict and master the actual combat capacity of the weapon system, the paper took a self-propelled artillery as the research subject and built the completely artillery system virtual prototype based on the dynamic theory. Extracted the dynamic characteristics of firepower system, running system and drive system, the performance variation and failure mechanism of the artillery system were studied by using the method of theoretical analysis, simulation and physical experiment. The paper built the fault evaluation and life prediction model in the process of shooting and drivingby combining data fusion, deep learning, etc. The performance evaluation and the prediction of fault of the full artillery system were realized. It can provide references for the life evaluation and prediction of complex equipment system.

The ability of amphiphilic Janus nanoparticles (JNPs) to partition at the oil–water and air–water interfaces can be especially attractive for a plethora of new applications. Unlike molecular surfactants, the JNPs could act as “bulk-to-surface” carriers of different small molecules/actives or bulklike properties—magnetic, optic, or electric—without a dramatic effect on their ability to partition at interfaces. Here we report surfactant-free JNPs with pH-triggered switchable amphiphilicity that could be used in such interfacial applications. The polarity balance of the JNPs can be tuned by the pH such that the amphiphilicity of JNPs is switched on or off at low (pH 7.0) pH values, respectively. When the amphiphilicity of JNPs is switched off, the interfacial activity of JNPs is comparable to that of homogeneous nanoparticles (HNPs), and when switched on, the interfacial activity is enhanced, proving that the amphiphilicity of JNPs plays a role in enhancing the interfacial activity even at...

Elucidating the mechanisms responsible for spontaneous adsorption of nanoparticles (NPs) at interfaces is important for their application as emulsifiers, bubble stabilizers, or foaming agents. In order to investigate the key factors that control the spontaneous adsorption of NPs at liquid-liquid interfaces, we synthesized seven different types of NPs from pH-responsive polymers poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) and poly(2-dimethylamino)ethyl methacrylate) (PDMAEMA) via surfactant-free emulsion polymerization or via "grafting from" polystyrene (PS) NPs. The dynamic interfacial tension (IFT) measurements at the toluene-water (Tol-H2O) interface reveal that when PDEAEMA and PDMAEMA are grafted from the surface of PS NPs the solubility of the grafted pH-responsive polymers in toluene is the key factor determining the NPs' interfacial adsorption. Under acidic conditions (pH < 6.0), PDEAEMA and PDMAEMA are protonated and show no solubility in toluene, and as a result, the grafted NPs do not adsorb at the Tol-H2O interface. Oppositely, under basic conditions (pH > 7.0), PDMAEMA dissolves in toluene and therefore the PDMAEMA-grafted NPs can adsorb at the Tol-H2O interface. Interestingly, when NPs are constituted of PDEAEMA, they can adsorb spontaneously at the Tol-H2O interface under acidic conditions (pH < 6.0) but not under basic conditions (pH > 7.0). In this case, the key factor determining the NPs' spontaneous adsorption at the Tol-H2O interface is the degree of softness of the NPs rather than the solubility of PDEAEMA in toluene. Furthermore, we found that the adsorption of NPs constituted of PDEAEMA- (pH 2.0-6.0) and PDMAEMA-grafted PS NPs (pH 7.0-10.0) at the Tol-H2O interface is a combination of diffusion-controlled and energy-barrier-controlled. The opposite trends observed for the interfacial attachment ΔE and activation energies Ea for the "constituted of" and "grafted from" NPs with pH suggest an opposite mechanisms of adsorption at the Tol-H2O interface. Finally, the synthesized NPs prove to be effective emulsifiers, where the phase of the Pickering emulsions can be changed dynamically by pH adjustment.

Hybrids composed of amphiphilic block copolymers and lipids constitute a new generation of biological membrane-inspired materials. Hybrid membranes resulting from self-assembly of lipids and polymers represent adjustable models for interactions between artificial and natural membranes, which are of key importance, e.g., when developing systems for drug delivery. By combining poly(dimethylsiloxane)-block-poly(2-methyl-2-oxazoline) amphiphilic copolymers (PDMS-b-PMOXA) with various phospholipids, we obtained hybrid films with modulated properties and topology, based on phase separation, and the formation of distinct domains. By understanding the factors driving the phase separation in these hybrid lipid-polymer films, we were able to use them as platforms for directed insertion of membrane proteins. Tuning the composition of the polymer-lipids mixtures favored successful insertion of membrane proteins with desired topological distributions (in polymer or/and lipid regions). Controlled insertion and location of membrane proteins in hybrid films make these hybrids ideal candidates for numerous applications where specific spatial functionality is required.

Polymersomes that encapsulate a hydrophilic polymer are prepared by conducting biocatalytic atom transfer radical polymerization (ATRP) in these hollow nanostructures. To this end, ATRPase horseradish peroxidase (HRP) is encapsulated into vesicles self-assembled from poly(dimethylsiloxane)-block-poly(2-methyl-2-oxazoline) (PDMS-b-PMOXA) diblock copolymers. The vesicles are turned into nanoreactors by UV-induced permeabilization with a hydroxyalkyl phenone and used to polymerize poly(ethylene glycol) methyl ether acrylate (PEGA) by enzyme-catalyzed ATRP. As the membrane of the polymersomes is only permeable for the reagents of ATRP but not for macromolecules, the polymerization occurs inside of the vesicles and fills the polymersomes with poly(PEGA), as evidenced by (1) H NMR. Dynamic and static light scattering show that the vesicles transform from hollow spheres to filled spheres during polymerization. Transmission electron microscopy (TEM) and cryo-TEM imaging reveal that the polymersomes are stable under the reaction conditions. The polymer-filled nanoreactors mimic the membrane and cytosol of cells and can be useful tools to study enzymatic behavior in crowded macromolecular environments.

Determining the interfacial energy of nanoparticles is very challenging via traditional methods that first require measuring the contact angle of several liquids of a sessile drop on pellets or capillary rise in powder beds. In this work, we propose an alternative way to model the interfacial energy of nanoparticles directly from emulsion phase inversion data in Pickering emulsions. This could establish itself as a universal and facile way to determine the polarity of nanoparticles relative to a series of standard particles without the need to measure contact angles. Pickering emulsions of several oils in water were generated with a series of snowman-like Janus nanoparticles (JNPs), whose polarity gradually increased with the size of the more polar lobe. Depending on the oil to water ratio and the JNPs lobe size, oil-in-water (o/w) or water-in-oil (w/o) Pickering emulsions were obtained and the affinity of the JNPs to either water or oil can be inferred from the evolution of the emulsion phase inversion curves with these parameters. We further demonstrate that by adopting a simple model for the work of adhesion of JNPs with the water and oil phases, one can quantitatively calculate the relative interfacial energy change of the JNPs with the liquid. In addition, a knowledge of the interfacial energy of nanoparticles is useful for employing these in suspension polymerization to create surface nanostructured materials. The o/w and w/o Pickering emulsions obtained from monomers, such as styrene, could be polymerized, resulting in colloidosomes or hollow-like materials. The hollow materials exhibited a rather high volume storage capacity for the aqueous phase for extended periods of time, which could be released upon microwaving, making them ideal for use in long-term storage applications of various water-soluble actives.

Amphiphilic block copolymers self-assemble into artificial membranes of enhanced strength and stability compared to lipid membranes and are still able to incorporate biological membrane proteins. Membrane fluidity is a key parameter for retaining function of incorporated proteins. In this study, lateral diffusion properties of membranes of diblock and triblock copolymers based on poly(2-methyl-2-oxazoline) and poly(dimethylsiloxane), with thicknesses between 6 and 21 nm, were systematically investigated. Z-scan fluorescence correlation spectroscopy was used to obtain highly accurate diffusion coefficients. The lateral diffusion coefficients (D) scale with the molecular weight of the hydrophobic block (Mh) for both diblock and triblock configurations as D ∝ Mh–1.25. A significant diffusion increase of diblocks compared to triblocks revealed that diffusion is primarily related to the different structural conformation of the macromolecules assembled in the membrane. Moreover, hindered diffusion for higher mo...

Many biological processes require precise regulation and synergy of proteins, and consequently involve molecular recognition and spatial constraints between biomolecules. Here, a library of poly(N-isopropylacrylamide-co-tris-nitrilotriacetic acid acrylamide) (PNTs) has been synthesized and complexed with Cu(2+) in order to serve as models for investigation of the combined effects of molecular recognition and spatial constraints in biomolecular interactions. The average distance between Cu(2+)-trisNTA binding sites in PNTs polymers was varied from 4.3 to 31.5 nm by adjusting their trisNTA contents. His tag (His6), His-tagged enhanced yellow fluorescent protein (His6-eYFP), and His6-tagged collagenase G (His6-ColG), with sizes ranging from 1 to 11 nm, were used as models to assess whether the binding ability is influenced by a cooperative topology based on molecular recognition interactions with Cu(2+)-trisNTA binding sites, and spatial constraints created by decreasing average distance between trisNTAs. His-tagged molecules bound to all PNTs polymers due to their molecular recognition interaction involving histidines and Cu(2+)-trisNTA pockets, but with a binding ability that was highly modulated by the average distance between the trisNTA binding sites. Small molecular mass molecules (His6) exhibit a high binding ability to all PNTs polymers, whereas his-tagged proteins bind to PNTs efficiently only when the average distance between trisNTA binding sites is larger than the protein dimensions.

Reliable prediction of the 3D structure of self-assembled amphiphilic copolymers is essential for applications in which specificity has to be carefully controlled, as for example in nanomedicine. Since supramolecular assemblies are strongly affected by the chemical nature of block copolymers and the preparation methods, it is essential to understand the influence of such parameters on the self-assembly process. We have now successfully synthesized a library of amphiphilic block copolymers, poly(dimethylsiloxane)-block-poly(2-methyl-2-oxazoline) (PDMS-b-PMOXA), and investigated the molecular parameters and self-assembly conditions that generate a specific architecture in particular polymersome. We found that 3D assemblies are strongly affected by the preparation method, but not by the initial concentration of block copolymer and solution pH. The phase diagrams of self-assembly behavior show a strong influence of the hydrophilic to hydrophobic ratio (fPMOXA), and the molecular mass of each block. In particu...

Subcellular compartmentalization of cells, a defining characteristic of eukaryotes, is fundamental for the fine tuning of internal processes and the responding to external stimuli. Reproducing and controlling such compartmentalized hierarchical organization, responsiveness, and communication is important toward understanding biological systems and applying them to smart materials. Herein, a cellular signal transduction strategy (triggered release from subcompartments) is leveraged to develop responsive, purely artificial, polymeric multicompartment assemblies. Incorporation of responsive nanoparticles-loaded with enzymatic substrate or ion channels-as subcompartments inside micrometer-sized polymeric vesicles (polymersomes) allowed to conduct bioinspired signaling cascades. Response of these subcompartments to an externally added stimulus is achieved and studied by using confocal laser scanning microscopy (CLSM) coupled with in situ fluorescence correlation spectroscopy (FCS). Signal triggered activity of an enzymatic reaction is demonstrated in multicompartments through recombination of compartmentalized substrate and enzyme. In parallel, a two-step signaling cascade is achieved by triggering the recruitment of ion channels from inner subcompartments to the vesicles' membrane, inducing ion permeability, mimicking endosome-mediated insertion of internally stored channels. This design shows remarkable versatility, robustness, and controllability, demonstrating that multicompartment polymer-based assemblies offer an ideal scaffold for the development of complex cell-inspired responsive systems for applications in biosensing, catalysis, and medicine.

The research on repeated loading and sinkage characteristics of soil can calculate the sinkage of wheel and track in driving process more precisely, so it can help calculate the vibration characteristics and driving resistance of vehicle more accurately. This paper analysis the soil repeated loading and sinkage characteristics based on finite element method. The results shows that the unloading and reloading process of soil can be assumed as a straight line with slope of k on load-sinkage curve, here k is called rebound coefficient. The research conclusion can provide reference to the vehicle terramachanics and other research involved soil deformation.

Medical applications of anticancer and antimalarial drugs often suffer from low aqueous solubility, high systemic toxicity, and metabolic instability. Smart nanocarrier-based drug delivery systems provide means of solving these problems at once. Herein, we present such a smart nanoparticle platform based on self-assembled, reduction-responsive amphiphilic graft copolymers, which were successfully synthesized through thiol-disulfide exchange reaction between thiolated hydrophilic block and pyridyl disulfide functionalized hydrophobic block. These amphiphilic graft copolymers self-assembled into nanoparticles with mean diameters of about 30-50 nm and readily incorporated hydrophobic guest molecules. Fluorescence correlation spectroscopy (FCS) was used to study nanoparticle stability and triggered release of a model compound in detail. Long-term colloidal stability and model compound retention within the nanoparticles was found when analyzed in cell media at body temperature. In contrast, rapid, complete reduction-triggered disassembly and model compound release was achieved within a physiological reducing environment. The synthesized copolymers revealed no intrinsic cellular toxicity up to 1 mg mL(-1). Drug-loaded reduction-sensitive nanoparticles delivered a hydrophobic model anticancer drug (doxorubicin, DOX) to cancer cells (HeLa cells) and an experimental, metabolically unstable antimalarial drug (the serine hydroxymethyltransferase (SHMT) inhibitor (±)-1) to Plasmodium falciparum-infected red blood cells (iRBCs), with higher efficacy compared to similar, non-sensitive drug-loaded nanoparticles. These responsive copolymer-based nanoparticles represent a promising candidate as smart nanocarrier platform for various drugs to be applied to different diseases, due to the biocompatibility and biodegradability of the hydrophobic block, and the protein-repellent hydrophilic block.

The ability to finely tune the amphiphilic balance of Janus nanoparticles (JNPs) could represent a step forward toward creating the next generation of solid-state amphiphiles with significant potential for applications. The inherent amphiphilicity of JNPs stemming from an intrinsic polarity contrast between two surface regions is well-acknowledged, but remained difficult to demonstrate experimentally in the absence of surfactants and stabilizers. We have designed two homologous series of surfactant-free polymeric JNPs starting from polystyrene (PS) seed nanoparticles (NPs) on which we grew Janus lobes of different sizes via seed polymerization and phase separation of the 3-(triethoxysilyl)propyl-methacrylate (3-TSPM) monomer. The two series differ only by the radical initiator used in the seed polymerization: polar ionic ammonium persulfate (APS) vs nonpolar oil-soluble 2,2'-azobis(2-methylpropionitrile) (AIBN). To compare the two series, we employed them in the emulsification of water with heptane or molten paraffin wax. A polarity reversal of the JNPs within AIBN-JNP series could be observed from the catastrophic and transitional emulsion phase inversions and occurred when the more polar lobe was larger than the nonpolar seed PS lobe. Furthermore, the AIBN-JNPs appeared to be amphiphilic and adopt preferred orientation within the monolayer at the oil/water interface. We therefore demonstrated that in the absence of surfactants the amphiphilicity of the JNPs depends not only on the relative size of the lobes, but also on the surface polarity contrast, which can be tuned by changing the nature of radical initiator.

Self-organization of nanocomponents was mainly focused on solid nanoparticles, quantum dots, or liposomes to generate complex architectures with specific properties, but intrinsically limited or not developed enough, to mimic sophisticated structures with biological functions in cells. Here, we present a biomimetic strategy to self-organize synthetic nanocompartments (polymersomes) into clusters with controlled properties and topology by exploiting DNA hybridization to interconnect polymersomes. Molecular and external factors affecting the self-organization served to design clusters mimicking the connection of natural organelles: fine-tune of the distance between tethered polymersomes, different topologies, no fusion of clustered polymersomes, and no aggregation. Unexpected, extended DNA bridges that result from migration of the DNA strands inside the thick polymer membrane (about 12 nm) represent a key stability and control factor, not yet exploited for other synthetic nano-object networks. The replacement of the empty polymersomes with artificial organelles, already reported for single polymersome architecture, will provide an excellent platform for the development of artificial systems mimicking natural organelles or cells and represents a fundamental step in the engineering of molecular factories.

Combining the concepts of supramolecular polymers and dendron- ized polymers provides the opportunity to create bulky polymers with easy structural modification and tunable properties. In the present work, a novel class of side-chain supramolecular dendronized polymethacrylates is pre- pared through the host-guest interac- tion. The host is a linear polymethacry- late (as the backbone) attached in each repeat unit with a b-cyclodextrin (b- CD) moiety, and the guest is constitut- ed with three-fold branched oligoethy- lene glycol (OEG)-based first- (G1) and second-generation (G2) dendrons with an adamantyl group core. The host and guest interaction in aqueous solution leads to the formation of the supramolecular polymers, which is sup- ported with 1 H NMR spectroscopy and dynamic light scattering measurements. The supramolecular formation was also examined at different host/guest ratios. The water solubility of hosts and guests increases upon supramolecular forma- tion. The supramolecular polymers show good solubility in water at room temperature, but exhibit thermorespon- sive behavior at elevated temperatures. Their thermoresponsiveness is thus in- vestigated with UV/Vis and 1 H NMR spectroscopy, and compared with their counterparts formed from individual b- CD and the OEG dendritic guest. The effect of polymer concentration and molar ratio of host/guest was exam- ined. It is found that the polar interior of the supramolecules contribute signif- icantly to the thermally-induced phase transitions for the G1 polymer, but this effect is negligible for the G2 polymer. Based on the temperature-varied proton NMR spectra, it is found that the host-guest complex starts to de- compose during the aggregation pro- cess upon heating to its dehydration temperature, and this decomposition is enhanced with an increase of solution temperature.

An improved strategy to synthesize oligo(ethylene glycol)-based secondary generation (G2) dendron is presented. The overall synthesis efficiency increased by 50% when comparing to the previous method, and the product purification by column chromatography becomes much easier. Based on this approach, the synthesis of the third-generation (G3) dendrons and the corresponding methacrylate-based G3 macromonomer becomes feasible. Because of the oil characteristics of this macromonomer, its polymerization was able to be conducted in bulk with AIBN as the initiator. The polymerization degree of the third-generation dendronized polymer (PG3) was found to be around 16 based on GPC measurement. The thermally induced dehydration processes of this polymer were monitored by temperature-varied proton NMR spectroscopy, and its thermoresponsive behaviors were investigated with turbidity measurements using UV–vis spectroscopy. Similar to the lower generation counterparts, this threefold branched dendronized polymer also shows characteristic fast and sharp phase transitions around its apparent lower critical solution temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6630–6640, 2009

Synthesis of novel zwitterionic block copolypeptides, poly(N-isopropylacrylamide)-block-poly(L-glutamic acid-co-L-lysine) [PNiPAM(n)(PLG(x)-co-PLLys(y))m , where n is the number-average degree of polymerization (DP(n)) of PNiPAM block, x and y are the mole fraction of glutamic acid and lysine residues, respectively, and m is the total DP(n) of the peptide block], and their stimuli-responsiveness to temperature and pH variation in aqueous solutions are described. Initiated with the amino-terminated poly(N-isopropylacrylamide) (PNiPAM(n)-NH2), ring-opening polymerization (ROP) of a mixture of gamma-benzyl-L-glutamate N-carboxyanhydride (BLG-NCA), and Boc-L-lysine N-carboxyanhydride (BLLys-NCA) afforded the block copolypeptides PNiPAM(n)(PBLG(x)-co-PBLLys(y))m, with a poly(N-isopropylacrylamide) block together with a random copolypeptide block, which was then deprotected with HBr/trifluoroacetic acid into the double hydrophilic block copolypeptides, PNiPAM(n)(PLG(x)-co-PLLys(y))m. Their block ratios and lengths, as well as the amino acid residue ratios in the random copolypeptide block are varied (n = 360, x = 0.4-0.5, y = 0.4-0.6, and m = 220-252). The secondary structures of the copolypeptides in aqueous solution at different pH conditions were examined. Phase transitions in aqueous solutions induced by both pH and temperature variation were investigated by (1)H NMR spectroscopy. The transitions induced by temperature were also explored by turbidity measurements using UV/vis spectroscopy for their lower critical aggregation temperature (LCAT) determination. Furthermore, these aggregation processes were followed by dynamic light scattering measurements.

Breechblock operating force is one of the key test parameters of the shock test bed for gun breechblock system. With the design principle determined, the dynamics principle model of the shock test bed is established based on the virtual prototype technology. The kinetic energy theorem is used to calculate the minimum theoretical force F, a standard value for shock test bed to open breechblock. As both the mass of breechblock operating cam and the breechblock operating distance are fixed, the simulation experiment is performed based on the principle model when the breechblock operating force is F.. The results show that the test bed fails to open breechblock under the working condition for energy loss during the impact. By the research, it is better to grasp the dynamics characteristics of test bed before the physical entity experiments, which is benefit to choose a suitable breechblock operating force.

For it is hard to develop experiments for the gun breechblock system, a shock test bed is designed for it. During designing, the breechblock operating force is one of the key test parameters of the shock test bed for gun breechblock system. In order to choose a reasonable value to open breechblock, influence of breechblock operating force on breechblock operating works of shock test bed is analyzed. With the design principle determined, the dynamics principle model of the shock test bed is established based on the virtual prototype technology. According to the minimum theoretical force F, a standard value for shock test bed to open breechblock. As both the mass of breechblock operating cam and the breechblock operating distance are fixed, the simulation experiments are performed based on the principle model when the breechblock operating force is F, 1.5F, 2F, 2.5F and 3F separately. The results show that the greater breechblock operating force is, the more total work, useful work and useless work have been done. But the wasted energy of work will increase. By the research, it is better to choose a less value of breechblock operating force.

Currently, research on polymers to be used as gene delivery systems is one of the most important directions in both polymer science and biomedicine. In this report, we describe a five-step procedure to synthesize a novel polymer-peptide hybrid system for gene transfection. The block copolymer based on the biocompatible polymer poly(2-methyl-2-oxazoline) (PMOXA) was combined with the biocleavable peptide block poly(aspartic acid) (PASP) and finally modified with diethylenetriamine (DET). PMOXA-b-PASP(DET) was produced in high yield and characterized by (1)H NMR and FT-IR. Our biopolymer complexed plasmid DNA (pDNA) efficiently, and highly uniform nanoparticles with a slightly negative zeta potential were produced. The polymer-peptide hybrid system was able to efficiently transfect HEK293 and HeLa cells with GFP pDNA in vitro. Unlike the commonly used polymer, 25 kDa branched poly(ethylenimine), our biopolymer had no adverse effects on cell growth and viability. In summary, the present work provides valuable information for the design of new polymer-peptide hybrid-based gene delivery systems with biocompatible and biodegradable properties.

The fight against most infectious diseases, including malaria, is often hampered by the emergence of drug resistance and lack or limited efficacies of vaccines. Therefore, new drugs, vaccines, or other strategies to control these diseases are needed. Here, we present an innovative nanotechnological strategy in which the nanostructure itself represents the active substance with no necessity to release compounds to attain therapeutic effect and which might act in a drug- and vaccine-like dual function. Invasion of Plasmodium falciparum parasites into red blood cells was selected as a biological model for the initial validation of this approach. Stable nanomimics-polymersomes presenting receptors required for parasite attachment to host cells-were designed to efficiently interrupt the life cycle of the parasite by inhibiting invasion. A simple way to build nanomimics without postformation modifications was established. First, a block copolymer of the receptor with a hydrophobic polymer was synthesized and then mixed with a polymersome-forming block copolymer. The resulting nanomimics bound parasite-derived ligands involved in the initial attachment to host cells and they efficiently blocked reinvasion of malaria parasites after their egress from host cells in vitro. They exhibited efficacies of more than 2 orders of magnitude higher than the soluble form of the receptor, which can be explained by multivalent interactions of several receptors on one nanomimic with multiple ligands on the infective parasite. In the future, our strategy might offer interesting treatment options for severe malaria or a way to modulate the immune response.

Planar solid-supported membranes based on amphiphilic block copolymers represent promising systems for the artificial creation of structural surfaces. Here we introduce a method for engineering functional planar solid-supported membranes through insertion of active biomolecules. We show that membranes based on poly(dimethylsiloxane)-block-poly(2-methyl-2-oxazoline) (PDMS-b-PMOXA) amphiphilic diblock copolymers, which mimic natural membranes, are suitable for hosting biomolecules. Our strategy allows preparation of large-area, well-ordered polymer bilayers via Langmuir-Blodgett and Langmuir-Schaefer transfers, and insertion of biomolecules by using Bio-Beads. We demonstrate that a model membrane protein, the potassium channel from the bacterium Mesorhizobium loti, remains functional after insertion into the planar solid-supported polymer membrane. This approach can be easily extended to generate a platform of functional solid-supported membranes by insertion of different hydrophobic biomolecules, and employing different types of solid substrates for desired applications. (C) 2014 Elsevier Ltd. All rights reserved.