Twistocaloric Modeling of Elastomer Fibers and Experimental Validation.

The twistocaloric effect is attributed to the change in entropy of the material driven by torsional stress. It is responsible for the torsional refrigeration of fiber materials that has been widely exploited as one of the solid-state cooling techniques with high efficiency and low volume change rate. The lack of theories and mathematical models of twistocaloric effect, however, limits broad applications of torsional refrigeration. In this work, a twistocaloric model is established to capture the relationship between twist density and temperature variation of natural rubber fibers and thermoplastic elastomer yarns. An experimental setup consisting torsion actuator and torque sensor coupled with a temperature measurement system is built to validate the model. Using the Maxwell relationship, twistocaloric coefficient is measured by quantifying the thermal effect induced by torsion under shear strain. The experimental characterization of the twistocaloric effect in natural rubber fiber and thermoplastic elastomer yarn are consistent with the theoretical predictions.

Pd(II)-Directed Encapsulation of Hydrogenase within the Layer-by-Layer Multilayers of Carbon Nanotube Polyelectrolyte Used as a Heterogeneous Catalyst for Oxidation of Hydrogen.

A metal-directed assembling approach has been developed to encapsulate hydrogenase (H2ase) within a layer-by-layer (LBL) multilayer of carbon nanotube polyelectrolyte (MWNT-PVPMe), which showed efficient biocatalytic oxidation of H2 gas. The MWNT-PVPMe was prepared via a diazonium process and addition reactions with poly(4-vinylpyridine) (PVP) and methyl iodide (MeI). The covalently attached polymers and organic substituents in the polyelectrolyte comprised 60-70% of the total weight. The polyelectrolyte was then used as a substrate for H2ase binding to produce MWNT-PVPMe@H2ase bionanocomposites. X-ray photoelectron spectra revealed that the bionanocomposites included the elements of Br, S, C, N, O, I, Fe, and Ni, which confirmed that they were composed of MWNT-PVPMe and H2ase. Field emission transmission electron microscope images revealed that the H2ase was adsorbed on the surface of MWNT-PVPMe with the domains ranging from 20 to 40 nm. Further, with the use of the bionanocomposites as nanolinkers and Na2PdCl4 as connectors, the (Pd/MWNT-PVPMe@H2ase)n multilayers were constructed on the quartz and gold substrate surfaces by the Pd(II)-directed LBL assembling technique. Finally, the as-prepared LBL multilayers were used as heterogeneous catalysts for hydrogen oxidation with methyl viologen (MV(2+)) as an electron carrier. The dynamic processes for the reversible color change between blue-colored MV(+) and colorless MV(2+) (catalyzed by the LBL multilayers) were video recorded, which confirmed that the H2ase encapsulated within the present LBL multilayers was of much stronger stability and higher biocatalytic activity of H2 oxidation resulting in potential applications for the development of H2 biosensors and fuel cells.

Interfacial self-assembly and characterization of chiral coordination polymer multilayers with bidentate ligands of hydroquinine anthraquinone-1,4-diyl diether as linkers.

Chiral coordination polymers (CPs) have been prepared at the air-water interface by using the ligand of 1,4-bis(9-O-dihydroquininyl)anthraquinone [(DHQ)2AQN] and its enantiomer of 1,4-bis(9-O-dihydroquinidinyl)anthraquinone [(DHQD)2AQN] as linkers and AgNO3 as the connector. Surface pressure-area isotherms indicated that both ligands could form insoluble monomolecular layers on the pure water and AgNO3 subphase surfaces. Compared with the average molecular area on the pure water surface, that of the ligand increased about 10% when its monolayer was formed on the AgNO3 subphase surface due to the formation of Ag-(DHQ)2AQN and Ag-(DHQD)2AQN chiral CPs. These monolayers were deposited on the quartz, Si, and indium tin oxide (ITO) substrate surfaces via the Langmuir-Blodgett (LB) method. The as-prepared LB films were characterized by using UV-vis absorption and fluorescence spectroscopy, circular dichroism and X-ray photoelectron spectroscopy, as well as by using a scanning electron microscope and atomic force microscope. Broad fluorescence emissions were measured at about 365 and 525 nm for the ligands in the methanol solutions. The second emission red shifted to about 555 nm in the LB films of both pure ligands and their Ag-directed CPs. A couple of well-reversible redox waves were recorded and centered at about -0.2 ~ -0.3 V (vs Ag/AgCl) for the ITO electrode covered by the LB films of (DHQ)2AQN, (DHQD)2AQN, or of the Ag(+)-directed CPs, which were designated to one electron transfer process of the ligands. Small aggregates were observed for the LB films prepared at the lower surface pressures, which were compressed to form more uniform two-dimensional layers at the higher surface pressures.

A Protein-Like Nanogel for Spinning Hierarchically Structured Artificial Spider Silk.

Spider dragline silk is draw-spun from soluble, ß-sheet-crosslinked spidroin in aqueous solution. This spider silk has an excellent combination of strength and toughness, which originates from the hierarchical structure containing ß-sheet crosslinking points, spiral nanoassemblies, a rigid sheath, and a soft core. Inspired by the spidroin structure and spider spinning process, a soluble and crosslinked nanogel is prepared and crosslinked fibers are drew spun with spider-silk-like hierarchical structures containing cross-links, aligned nanoassemblies, and sheath-core structures. Introducing nucleation seeds in the nanogel solution, and applying prestretch and a spiral architecture in the nanogel fiber, further tunes the alignment and assembly of the polymer chains, and enhances the breaking strength (1.27 GPa) and toughness (383 MJ m-3 ) to approach those of the best dragline silk. Theoretical modeling provides understanding for the dependence of the fiber's spinning capacity on the nanogel size. This work provides a new strategy for the direct spinning of tough fiber materials.

Layer-by-layer assembly and characterization of multilayers of a manganese porphyrin linked poly(4-vinylpyridinium) derivative and poly(styrenesulfonic acid-o-maleic) acid.

Multilayers of manganese(III) porphyrin-linked poly(vinylpyridinium) (MnTMPyP-PVPMe) polyelectrolyte and poly(styrenesulfonic acid-o-maleic) acid (PSS) have been assembled on gold, quartz, and indium tin oxide surfaces by a layer-by-layer (LBL) technique. The assembly process was monitored by measuring their absorption spectra and frequency change after each assembly, both of which confirmed the formation of three-dimensional MnTMPyP-PVPMe/PSS multilayers. The Soret absorption band of porphyrin red shifted about 8 nm in the multilayer compared with that in the dilute aqueous solution. The average mass changes for each assembly of MnTMPyP-PVPMe and PSS were estimated to be about 2.9 and 0.25 µg/cm(2), respectively. X-ray photoelectron spectra revealed that the as-prepared multilayers were composed of S 2p, C 1s, N 1s, O 1s, and Mn 2p, corresponding to polymers of MnTMPyP-PVPMe and PSS. A rough surface was observed after the assembly of MnTMPyP-PVPMe on the gold surface, but it became smoother when the PSS layer was adsorbed. The significant difference in the mass change and film morphology after the assembly of MnTMPyP-PVPMe compared to those after the assembly of PSS was ascribed to the reason that the MnTMPyP-PVPMe polyelectrolyte contained large metalloporphyrin macrocycles, which were axially coordinated to the pyridyl substituents of the PVP polymeric backbones. The cyclic voltammograms revealed two couples of redox waves in the phosphate electrolyte solution at pH 11, which corresponded to the electron-transfer processes of Mn(II)/Mn(III) and Mn(III)/Mn(IV) of polymeric manganese porphyrin MnTMPyP-PVPMe. The charge-transfer process was also investigated. Finally, the present MnTMPyP-PVPMe/PSS multilayers were used as a heterogeneous catalyst for the decoloration of an azo dye.

Nanoparticle-based applications for cervical cancer treatment in drug delivery, gene editing, and therapeutic cancer vaccines.

Cervical cancer is a leading cause of gynecological tumor related deaths worldwide. The applications of conventional approaches such as chemoradiotherapy and surgery are restricted due to their side effects and drug resistances. Although immune checkpoint inhibitors (ICIs) have emerged as novel choices, their clinical response rates are rather limited. To date there is a lack of effective treatment regimens for patients with metastatic or recurrent cervical cancer. Recently nanomaterials like liposomes, dendrimers, and polymers are considered as promising delivery carriers with advantages of tumor-specific administration, reduced toxicity, and improved biocompatibility. Here, we review the applications of nanoparticles in the fields of drug delivery, CRISPR based genome-editing and therapeutic vaccines in cervical cancer treatment. This article is categorized under: Therapeutic Approaches and Drug Discovery > Nanomedicine for Oncologic Disease.

Sheath-run artificial muscles.

Although guest-filled carbon nanotube yarns provide record performance as torsional and tensile artificial muscles, they are expensive, and only part of the muscle effectively contributes to actuation. We describe a muscle type that provides higher performance, in which the guest that drives actuation is a sheath on a twisted or coiled core that can be an inexpensive yarn. This change from guest-filled to sheath-run artificial muscles increases the maximum work capacity by factors of 1.70 to 2.15 for tensile muscles driven electrothermally or by vapor absorption. A sheath-run electrochemical muscle generates 1.98 watts per gram of average contractile power-40 times that for human muscle and 9.0 times that of the highest power alternative electrochemical muscle. Theory predicts the observed performance advantages of sheath-run muscles.

Ag/N-doped reduced graphene oxide incorporated with molecularly imprinted polymer: An advanced electrochemical sensing platform for salbutamol determination.

In this work, the metallic silver and non-metallic nitrogen co-doped reduced graphene oxide (Ag-N-RGO) was first synthesized by a simple and cost-effective strategy, and then a molecularly imprinted polymer (MIP) was formed in situ at the surface of the prepared composite via electropolymerization of o-phenylenediamine in the presence of salbutamol as the template molecule. The electrochemical characterizations demonstrate that the bifunctional graphene-based composite shows improved catalytic performance than that of pristine graphene doped with one-component or none. The MIP sensor based on Ag-N-RGO owns high porous surface structure, resulting in the increased current response and enhanced recognition capacity than that of non-imprinted sensor. The outstanding performance of the developed sensor derives from the combined advantages of Ag-N-RGO with effective catalytic property and MIP with excellent selectivity. Under the optimal conditions, the electrochemical response of the developed sensor is linearly proportional to the concentration of salbutamol in the range of 0.03-20.00µmolL-1 with a low detection limit of 7 nmol L-1. The designed sensor has exhibited the multiple advantages such as low cost, simple manufacture, convenient use, excellent selectivity and good reproducibility. Finally, the proposed method has been extended for the determinations of salbutamol in human urine and pork samples, and the satisfactory recoveries between 98.9-105.3% are achieved.

Preparation and study of polyacryamide-stabilized silver nanoparticles through a one-pot process.

A one-pot route was illustrated to synthesize stable well-dispersed silver colloids stabilized by polyacrylamide on a large scale. Reduction of silver ions and polymerization of acrylamide occurred almost simultaneously in the absence of a commonly used reducing agent and initiator. A possible mechanism for the formation of silver nanoparticles with bimodal size distribution was proposed. The structure and composition of the obtained nanoparticles were characterized carefully. Furthermore, light scattering simulation and UV-vis absorption studies confirmed that the obtained colloids were the mixture of Ag and Ag2O nanoparticles. The presence of silver oxide layers on the nanoparticle surface should be responsible for the broadening of the surface plasmon band of silver nanoparticles. Ag2O layers could be added or removed from Ag nanoparticle surfaces by the addition of HNO3, HAc, or NaCl solution to the as-obtained silver colloids.

Surface amorphization of NiTi alloy induced by Ultrasonic Nanocrystal Surface Modification for improved mechanical properties.

We report herein the effects of Ultrasonic Nano-crystal Surface Modification (UNSM), a severe surface plastic deformation process, on the microstructure, mechanical (hardness, wear), wettability and biocompatibility properties of NiTi shape memory alloy. Complete surface amorphization of NiTi was achieved by this process, which was confirmed by X-ray diffraction and high-resolution transmission electron microscopy. The wear resistance of the samples after UNSM processing was significantly improved compared with the non-processed samples due to increased surface hardness of the alloy by this process. In addition, cell culture study demonstrated that the biocompatibility of the samples after UNSM processing has not been compromised compared to the non-processed sample. The combination of high wear resistance and good biocompatibility makes UNSM an appealing process for treating alloy-based biomedical devices.

Disulfide-bridged cleavable PEGylation in polymeric nanomedicine for controlled therapeutic delivery.

PEGylation in polymeric nanomedicine has gained substantial predominance in biomedical applications due to its resistance to protein absorption, which is critically important for a therapeutic delivery system in blood circulation. The shielding layer of PEGylation, however, creates significant steric hindrance that negatively impacts cellular uptake and intracellular distribution at the target site. This unexpected effect compromises the biological efficacy of the encapsulated payload. To address this issue, one of the key strategies is to tether the disulfide bond to PEG for constructing a disulfide-bridged cleavable PEGylation. The reversible disulfide bond can be cleaved to enable selective PEG detachment. This article provides an overview on the strategy, method and progress of PEGylation nanosystem with the cleavable disulfide bond.

A hydrogen biosensor made of clay, poly(butylviologen), and hydrogenase sandwiched on a glass carbon electrode.

A hydrogen gas (H(2)) biosensor was developed in which hydrogenase (H(2)ase) was immobilized and sandwiched between two layers of a montmorillonite clay and poly(butylviologen) (PBV) mixture on a glass carbon electrode. The immobilized PBV efficiently enhanced the electron transfer among the electrode, H(2)ase, and methyl viologen in solution. Both PBV and methyl viologen acted as the electron carrier in the clay-PBV-H(2)ase modified electrode. The clay-PBV-H(2)ase electrode catalyzed the oxidation of H(2) to protons (H(+)) with the electrons being transferred by viologen groups to the electrode. The activation energy of this process was 38+/-2 kJ/mol at pH 7. The catalytic current of the clay-PBV-H(2)ase electrode increased linearly when exposed to increasing concentrations of H(2) gas. In contrast, this electrode showed no activity when exposed to three combustible compounds, namely, carbon monoxide, methane and methanol. The optimum pH range for the oxidation of H(2) by the clay-PBV-H(2)ase electrode was from 7 to 10. Electron transfer process in the clay-PBV-H(2)ase electrode is discussed.

[Technological experience of occlusal reconstruction with IPS e.max Press for severely worn dentition].

PURPOSE: To investigate the feasibility of occlusal reconstruction with IPS e.max Press for patients suffering from severely worn dentition, and to summarize the technological experience. METHODS: IPS e.max Press was used to reconstruct occlusion for one patient with severely worn dentition. Provisional restorations were fitted in worn teeth to rehabilitate the vertical dimension and centric relationship almost 3 months before final treatment. Face bow was used to transfer the general information of provisional restorations to articulator, including the plane of occlusion, anatomical outline and intercuspal position of teeth. RESULTS: After 24 months of follow-up, the masticatory efficiency and facial appearance were improved significantly, and TMJ disorder was not observed. The patient was satisfied with the prostheses. CONCLUSIONS: IPS e.max Press is an effective and reliable treatment of occlusal reconstruction.The short term effect is promoting. Supported by Clinical Medical Research Fund of Bureau of Science and Technology, Jiangsu Province(SBL201230169).

[The prefabricated post and composite resin core technique used in restoring residual crown of posterior tooth].

PURPOSE: To investigate the clinical effect of repairing posterior residual crown using titanium alloy post combined with composite resin core technique. METHODS: Twenty-one patients (26 residual crown) with perfect root canal therapy were selected. Modern bonding technique was used to build up the core with titanium alloy post and flow composite resin together for crown restoration. RESULTS: After ten years of clinical observation, only 4 cases among the 21 patients failed in restoration. The rate of success was 85%. X-ray showed that the periapical alveolar bone density was enhanced after restoration. CONCLUSIONS: Standard root canal therapy and effective post-core strengthening can restore the function of the residual crown and retain the tooth.

Electrochemically driven generation of manganese(IV,V)-oxo multiporphyrin arrays and their redox properties with manganese(III) species in Langmuir-Blodgett films.

High-valency manganese (IV,V)-oxo porphyrins have been electrochemically generated and in situ spectrally characterized in multiporphyrin arrays, which were formed by an interfacial coordination reaction of Na2PdCl4 with manganese (III) tetrapyridylporphyrin (MnTPyP). Multilayers of the Pd-MnTPyP multiporphyrin arrays were obtained by the Langmuir-Blodgett (LB) method. The redox behaviors of manganese in the multiporphyrin arrays were pH-dependent. Spectroelectrochemical experiments revealed a reversible redox process between Pd-Mn(III)TPyP and its Mn(IV)-oxo species, but an irreversible process between Pd-Mn(III)TPyP and its Mn(V)-oxo species. The Pd-Mn(IV)TPyP multiporphyrin arrays could be spontaneously reduced to their Mn(III) complex, while the Pd-Mn(V)TPyP arrays were rather stable in basic solutions (pH > 10.5). However, when the Pd-Mn(V)TPyP multiporphyrin arrays were washed by or immersed in water, they were immediately reduced to their Mn(III) complex. Because these well-organized multiporphyrin arrays are of high thermal and chemical stability, they are potential molecular materials in the studies of natural and artificial catalytic processes as well as redox-based molecular switches.