In vitro evaluation of shape-memory hydrogels for removable dental prostheses and optimization of phase-transition temperature for intraoral use.

STATEMENT OF PROBLEM: Removable dental prostheses require periodic relining with the loss of intaglio surface fit because of mucosal shape changes over time. Therefore, a new material with high adaptability to tissue changes over time would be beneficial. PURPOSE: This study focused on a shape-memory gel (SMG) that softens when heated, retains its shape when cooled, and returns to its original shape when reheated. The purpose was to optimize SMG for intraoral use by controlling the ratio of 2 acrylate monomers and to evaluate the changes in the shape memory and physical properties of SMG with temperature and to evaluate biocompatibility. MATERIAL AND METHODS: SMG specimens were synthesized using the following mixing ratios of 2 monomers, docosyl acrylate (DA) and stearyl acrylate (SA): 0:100, 25:75, 50:50, 75:25, and 100:0. SMG specimens were photopolymerized using a fluorescent light-polymerizing unit. To evaluate shape memory as a function of temperature, permanent deformation was measured based on the standardized compression set test for thermoplastic rubber. For evaluation of the physical properties and cytotoxicity, a 3-dimensionally printed denture base material was used as the control material. All assessments were compared between the groups by using 1-way analysis of variance followed by the Tukey-Kramer multiple comparison test (α=.05). RESULTS: SMGs with a higher amount of DA maintained their compressed shape at room and intraoral temperatures. However, the SMG matrices softened and recovered their original shapes above 60 °C. SMGs showed Shore A hardness equivalent to that of the denture-base polymer material at intraoral temperatures because of the high phase-transition temperature. The low water solubility of SMGs supported the biocompatibility test results. CONCLUSIONS: SMG, in which the phase-transition temperature was controlled by mixing acrylate monomers with different melting points, exhibited shape memory in the intraoral environment. The results indicate the feasibility of applying SMG for the fabrication of removable dental prostheses because of its high adaptability to tissue changes over time and biocompatibility.

Effect of the constituent networks of double-network gels on their mechanical properties and energy dissipation process.

Double-network (DN) gels, consisting of brittle first and ductile second networks, possess extraordinary strength, extensibility, and fracture toughness while maintaining a high solvent content. Herein, we prepare DN gels consisting of various concentrations of the first and second networks to investigate the effect of each network structure on the tensile and fracture properties of DN gels. The results showed that the tensile properties of DN gels before yielding are mainly dominated by the first network, serving as a skeleton, whereas the properties after necking are determined by both networks. Moreover, we found that the DN gels with significant energy dissipation capacities exhibit high fracture resistance. Thus, this study not only confirms the factors determining the mechanical characteristics of DN gels but also explains how the two networks concertedly improve the toughness of DN gels.

3D printing of shape memory hydrogels with tunable mechanical properties.

Utilization of soft material like hydrogels for task-specific applications such as in soft robotics requires freedom in the manufacturing process and designability. Here, we have developed highly robust thermoresponsive poly(dimethyl acrylamide-co-stearyl acrylate and/or lauryl acrylate) (PDMAAm-co-SA and/or LA)-based shape memory gels (SMGs) using a customized optical 3D gel printer. This process enabled rapid and moldless fabrication of SMGs with a variety of shapes and sizes. By varying the compositions of the constituent monomers, a wide variety of SMGs with tunable mechanical, thermal, optical and swelling properties have been obtained. Printed SMGs with excellent fixity and recovery ratios have exhibited a wide range of values of Young's modulus (0.04-17.35 MPa) and strain (612-2363%) at room temperature when the acrylate co-monomer (SA and LA) content was varied and the value of strain has been found to be enhanced at elevated temperatures. Thermogravimetric analysis (TGA) of the SMGs shows one step peak degradation (407-417 °C) regardless of composition after an initial mass loss due to water evaporation. Dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) revealed variable transition temperatures (29-49.5 °C) depending on the SA and LA content. SMGs with all of the composition ratios possess high transparency with variable swelling degrees in water and different organic solvents and exhibit refractive index values in the range of intraocular lenses, making them suitable for applications in the optical field. These unique properties of 3D printed SMGs with free formability and tunable properties are expected to generate rapid demand in a variety of sectors in biomedicine, robotics and sensing applications.

Deformation of contacting interface between polymer hydrogel and silica sphere studied by resonance shear measurement.

The deformation of the interfaces between a soft material and hard material in contact plays an important role in the friction and lubrication between them. We recently reported that the elastic property of the contact interface dominated the friction of the interface between a flat polymer hydrogel [double network (DN) gel of 2-acrylamide-2-methylpropanesulfonic acid and N,N-dimethylacrylamide] and a silica sphere [Ren et al., Soft Matter 11, 6192-6200 (2015)]. In this study, in order to quantitatively describe the dependence of the elastic response on the geometrical parameters of the deformed interfaces, we employed the resonance shear measurement (RSM) and investigated the deformation of the interfaces between a flat DN gel and silica spheres by varying the curvature radius (R = 18.3, 13.8, 9.2, 6.9 mm). Resonance curves were analyzed using a mechanical model consisting of the elastic (k 2) and viscous (b 2) parameters of the contact interface. The obtained elastic parameter (k 2) increases at higher loads and for smaller silica spheres, while the viscous parameter (b 2) was negligibly low for all the conditions. The relations between the elastic parameter (k 2), geometric parameters of the deformed contact interface, and the applied normal load were investigated. The elastic parameter (k 2) was found to be proportional to the arc length (arc) (radius of contact area, r), i.e., k 2 ∝ arc or k 2 ∝ r. We introduced the term "elastic modulus of the contact interface, E contact" as a proportionality constant to describe the elastic parameter of the deformed interfaces (k 2): k 2 (N/m) = arc (m) × E contact (Pa). Thus, the friction (f) between the DN gel and the silica sphere can be described by the following equation: f = f elastic = arc (m) × E contact (N/m2) × Δx (m) (Δx: shear deformation of the contact interface between the DN gel and silica sphere). The E contact value determined from the slope k 2 vs arc was 493 ± 18 kPa. The RSM measurement and the analysis presented here can be a unique method for characterizing the specific properties of the deformed interfaces between soft and hard materials.

Friction of polymer hydrogels studied by resonance shear measurements.

The friction between an elastomer and a hard surface typically has two contributors, i.e., the interfacial and deformation components. The friction of viscoelastic hydrogel materials has been extensively studied between planar gel and planar substrate surfaces from the viewpoint of an interfacial interaction. However, the geometry of the contact in practical applications is much more complex. The contribution of geometric and elastic deformation terms of a gel to friction could not be neglected. In this study, we used resonance shear measurements (RSMs) for characterizing the shear response of a glass sphere on a flat polymer hydrogel, a double network (DN) gel of 2-acrylamide-2-methylpropanesulfonic acid and N,N-dimethylacrylamide. The contact mechanics conformed to the Johnson-Kendall-Roberts theory. The observed resonance curves exhibited rather sharp peaks when the DN gel and the silica sphere were brought into contact, and their intensity and frequency increased with the increase in the normal load. We proposed a simple physical model of the shearing system, and the elastic (k2) and viscous (b2) parameters of the interface between a silica sphere and a flat DN gel were obtained. The friction force from elastic deformation and viscous dissipation terms was then estimated using the obtained parameters. It was revealed that the elastic parameter (k2) increased up to 1780 N m(-1) at a normal load of 524 mN, while the viscous parameter (b2) was zero or quite low (<0.1 N s m(-1)) for a silica sphere (radius of 18.4 mm). Thus, the friction force between a flat DN gel and a silica sphere in air was dominated by the elastic term due to the local deformation by contact with the silica sphere. By adding water, the elastic parameter (k2) remained the same, while the viscous parameter (b2) slightly increased. However, the viscous term fviscous was still much smaller than felastic. To the best of our knowledge, this study was the first quantitative estimation of the contribution of the elastic deformation term to the friction in the case when deformation of non-flat contact regions occurs. The obtained results can be basic knowledge for designing gels for applications such as artificial cartilages and sliding bearings.

In situ observation of a hydrogel-glass interface during sliding friction.

Direct observation of hydrogel contact with a solid surface in water is indispensable for understanding the friction, lubrication, and adhesion of hydrogels under water. However, this is a difficult task since the refractive index of hydrogels is very close to that of water. In this paper, we present a novel method to in situ observe the macroscopic contact of hydrogels with a solid surface based on the principle of critical refraction. This method was applied to investigate the sliding friction of a polyacrylamide (PAAm) hydrogel with glass by using a strain-controlled parallel-plate rheometer. The study revealed that when the compressive pressure is not very high, the hydrogel forms a heterogeneous contact with the glass, and a macro-scale water drop is trapped at the soft interface. The pre-trapped water spreads over the interface to decrease the contact area with the increase in sliding velocity, which dramatically reduces the friction of the hydrogel. The study also revealed that this heterogeneous contact is the reason for the poor reproducibility of hydrogel friction that has been often observed in previous studies. Under the condition of homogeneous full contact, the molecular origin of hydrogel friction in water is discussed. This study highlights the importance of direct interfacial observation to reveal the friction mechanism of hydrogels.

A new training model using the self-healing properties of supramolecular hydrogels for endoscopic combined intrarenal surgery.

The combination of hydronephrosis formation, ureteroscopic imaging, and ultrasound delineation has not been included in any non-biological training model of percutaneous nephrolithotomy or endoscopic combined intrarenal surgery. We aimed to develop a realistic kidney phantom using the self-healing properties of supramolecular hydrogels for percutaneous nephrolithotomy and endoscopic combined intrarenal surgery and evaluate its suitability as a training model.Expert and resident urologists performed ultrasound-guided renal pelvic punctures and flexible ureteroscopies for endoscopic combined intrarenal surgery using a training model. Subsequently, the training model was evaluated using a 17-item Likert scale questionnaire (range, 1-5 points). After being filled with carrageenan, the collecting system was inflated, and the relationship between the collecting system volume and collecting system pressure was determined. The durability of the model was verified by repeatedly inserting a 16-Fr access sheath. Five novices and seven urology experts performed the procedure. The mean questionnaire score was 4.25 (standard deviation, 0.37). The model was able to hold 50 mL of air, and the pressure in the collecting system ranged from 6 to 33 mmHg. Repeated punctures were possible even when a 16-Fr access sheath was inserted. Our new training model included the self-healing properties of supramolecular hydrogels, which are tough and flexible and can be evaluated using ultrasonography. According to the questionnaire score, the model was highly satisfactory and has potential as a new educational tool.

Assessing temporal correlation in environmental risk factors to design efficient area-specific COVID-19 regulations: Delhi based case study.

Amid ongoing devastation due to Serve-Acute-Respiratory-Coronavirus2 (SARS-CoV-2), the global spatial and temporal variation in the pandemic spread has strongly anticipated the requirement of designing area-specific preventive strategies based on geographic and meteorological state-of-affairs. Epidemiological and regression models have strongly projected particulate matter (PM) as leading environmental-risk factor for the COVID-19 outbreak. Understanding the role of secondary environmental-factors like ammonia (NH3) and relative humidity (RH), latency of missing data structuring, monotonous correlation remains obstacles to scheme conclusive outcomes. We mapped hotspots of airborne PM2.5, PM10, NH3, and RH concentrations, and COVID-19 cases and mortalities for January, 2021-July,2021 from combined data of 17 ground-monitoring stations across Delhi. Spearmen and Pearson coefficient correlation show strong association (p-value < 0.001) of COVID-19 cases and mortalities with PM2.5 (r > 0.60) and PM10 (r > 0.40), respectively. Interestingly, the COVID-19 spread shows significant dependence on RH (r > 0.5) and NH3 (r = 0.4), anticipating their potential role in SARS-CoV-2 outbreak. We found systematic lockdown as a successful measure in combatting SARS-CoV-2 outbreak. These outcomes strongly demonstrate regional and temporal differences in COVID-19 severity with environmental-risk factors. The study lays the groundwork for designing and implementing regulatory strategies, and proper urban and transportation planning based on area-specific environmental conditions to control future infectious public health emergencies.

Exploring phytochemical composition, photocatalytic, antibacterial, and antifungal efficacies of Au NPs supported by Cymbopogon flexuosus essential oil.

Biofabrication of gold nanoparticles (AuNPs) using the aromatic essential oils is highlighted due to its simple, economical, low toxicity, and eco-friendly nature. Essential oil of Cymbopogon flexuosus (CF), an economically valuable medicinal plant, exhibits anti-inflammatory, anti-tumor, antioxidant, and antimicrobial activities. For the first time, this research accounts for the biosynthesis, physicochemical, photocatalytic, antifungal, antibacterial properties of biogenic AuNPs, fabricated using CF essential oil collected from different altitudes (S1-Palampur, S2-Haryana, S3-Dehradun). The altitudinal disparity in the phytochemical composition of essential oils is highlighted. The average crystallite size ranged from 10 to 32 nm and was influenced by CF samples used in the synthesis. The spectroscopic outcomes revealed the involvement of bioactive reagents from CF essential oil in the fabrication and stabilization of AuNPs. The fabricated AuNPs exhibited excellent antimicrobial activities against all tested strains (Staphyloccucs aureus, Escherichia coli, Fusarium oxysporum), showing their efficacy as an antimicrobial agent to treat infectious diseases. Moreover, AuNPs exhibited excellent photocatalytic efficacy of around 91.8% for the degradation of methylene blue under exposure of direct sunlight for 3 h without the assistance of an external reducing agent. The outcomes highlight a potential economic and environmentally friendly strategy to fabricate biogenic AuNPs for diversified industrial applications where antimicrobial and photocatalytic efficacies are the key requirements.

Essential oil-mediated biocompatible magnesium nanoparticles with enhanced antibacterial, antifungal, and photocatalytic efficacies.

Emergent application of antimicrobial strategies as symptomatic treatment in coronavirus disease (COVID-19) and linkage of severe acute respiratory syndrome coronavirus2 with microbial infections, has created colossal demand for antimicrobials. For the first time, this communication explore the physicochemical, antifungal, antibacterial, and photocatalytic properties of biogenic magnesium nanoparticles (MgNPs), synthesized using essential oil of Cymbopogon flexuosus's as an efficient multifunctional reducing and stabilizing/capping reagent. It is observed that MgNPs (ranging in size: 8-16 nm) of varying phytochemical compositions (MgS1, MgS2, MgS3) exhibited various useful physicochemical, antimicrobial, and photocatalytic properties. FTIR outcomes highlight the functional biomolecules-assisted reduction of Mg from Mg+ to Mg0. Among all, MgS3-Nps owing to the smallest particle size exhibited superior photocatalytic efficacy (91.2%) for the methylene blue degradation upon direct exposure to the sunlight for 3 h without using any reducing agents. Fabricated MgNPs also exhibited excellent antifungal (against Fusarium oxysporum) and antibacterial (versus Staphylococcus aureus and Escherichia coli) efficacies compared to state-of-the-art antimicrobial agents deployed for the treatment of infectious diseases. Based on this investigated greener approach, imperative from economic and environmental viewpoint, such essential oil based-MgNPs can be a potential nanosystem for various industrial applications where photocatalytic, and biomedical attributes are the key requirements.

Recent Advances in Electrochemical Biosensors: Applications, Challenges, and Future Scope.

The electrochemical biosensors are a class of biosensors which convert biological information such as analyte concentration that is a biological recognition element (biochemical receptor) into current or voltage. Electrochemical biosensors depict propitious diagnostic technology which can detect biomarkers in body fluids such as sweat, blood, feces, or urine. Combinations of suitable immobilization techniques with effective transducers give rise to an efficient biosensor. They have been employed in the food industry, medical sciences, defense, studying plant biology, etc. While sensing complex structures and entities, a large data is obtained, and it becomes difficult to manually interpret all the data. Machine learning helps in interpreting large sensing data. In the case of biosensors, the presence of impurity affects the performance of the sensor and machine learning helps in removing signals obtained from the contaminants to obtain a high sensitivity. In this review, we discuss different types of biosensors along with their applications and the benefits of machine learning. This is followed by a discussion on the challenges, missing gaps in the knowledge, and solutions in the field of electrochemical biosensors. This review aims to serve as a valuable resource for scientists and engineers entering the interdisciplinary field of electrochemical biosensors. Furthermore, this review provides insight into the type of electrochemical biosensors, their applications, the importance of machine learning (ML) in biosensing, and challenges and future outlook.

Hydrogels with cylindrically symmetric structure at macroscopic scale by self-assembly of semi-rigid polyion complex.

A hydrogel with cylindrically symmetric structure at macroscopic scale has been developed by polymerization of a cationic monomer in the presence of a small amount of semi-rigid polyanion poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT) in a cylinder glass tube. The polyion complex radially aligns in the outer region of the synthesized cylinder gel. On the other hand, it orients in concentric and axial directions in the inner region. To the authors' knowledge, this is the first report of such millimeter-scale ordered structure developed in a polymeric hydrogel. We elucidate that homeotropic alignment on the glass wall is energetically favorable for the semi-rigid polyion complex, resulting in the radial orientation in the outer region. In the inner region, the oriented structures result from the monomer difffusion (due to the heterogeneous polymerization) that induces PBDT orientation perpendicular to the diffusion direction. The structured gels showing sensitive response of birefringence to external force are expected to find applications in optical sensors.

Light Scattering and Rheological Studies of 3D/4D Printable Shape Memory Gels Based on Poly (N,N-Dimethylacrylamide-co-Stearyl Acrylate and/or Lauryl Acrylates).

In this work, we present the structural analysis of 3D/4D printable N,N-dimethylacrylamide (DMAAm)-co-stearyl acrylate (SA) and/or lauryl acrylate (LA)-based shape memory gels (SMGs). We characterized these gels by scanning microscopic light scattering technique (SMILS) where a time- and space-averaged correlation function is obtained to overcome the inhomogeneous media. Thus, the characteristic size of the gel internal network (mesh size, ξ) and crosslinking densities are estimated from the Einstein-Stokes formula. The rheological study of the SMGs revealed information about their mechanical strength and transition temperature. From the experimental storage modulus measured by rheological study, crosslinking density and mesh size of the network were also calculated. Both the techniques suggest that SMG with high crystalline content of SA monomer in the gel network contain smaller mesh size (1.13 nm for SMILS and 9.5 nm for rheology study) and high crosslinking density. The comparative study between the light scattering technique and rheological analysis through the quantitative analysis of crosslinking densities will be important to understand the structural properties of the SMGs.

Rheological and mechanical properties of edible gel materials for 3D food printing technology.

3D food printing sectors require comprehensive knowledge on viscoelastic and mechanical properties of diverse food materials in order to effectively utilize them in rapid and customized 3D production for supply and manufacturing chains. In this work, we present mechanical and rheological properties of Agar and Konjac based edible gels at different Agar and Konjac weight ratio and discuss their 3D printing performance. Gel samples with higher Konjac content positively contributed to the viscoelastic properties of the gel samples which in return has been found viable for extrusion-based 3D printing. By choosing appropriate printing parameters, different shapes are printed to demonstrate printing resolution. We expect, this study will add potential scope for evaluating and optimizing soft-gel materials for 3D food printing sector.

Formation of well-oriented microtubules with preferential polarity in a confined space under a temperature gradient.

Tubulin polymerization in a confined space under a temperature gradient produced well-oriented microtubule assemblies with preferential polarity. We analyzed the structure and polarity of these assemblies at various levels of resolution by performing polarized light microscopy (millimeter order), fluorescence microscopy (micrometer order), and transmission electron microscopy (nanometer order).

Identification of novel protein domain for sialyloligosaccharide binding essential to Mycoplasma mobile gliding.

Sialic acids, terminal structures of sialylated glycoconjugates, are widely distributed in animal tissues and are often involved in intercellular recognitions, including some bacteria and viruses. Mycoplasma mobile, a fish pathogenic bacterium, binds to sialyloligosaccharide (SO) through adhesin Gli349 and glides on host cell surfaces. The amino acid sequence of Gli349 shows no similarity to known SO-binding proteins. In the present study, we predicted the binding part of Gli349, produced it in Escherichia coli and proved its binding activity to SOs of fetuin using atomic force microscopy. Binding was detected with a frequency of 10.3% under retraction speed of 400 nm/s and was shown to be specific for SO, as binding events were competitively inhibited by the addition of free 3'-sialyllactose. The histogram of the unbinding forces showed 24 pN and additional peaks. These results suggested that the distal end of Gli349 constitutes a novel sialoadhesin domain and is directly involved in the gliding mechanism of M. mobile.

Development of Tungsten Oxide Nanoparticle Modified Carbon Fibre Cloth as Flexible pH Sensor.

A reagent-less pH sensor based on disposable and low cost carbon fibre cloth (CFC) is demonstrated for the first time, where tungsten oxide nanoparticles were grown directly onto the CFC substrate. For comparison purpose, tungsten oxide nanoparticle modified glassy carbon electrode (GCE) was also fabricated as a pH sensor, where hydrothermally synthesized tungsten oxide nanoparticles were drop casted onto the GCE surface. The corresponding equilibrium potential using tungsten oxide/CFC as a pH sensor was measured using open circuit potential (OCP), and was found to be linear over the pH range of 3-10, with a sensitivity of 41.38 mVpH-1, and response time of 150 s. In the case of tungsten oxide/GCE as a pH sensor, square wave voltammetry (SWV) was used to measure the shifts in peak potential and was found to be linear with a pH range of 3-11, and a sensitivity of 60 mVpH-1 with a potential drift of 2.4-5.0% after 3 hour of continuous use. The advantages of tungsten oxide/CFC and tungsten oxide/GCE as pH sensing electrode have been directly compared with the commercial glass probe based electrode, and validated in real un-buffered samples. Thereby, tungsten oxide nanoparticles with good sensitivity and long term stability could be potentially implemented as a low cost and robust pH sensor in numerous applications for the Internet of Things (IoT).

Observation of the three-dimensional structure of actin bundles formed with polycations.

Three-dimensional structures of actin bundles formed with polycations were observed by using transmission electron microtomography and atomic force microscopy. We found, for the first time, that the cross-sectional morphology of actin bundles depends on the polycation species and ionic strength, while it is insensitive to the degree of polymerization and concentration of polycation. Actin bundles formed with poly-N-[3-(dimethylamino)propyl] acrylamide methyl chloride quaternary show a ribbon-like cross-sectional morphology in low salt concentrations that changes to cylindrical cross-sectional morphology with hexagonal packing of the actin filaments in high salt concentrations. Contrastingly, actin bundles formed with poly-L-lysine show triangular cross-sectional morphology with hexagonal packing of the actin filaments. These variations in cross-sectional morphology are discussed in terms of anisotropy in the electrostatic energy barrier.

Effect of substrate adhesion and hydrophobicity on hydrogel friction.

In this paper, the frictional behavior of a neutral hydrogel, polyvinyl alcohol (PVA), on smooth solid substrates with various levels of hydrophobicity have been investigated in water using a strain-controlled parallel-plate rheometer. For the sliding velocity dependence of friction, we detected a distinct friction transition on hydrophobic substrates that are strongly adhesive to the gel, while no clear transition was observed on hydrophilic substrates that are weakly adhesive to the gel. Even on the most hydrophobic substrate, the maximum frictional stress is approximately 1/10-1/5 of the gel's elastic modulus under a large normal strain of 26%. Furthermore, the frictional stress on hydrophobic substrates in the high velocity region, larger than the transition, is much lower than that on hydrophilic ones. We attempted to explain these phenomena with the help of two models: a molecular model based on the thermal fluctuations occurring during adsorption-desorption of polymers and a continuum mechanics model based on elastic dewetting and forced wetting.

Friction of a soft hydrogel on rough solid substrates.

We investigated the sliding friction between a soft hydrogel and rough and weakly adhesive solid substrates in a water environment. Polyvinyl alcohol (PVA) hydrogels of different elastic moduli and two sets of glass substrates with different contact angles to water, all of which varied in their surface roughness, were used. The friction measurement was performed by using a strain-controlled parallel-plate rheometer. With an increase in substrate roughness, the friction in the low velocity region increased slightly, while it decreased significantly above a critical velocity on a surface with a roughness larger than 1 µm. Below this critical velocity, the frictional stress changed with the glass substrate surface energy, while above this critical velocity, it was not sensitive to the glass substrate surface energy. The velocity-dependence of friction on rough surfaces is explained in terms of surface contact dynamics and is characterized by two velocities, i.e., vf and vdrainage. The former is determined by the cooperative diffusion constant of the gels, and the latter is by the surface roughness of the substrate and the normal pressure applied on the gel.