Hydrogel Mesh Research Articles

Prediction of Viscoelastic Properties of Enzymatically Crosslinkable Tyramine-Modified Hyaluronic Acid Solutions Using a Dynamic Monte Carlo Kinetic Approach.

The present study deals with the mathematical modeling of crosslinking kinetics of polymer–phenol conjugates mediated by the Horseradish Peroxidase (HRP)-hydrogen peroxide (H2O2) initiation system. More specifically, a dynamic Monte Carlo (MC) kinetic model is developed to quantify the effects of crosslinking conditions (i.e., polymer concentration, degree of phenol substitution and HRP and H2O2 concentrations) on the gelation onset time; evolution of molecular weight distribution and number and weight average molecular weights of the crosslinkable polymer chains and gel fraction. It is shown that the MC kinetic model can faithfully describe the crosslinking kinetics of a finite sample of crosslinkable polymer chains with time, providing detailed molecular information for the crosslinkable system before and after the gelation point. The MC model is validated using experimental measurements on the crosslinking of a tyramine modified Hyaluronic Acid (HA-Tyr) polymer solution reported in the literature. Based on the rubber elasticity theory and the MC results, the dynamic evolution of hydrogel viscoelastic and molecular properties (i.e., number average molecular weight between crosslinks, Mc, and hydrogel mesh size, ξ) are calculated.

Organisation of clay nanoplatelets in a polyelectrolyte-based hydrogel

We investigate the organisation of clay nanoplatelets within a hydrogel based on modified ionenes, cationic polyelectrolytes forming physically crosslinked hydrogels induced by hydrogen bonding and π-π stacking. Combination of small angle X-ray and neutron scattering (SAXS, SANS) reveals the structure of the polyelectrolyte network as well as the organisation of the clay additives. The clay-free hydrogel network features a characteristic mesh-size between 20 and 30 nm, depending on the polyelectrolyte concentration. Clay nanoplatelets inside the hydrogel organise in a regular face-to-face stacking manner, with a large repeat distance, following rather closely the hydrogel mesh-size. The presence of the nanoplatelets does not modify the hydrogel mesh size. Further, the clay-compensating counterions (Na+, Ca2+ or La3+) and the clay type (montmorillonite, beidellite) both have a significant influence on nanoplatelet organisation. The degree of nanoplatelet ordering in the hydrogel is very sensitive to the negative charge location on the clay platelet (different for each clay type). Increased nanoplatelet ordering leads to an improvement of the elastic properties of the hydrogel. On the contrary, the presence of dense clay aggregates (tactoids), induced by multi-valent clay counterions, destroys the hydrogel network as seen by the reduction of the elastic modulus of the hydrogel.

Hydrogel–mesh composite for wound closure

During operations, surgical mesh is commonly fixed on tissues through fasteners such as sutures and staples. Attributes of surgical mesh include biocompatibility, flexibility, strength, and permeability, but sutures and staples may cause stress concentration and tissue damage. Here, we show that the functions of surgical mesh can be significantly broadened by developing a family of materials called hydrogel-mesh composites (HMCs). The HMCs retain all the attributes of surgical mesh and add one more: adhesion to tissues. We fabricate an HMC by soaking a surgical mesh with a precursor, and upon cure, the precursor forms a polymer network of a hydrogel, in macrotopological entanglement with the fibers of the surgical mesh. In a surgery, the HMC is pressed onto a tissue, and the polymers in the hydrogel form covalent bonds with the tissue. To demonstrate the concept, we use a poly(N-isopropylacrylamide) (PNIPAAm)/chitosan hydrogel and a polyethylene terephthalate (PET) surgical mesh. In the presence a bioconjugation agent, the chitosan and the tissue form covalent bonds, and the adhesion energy reaches above 100 J⋅m-2 At body temperature, PNIPAAm becomes hydrophobic, so that the hydrogel does not swell and the adhesion is stable. Compared with sutured surgical mesh, the HMC distributes force over a large area. In vitro experiments are conducted to study the application of HMCs to wound closure, especially on tissues under high mechanical stress. The performance of HMCs on dynamic living tissues is further investigated in the surgery of a sheep.

Selectively Cross-Linked Tetra-PEG Hydrogels Provide Control over Mechanical Strength with Minimal Impact on Diffusivity.

Synthetic hydrogels formed from poly(ethylene glycol) (PEG) are widely used to study how cells interact with their extracellular matrix. These in vivo-like 3D environments provide a basis for tissue engineering and cell therapies but also for research into fundamental biological questions and disease modeling. The physical properties of PEG hydrogels can be modulated to provide mechanical cues to encapsulated cells; however, the impact of changing hydrogel stiffness on the diffusivity of solutes to and from encapsulated cells has received only limited attention. This is particularly true in selectively cross-linked “tetra-PEG” hydrogels, whose design limits network inhomogeneities. Here, we used a combination of theoretical calculations, predictive modeling, and experimental measurements of hydrogel swelling, rheological behavior, and diffusion kinetics to characterize tetra-PEG hydrogels’ permissiveness to the diffusion of molecules of biologically relevant size as we changed polymer concentration, and thus hydrogel mechanical strength. Our models predict that hydrogel mesh size has little effect on the diffusivity of model molecules and instead predicts that diffusion rates are more highly dependent on solute size. Indeed, our model predicts that changes in hydrogel mesh size only begin to have a non-negligible impact on the concentration of a solute that diffuses out of hydrogels for the smallest mesh sizes and largest diffusing solutes. Experimental measurements characterizing the diffusion of fluorescein isothiocyanate (FITC)-labeled dextran molecules of known size aligned well with modeling predictions and suggest that doubling the polymer concentration from 2.5% (w/v) to 5% produces stiffer gels with faster gelling kinetics without affecting the diffusivity of solutes of biologically relevant size but that 10% hydrogels can slow their diffusion. Our findings provide confidence that the stiffness of tetra-PEG hydrogels can be modulated over a physiological range without significantly impacting the transport rates of solutes to and from encapsulated cells.

3D Hyaluronic Acid Hydrogels for Modeling Oligodendrocyte Progenitor Cell Behavior as a Function of Matrix Stiffness.

The lack of regenerative solutions for demyelination within the central nervous system motivates the development of strategies to expand and drive the bioactivity of the cells, including oligodendrocyte progenitor cells (OPCs), that ultimately give rise to myelination. In this work, we introduce a 3D hyaluronic acid (HA) hydrogel system to study the effects of microenvironmental mechanical properties on the behavior of OPCs. We tuned the stiffness of the hydrogels to match the brain tissue (storage modulus 200-2000 Pa) and studied the effects of stiffness on metabolic activity, proliferation, and cell morphology of OPCs over a 7 day period. Although hydrogel mesh size decreased with increasing stiffness, all hydrogel groups facilitated OPC proliferation and mitochondrial metabolic activity to similar degrees. However, OPCs in the two lower stiffness hydrogel groups (170 ± 42 and 794 ± 203 Pa) supported greater adenosine triphosphate levels per cell than the highest stiffness hydrogels (2179 ± 127 Pa). Lower stiffness hydrogels also supported higher levels of cell viability and larger cell spheroid formation compared to the highest stiffness hydrogels. Together, these data suggest that 3D HA hydrogels are a useful platform for studying OPC behavior and that OPC growth/metabolic health may be favored in lower stiffness microenvironments mimicking brain tissue mechanics.

Hydrogel Properties May Influence Mesenchymal Stem Cell Lineage Progression Through Modulating GAPDH Activity

Cell traction forces, biochemical signals, and cell metabolism are each known to regulate mesenchymal stem cell (MSC) differentiation. Biomaterials have therefore been designed to manipulate cell traction force (via their viscoelasticity and adhesion ligands) to guide MSC fate decisions. Similarly, the type and density of biochemical signals presented by a material have been tailored to influence MSC differentiation. However, the potential impact of biomaterial properties on regulating MSC differentiation through modulating cell metabolism is relatively unstudied. Here, we present data indicating that hydrogel elastic modulus and mesh size regulate MSC differentiation in part through modulating the activity of the metabolic enzyme glyceraldehyde-3-phosphate-dehydrogenase (GAPDH). Toward this end, we first confirm that the differentiation profile of MSCs cultured in 2D on highly elastic, covalently crosslinked poly(ethylene glycol) diacrylate (PEGDA) hydrogels differs substantially from that of MSCs encapsulated within the same hydrogel formulations, indicating a dependence in 3D on a variable(s) beyond elastic modulus. Further results indicate that the GAPDH activity of MSCs in 3D hydrogels is a function of elastic modulus and mesh size, suggesting that GAPDH activity may be one of these variables. Studies in 2D supported a positive correlation between hydrogel elastic modulus and GAPDH activity. Additionally, inhibition of GAPDH activity on 2D surfaces induced alterations in the profiles of key differentiation markers, indicating that GAPDH activity can impact lineage progression. Cumulatively, these findings suggest that the potential impact of hydrogel properties on cell metabolism should be considered when evaluating biomaterial-driven MSC differentiation. Cell traction forces, biochemical signals, and cell metabolism are each known to regulate mesenchymal stem cell (MSC) differentiation. Biomaterials have therefore been designed to manipulate cell traction force (via their viscoelasticity and adhesion ligands) to guide MSC fate decisions. Similarly, the type and density of biochemical signals presented by a material have been tailored to influence MSC differentiation. However, the impact of biomaterial properties on regulating MSC differentiation through modulating cell metabolism is relatively unstudied. Here, we present data indicating that hydrogel elastic modulus and mesh size regulate MSC differentiation in part through modulating the activity of the metabolic enzyme glyceraldehyde-3-phosphate-dehydrogenase (GAPDH).

Matrix metalloproteinase 9-activatable peptide-conjugated hydrogel-based fluorogenic intraocular-lens sensor

The eye is an extension of the central nervous system (CNS) and contains aqueous humor (AH), which is a fluid rich in biomolecules secreted from intraocular tissues; thus, this organ allows for non-invasive visualization of early changes in CNS disorders. There is a growing interest in developing implantable devices, such as intraocular-lens (IOL), for specific medical uses, including intraocular monitoring. We describe a novel IOL-sensing system for detecting AH biomarkers via biocompatible enzyme-activatable fluorogenic hydrogel sensors. Matrix-metalloproteinase-9, a biomarker of degenerative CNS and eye disorders, was selected as a target. A peptide-probe-incorporated fluorogenic IOL (FIOL) was developed using diacrylamide-group-modified poly(ethyleneglycol) (PEGDAAm) biocompatible hydrogels, adjusting the hydrogel mesh size to allow selective penetration of the target while blocking non-targets, using label-free detection with semi-permanently implantable sensors, and demonstrating the clinical feasibility of FIOL through in vivo testing. This novel FIOL-based sensing system represents a promising approach for liquid biopsy of intraocular fluids.

Hydrogel compression and polymer osmotic pressure

Controlling the elastic modulus of simple synthetic hydrogels like polyacrylamide is essential to their use in many areas of biotechnology, including tissue engineering, medical device development, and drug delivery applications. Indentation-based methods for measuring hydrogel elastic moduli are preferred over measurements in shear rheometers or tensile testing instruments when the freedom to choose sample volume and shape are restricted; contact lenses represent such an example. It is often believed that the local application of indentation loads will volumetrically compress hydrogels, increasing the sample's polymer concentration even when the applied pressure is less than the hydrogel's osmotic pressure. Here, we test this idea by volumetrically compressing polyacrylamide hydrogels of different compositions while measuring the degree of compression with increasing applied pressure. Our results reveal that at applied pressures below the hydrogel osmotic pressure, the gels exhibit only marginal compression, while above the osmotic pressure the gels compress as predicted by classical polymer physics theory. Combining measurements of osmotic pressure and polymer mesh size, we determine the scaling relationships between hydrogel composition, mesh size, and osmotic pressure. By demonstrating agreement between experiment and theory, we use our measurements to determine the Kuhn length of the individual polymer chains constituting the hydrogels.

Combination of Polypropylene Mesh and in Situ Injectable Mussel-Inspired Hydrogel in Laparoscopic Hernia Repair for Preventing Post-Surgical Adhesions in the Piglet Model.

Polypropylene (PP) mesh has been used successfully for a long time in clinical practice as an impressive prosthesis for ventral hernia repair. To utilize a physical barrier for separating mesh from viscera is a general approach for preventing adhesions in clinical practice. However, a serious abdominal adhesion between the mesh and viscera can possibly occur post-hernia, especially with the small intestine; this can lead to a series of complications, such as chronic pain, intestinal obstruction, and fistula. Thus, determining how to prevent abdominal adhesions between the mesh and viscera is still an urgent clinical problem. In this study, a dopamine-functionalized polysaccharide derivative (oxidized-carboxymethylcellulose-g-dopamine, OCMC-DA) was synthesized; this was blended with carboxymethylchitosan (CMCS) to form a hydrogel (OCMC-DA/CMCS) in situ at the appropriate time. The physical and chemical properties of the hydrogel were characterized successfully, and its excellent biocompatibility was presented by the in vitro cell test. The combination of this hydrogel and PP mesh was used in laparoscopic surgery for repairing the abdominal wall defect, where the hydrogel could become fixed in situ on the PP mesh to form an anti-adhesion gel-mesh. The results showed that the gel-mesh could prevent abdominal adhesions effectively in the piglet model. Moreover, the histology and immunohistochemical staining proved that the gel-mesh could effectively alleviate the inflammation reaction and deposition of collagen around the mesh, and it did not disturb the integration between mesh and abdominal wall. Thus, the gel-mesh has superior tissue compatibility.

Computational-Based Design of Hydrogels with Predictable Mesh Properties.

Hydrogel systems are an appealing class of therapeutic delivery vehicles, though it can be challenging to design hydrogels that maintain desired spatiotemporal presentation of therapeutic cargo. In this work, we propose a different approach in which computational tools are developed that creates a theoretical representation of the hydrogel polymer network to design hydrogels with predefined mesh properties critical for controlling therapeutic delivery. We postulated and confirmed that the computational model could incorporate properties of alginate polymers, including polymer content, monomer composition and polymer chain radius, to accurately predict cross-link density and mesh size for a wide range of alginate hydrogels. Additionally, the simulations provided a robust strategy to determine the mesh size distribution and identified properties to control the mesh size of alginate hydrogels. Furthermore, the model was validated for additional hydrogel systems and provided a high degree of correlation (R2 > 0.95) to the mesh sizes determined for both fibrin and polyethylene glycol (PEG) hydrogels. Finally, a full factorial and Box-Behnken design of experiments (DOE) approach utilized in combination with the computational model predicted that the mesh size of hydrogels could be varied from approximately 5 nm to 5 μm through controlling properties of the polymer network. Overall, this computational model of the hydrogel polymer network provides a rapid and accessible strategy to predict hydrogel mesh properties and ultimately design hydrogel systems with desired mesh properties for potential therapeutic applications.

Influence of Loading Conditions and Temperature on Static Friction and Contact Aging of Hydrogels with Modulated Microstructures.

Biological tribosystems enable diverse functions of the human body by maintaining extremely low coefficients of friction via hydrogel-like surface layers and a water-based lubricant. Although stiction has been proposed as a precursor to damage, there is still a lack of knowledge about its origin and its relation to the hydrogel's microstructure, which impairs the design of soft matter as replacement biomaterials. In this work, the static friction of poly(acrylamide) hydrogels with modulated composition was investigated by colloidal probe lateral force microscopy as a function of load, temperature, and loading time. Temperature-dependent studies enable to build a phase diagram for hydrogel's static friction, which explains stiction via (polymer) viscoelastic and poroelastic relaxation, and a subtle transition from solid- to liquid-like interfacial behavior. At room temperature, the static friction increases with loading time, a phenomenon called contact aging, which stems from the adhesion of the polymer to the colloid and from the drainage-induced increase in contact area. Contact aging is shown to gradually vanish with increase in temperature, but this behavior strongly depends on the hydrogel's composition. This work scrutinizes the relation between the microstructure of hydrogel-like soft matter and interfacial behavior, with implications for diverse areas of inquiry, not only in biolubrication and biomedical applications but also in soft robotics and microelectromechanical devices, where the processes occurring at the migrating hydrogel interface are of relevance. The results support that modulating both the hydrogel's mesh size and the structure of the near-surface region is a means to control static friction and adhesion. This conceptual framework for static friction will foster further understanding of the wear of hydrogel-like materials.

3D bioprinted endometrial stem cells on melt electrospun poly ε-caprolactone mesh for pelvic floor application promote anti-inflammatory responses in mice

Endometrial mesenchymal stem/stromal cells (eMSCs) exhibit excellent regenerative capacity in the endometrial lining of the uterus following menstruation and high proliferative capacity in vitro. Bioprinting eMSCs onto a mesh could be a potential therapy for Pelvic Organ Prolapse (POP). This study reports an alternative treatment strategy targeting vaginal wall repair using bioprinting of eMSCs encapsulated in a hydrogel and 3D melt electrospun mesh to generate a tissue engineering construct. Following a CAD, 3D printed poly ε-caprolactone (PCL) meshes were fabricated using melt electrospinning (MES) at different temperatures using a GMP clinical grade GESIM Bioscaffolder. Electron and atomic force microscopies revealed that MES meshes fabricated at 100 °C and with a speed 20 mm/s had the largest open pore diameter (47.2 ± 11.4 μm) and the lowest strand thickness (121.4 ± 46 μm) that promoted optimal eMSC attachment. An Aloe Vera-Sodium Alginate (AV-ALG) composite based hydrogel was optimised to a 1:1 mixture (1%AV-1%ALG) and eMSCs, purified from human endometrial biopsies, were then bioprinted in this hydrogel onto the MES printed meshes. Acute in vivo foreign body response assessment in NSG mice revealed that eMSC printed on MES constructs promoted tissue integration, eMSC retention and an anti-inflammatory M2 macrophage phenotype characterised by F4/80+CD206+ colocalization. Our results address an unmet medical need highlighting the potential of 3D bioprinted eMSC-MES meshes as an alternative approach to overcome the current challenges with non-degradable knitted meshes in POP treatment. Statement of SignificanceThis study presents the first report of bioprinting mesenchymal stem cells derived from woman endometrium (eMSCs) to boost Pelvic Organ Prolapse (POP) treatment. It impacts over 50% of elderly women with no optimal treatment at present. The overall study is conducted in three stages as fabricating a melt electrospun (MES) mesh, bioprinting eMSCs into a Ca2+ free Aloe Vera-Alginate (AV-Alg) based hydrogel and in vivo study. Our data showed that AV-ALG hydrogel potentially suppresses the foreign body response and further addition of eMSCs triggered a high influx of anti-inflammatory CD206+ M2 macrophages. Our final construct demonstrates a favourable foreign body response to predict expected tissue integration, therefore, provides a potential for developing an alternative treatment for POP.

Effective Suppression of Oxidative Stress on Living Cells in Hydrogel Particles Containing a Physically Immobilized WS2 Radical Scavenger.

We report a tungsten disulfide (WS2) nanosheet-immobilized hydrogel system that can inhibit oxidative stress on living cells. First, we fabricated a highly stable suspension of WS2 nanosheets as a radical scavenger by enveloping them with the amphiphilic poly(ε-caprolactone)- b-poly(ethylene oxide) copolymer (PCL- b-PEO) during in situ liquid exfoliation in aqueous medium. After the PCL- b-PEO-enveloped WS2 nanosheets were embedded in three types of hydrogel systems, including carrageenan gum/locust bean gum bulk hydrogels, physically cross-linked alginate microparticles, and covalently cross-linked PEG hydrogel microparticles, they retained their characteristic optical properties. Intriguingly, the WS2 nanosheet-immobilized hydrogel particles exhibited sustainable radical scavenging performance without any deterioration in the original activity of the WS2 nanosheets, even after repeated use. This implies that the hydrogen atoms dissociated from the chalcogen of the WS2 nanosheets effectively scavenged free radicals through the hydrogel mesh. Because of this unique behavior, the coexistence of the WS2 nanosheets with living cells in the hydrogel matrix improved cell viability up to 40%, which demonstrates that the WS2 nanosheets can suppress oxidative stress on living cells.

A 3D bioprinted hydrogel mesh loaded with all-trans retinoic acid for treatment of glioblastoma

Treatment of glioblastoma (GBM), as the most lethal type of brain tumor, still remains a major challenge despite the various therapeutic approaches developed over the recent decades. GBM is considered as one of the most therapy-resistant human tumors. Treatment with temozolomide (TMZ) chemotherapy and radiotherapy in GBM patients has led to 30% of two-year survival rate (American Brain Tumor Association), representing a demanding field to develop more effective therapeutic strategies. This study presents a novel method for local delivery of all-trans retinoic acid (ATRA) for targeting GBM cells as a possible adjuvant therapeutic strategy for this disease. We have used 3D bioprinting to fabricate hydrogel meshes laden with ATRA-loaded polymeric particles. The ATRA-loaded meshes have been shown to facilitate a sustained release of ATRA with tunable release rate. Cell viability assay was used to demonstrate the ability of fabricated meshes in reducing cell growth in U-87 MG cell line. We later showed that the developed meshes induced apoptotic cell death in U-87 MG. Furthermore, the use of hydrogel for embedding the ATRA-loaded particles can facilitate the immobilization of the drug next to the tumor site. Our current innovative approach has shown the potential to open up new avenues for treatment of GBM, benefiting patients who suffer from this debilitating disease.

Molecular simulation of diffusion of rigidity-tuned nanoparticles in biological hydrogels

The penetration capability of drug nano-carriers (NCs) in biological hydrogels such, as mucus and tumor interstitial matrix, typically influence the efficiency of drug delivery. Therefore, understanding the effect of the physicochemical properties of drug carriers on their diffusion capability in biological hydrogels is important for the design and optimization of nano-carriers. Here, using a coarse-grained molecular dynamics model, we studied how the rigidity of NCs affected their diffusivity in biological hydrogels. The results showed that semi-elastic NCs have higher diffusivity than the hard and soft NCs. Furthermore, the affinity between the NCs and biological hydrogels and the size ratio between the hydrogel meshes and NCs also affect NC diffusivity. Further analysis revealed the mechanism that the deformation of the NCs dominates their diffusivity. These findings demonstrate that the rigidity of NCs is a key parameter in designing efficient NCs for deep penetration into biological hydrogels.

Interfacial fluid transport is a key to hydrogel bioadhesion

Attaching hydrogels to soft internal tissues is a key to the development of a number of biomedical devices. Nevertheless, the wet nature of hydrogels and tissues renders this adhesion most difficult to achieve and control. Here, we show that the transport of fluids across hydrogel-tissue interfaces plays a central role in adhesion. Using ex vivo peeling experiments on porcine liver, we characterized the adhesion between model hydrogel membranes and the liver capsule and parenchyma. By varying the contact time, the tissue hydration, and the swelling ratio of the hydrogel membrane, a transition between two peeling regimes is found: a lubricated regime where a liquid layer wets the interface, yielding low adhesion energies (0.1 J/m2 to 1 J/m2), and an adhesive regime with a solid binding between hydrogel and tissues and higher adhesion energies (1 J/m2 to 10 J/m2). We show that this transition corresponds to a draining of the interface inducing a local dehydration of the tissues, which become intrinsically adhesive. A simple model taking into account the microanatomy of tissues captures the transition for both the liver capsule and parenchyma. In vivo experiments demonstrate that this effect still holds on actively hydrated tissues like the liver capsule and show that adhesion can be strongly enhanced when using superabsorbent hydrogel meshes. These results shed light on the design of predictive bioadhesion tests as well as on the development of improved bioadhesive strategies exploiting interfacial fluid transport.

Chemically Modified Hydrogel-Filled Nanopores: A Tunable Platform for Single-Molecule Sensing.

Label-free, single-molecule sensing is anideal candidate for biomedical applications that rely on the detection of low copy numbers in small volumes and potentially complex biofluids. Among them, solid-state nanopores can be engineered to detect single molecules of charged analytes when they are electrically driven through the nanometer-sized aperture. When successfully applied to nucleic acid sensing, fast transport in the range of 10-100 nucleotides per nanosecond often precludes the use of standard nanopores for the detection of the smallest fragments. Herein, hydrogel-filled nanopores (HFN) are reported that combine quartz nanopipettes with biocompatible chemical poly(vinyl) alcohol hydrogels engineered in-house. Hydrogels were modified physically or chemically to finely tune, in a predictable manner, the transport of specific molecules. Controlling the hydrogel mesh size and chemical composition allowed us to slow DNA transport by 4 orders of magnitude and to detect fragments as small as 100 base pairs (bp) with nanopores larger than 20 nm at an ionic strength comparable to physiological conditions. Considering the emergence of cell-free nucleic acids as blood biomarkers for cancer diagnostics or prenatal testing, the successful sensing and size profiling of DNA fragments ranging from 100 bp to >1 kbp long under physiological conditions demonstrates the potential of HFNs as a new generation of powerful and easily tunable molecular diagnostics tools.

DNA molecules deviate from shortest trajectory when driven through hydrogel.

Dynamic fluorescence-based single-molecule imaging of λ-DNA molecules driven through agarose hydrogels by DC electric fields reveals that passage through the hydrogel (98.5% water content) induces mobility orthogonal to the external field. Tortuous paths followed by the DNA molecules, which are heavily entangled in the hydrogel mesh as their contour length is nearly 100 times the hydrogel mesh size of 200 nm, cause them to appear to diffuse orthogonal to the driving force. The higher the driving field, from 2 to 16 V/cm, the higher the off-axis dispersion is, over the same time interval. We measure the off-axis displacement distribution over 3 orders of magnitude of probability density and find a master curve after normalizing for time (t) elapsed, but the power of time for normalizing increases with the external field, from t0.25 to t0.6 with increasing field. Comparing trajectories over the same distance traveled in the electric field direction, we observe whereas for the highest field strengths DNA molecules come closest to taking the shortest trajectory between two points in space, deviations from the shortest trajectory grow larger and larger (up to 40% larger) as one approaches the case of small yet finite external field strength.

Adjustable Tribological Behavior of Glucose-Sensitive Hydrogels.

Stimuli-responsive hydrogels have been considered to have various applications in numerous fields. In the present work, a double-network (DN) hydrogel has been synthesized. The copolymers of 2-acrylamide-2-methylpropane sulfonic acid (AMPS) and acrylamide (AM) [P(AMPS- co-AM)] are prepared as the 1st network and poly(acrylic acid) as the 2nd network. This DN hydrogel is sensitive to glucose by introducing the glucose-sensitive group phenylboronic acid to the network. The tribological properties of this glucose-sensitive DN hydrogel have been investigated using a universal mechanical tester (UMT-5). The tribological results show that the friction coefficient varied with the glucose solution. The friction coefficient increased to a maximum of 0.06, and finally decreased to 0.025 with the increase in the glucose concentration. An adjustable friction coefficient of the hydrogel, between 0.025 and 0.056, was achieved along with the change of lubricant. According to the tribological experimental results and the analysis of the DN structure, it can be deduced that a hydrated layer exists in the interface of the hydrogel. The hydrated layers consisting of water molecules are bounded with the hydrophilic group of the hydrogel network by hydrogen bonds. The change in the number of water molecules leads to the difference in the water content of the hydrogel, which further resulted in the various tribological properties. In addition, the hydrogel's mesh size also has an impact on the change in friction coefficient. In general, the adjustable friction of the hydrogel in a glucose environment is achieved.

Experimental Investigation on the Nanosilica-Reinforcing Polyacrylamide/Polyethylenimine Hydrogel for Water Shutoff Treatment

Polyacrylamide hydrogel used in conformance control is subjected to poor stability at an elevated temperature. In this paper, nanosilica has been found to be a very effective stabilizing agent for the polyacrylamide/polyethylenimine hydrogel, and the reinforcing performance of nanosilica on the hydrogel was investigated in detail. The result showed that the strength of hydrogel is enhanced obviously by the nanosilica, and the hydrogel syneresis is also significantly inhibited by the nanosilica, which can increase the hydrogel stability time from 18 to 180 days at 130 °C. Besides, nanosilica can increase the shear viscosity and hydrodynamic radius of polyacrylamide, and the bound water in the hydrogel is also grown in the presence of nanosilica. In comparison to the micromorphology of common hydrogel, the dense and strong mesh structure is formed as a result of the reinforcing behavior of nanosilica. According to the above results, it is inferred that the silanol group of nanosilica cross-links with the am...