Amination and crosslinking of acetone-fractionated hardwood kraft lignin using different amines and aldehydes for sustainable bio-based wood adhesives.

Hardwood kraft lignin from the pulping industry is burned or discarded. Its valorization was conducted by subjecting fractionation, amination with ethylenediamine, diethylenetriamine, and monoethanolamine, and crosslinking with formaldehyde or glyoxal to obtain bio-based wood adhesives. Acetone-soluble and insoluble hardwood kraft lignin were prepared and subjected to amination and then crosslinking. Fourier transform infrared, 13C NMR, 15N NMR, and X-ray photoelectron spectroscopy results revealed successful amination with amide, imine, and ether bonds and crosslinking of all samples. Hardwood kraft lignin aminated with diethylenetriamine/ethylenediamine and crosslinked using glyoxal exhibited excellent results in comparison with samples crosslinked using formaldehyde. Acetone-insoluble hardwood kraft lignin aminated and crosslinked using diethylenetriamine and formaldehyde, respectively, exhibited excellent adhesion strength with plywood, satisfying the requirements of the Korean standards. The amination and crosslinking of industrial waste hardwood kraft lignin constitute a beneficial valorization method.

Effect of Nisin-based pretreatment solution on dentin bond strength, antibacterial property, and MMP activity of the adhesive interface.

OBJECTIVE: To evaluate the effect of a Nisin-based dentin pretreatment solution on microtensile bond strength, antibacterial activity, and matrix metalloproteinase (MMP) activity of the adhesive interface. MATERIALS AND METHODS: 100 human molars were sectioned to expose dentin. The teeth were assigned to five groups (n = 20), according to the dentin pretreatment: 0.5%, 1.0%, or 1.5% Nisin; 0.12% chlorhexidine (positive control), and no solution (negative control), and divided into 2 subgroups: no aging, and thermomechanical aging. Specimens were etched with 37% H3PO4 for 15 s and submitted to the dentin pretreatment. Then, they were bonded with an adhesive (Adper Single Bond 2) and a resin composite for microtensile bond strength (µTBS) evaluation. Antibacterial activity against Streptococcus mutans was qualitatively examined using an agar diffusion test. Anti-MMP activity within hybrid layers was examined using in-situ zymography. Data were analyzed with two-factor ANOVA and post-hoc Tukey's test (α = 0.050). RESULTS: For µTBS, significant differences were identified for the factors "solutions" (p = 0.002), "aging" (p = 0.017), and interaction of the two factors (p = 0.002). In the absence of aging, higher µTBS was observed for the group 0.5% Nisin. In the presence of aging, all groups showed similar µTBS values. All Nisin concentrations were effective in inhibiting the growth of S. mutans. Endogenous MMP activity was more significantly inhibited using 0.5% and 1.0% Nisin (p < 0.050). CONCLUSION: 0.5% and 1.0% Nisin solutions do not adversely affect resin-dentin bond strength and exhibit a potential bactericidal effect against S. mutans. Both concentrations effectively reduce endogenous gelatinolytic activity within the hybrid layer. CLINICAL RELEVANCE: The use of 0.5% and 1.0% Nisin solutions for dentin pretreatment potentially contributes to preserving the adhesive interface, increasing the longevity of composite restorations.

Valorization of sewage sludge for facile and green wood bio-adhesives production.

A method is presented herein for the design of wood bio-adhesives using sewage sludge extracts (SSE). SSE was extracted from SS using deep eutectic solvents and processed with glycerol triglycidyl ether (GTE) to disrupt the secondary structure of proteins. An additive was also used to improve mechanical performance. The resulting bio-adhesive (SSE/GTE@TA) had a wet shear strength of 0.93 MPa, meeting the Chinese national standard GB/T 9846-2015 (≥0.7 MPa). However, the high polysaccharide content in SSE would weaken the mechanical properties of wood bio-adhesives. The key to improve bio-adhesive quality was the formation of a strong chemical bond via Maillard reaction as well as higher temperatures (140 °C) to reduce polysaccharide content via dehydration. This approach has lower environmental impact and higher economic efficiency compared to incineration and anaerobic digestion of sewage sludge. This work provides a new perspective on the high-value utilization of SS and offers a novel approach to developing bio-adhesives for the wood industry.

Biomodification of eroded and abraded dentin with epigallocatechin-3-gallate (EGCG).

This study aimed to evaluate in vitro the effects of epigallocatechin-3-gallate (EGCG) as a biomodifier of eroded and abraded dentin. Forty dentin specimens were obtained from the buccal surface of bovine teeth. The specimens were randomly distributed in 4 groups according to dentin substrate: sound or eroded/abraded and dentin biomodification: with 0.5% EGCG and no biomodification (control group). Specimens were subdivided according to aging time: 24 h and 3 months for the analysis of microtensile bond strength (n = 10), morphology of the adhesive interface by SEM (n = 3) and dentin micropermeability by fluorescence microscope (n = 8). Statistical analysis was performed using SPSS system version 20.0 with a significance level of 5%. The results revealed that the control group with eroded-abraded dentin exhibited the lowest bond strength values at 24 h and 3 months. However, the application of 0.5% EGCG as a biomodifier significantly increased bond strength on both sound and eroded-abraded substrates. After 3 months, all groups exhibited an adhesive interface with a more intense fluorescence in the adhesive layer, indicating an increase in porosity at the interface. In conclusion, the EGCG application as a biomodifier enhanced bond strength on both sound and eroded-abraded dentin substrates, however, adhesive interfaces are more regular when restorations are performed on sound dentin, regardless of the biomodification with EGCG.

Electrostatic Assembly of Multiarm PEG-Based Hydrogels as Extracellular Matrix Mimics: Cell Response in the Presence and Absence of RGD Cell Adhesive Ligands.

Synthetic hydrogels have been used widely as extracellular matrix (ECM) mimics due to the ability to control and mimic physical and biochemical cues observed in natural ECM proteins such as collagen, laminin, and fibronectin. Most synthetic hydrogels are formed via covalent bonding resulting in slow gelation which is incompatible with drop-on-demand 3D bioprinting of cells and injectable hydrogels for therapeutic delivery. Herein, we developed an electrostatically crosslinked PEG-based hydrogel system for creating high-throughput 3D in vitro models using synthetic hydrogels to mimic the ECM cancer environment. A 3-arm PEG-based polymer backbone was first modified with either permanent cationic charged moieties (2-(methacryloyloxy)ethyl trimethylammonium) or permanent anionic charged moieties (3-sulfopropyl methacrylate potassium salt). The resulting charged polymers can be conjugated further with various amounts of cell adhesive RGD motifs (0, 25, 75, and 98%) to study the influences of RGD motifs on breast cancer (MCF-7) spheroid formation. Formation, stability, and mechanical properties of hydrogels were tested with, and without, RGD to evaluate the cellular response to material parameters in a 3D environment. The hydrogels can be degraded in the presence of salts at room temperature by breaking the interaction of oppositely charged polymer chains. MCF-7 cells could be released with high viability through brief exposure to NaCl solution. Flow cytometry characterization demonstrated that embedded MCF-7 cells proliferate better in a softer (60 Pa) 3D hydrogel environment compared to those that are stiffer (1160 Pa). As the stiffness increases, the RGD motif plays a role in promoting cell proliferation in the stiffer hydrogel. Flow cytometry characterization demonstrated that embedded MCF-7 cells proliferate better in a softer (60 Pa) 3D hydrogel environment compared to those that are stiffer (1160 Pa). As the stiffness increases, the RGD motif plays a role in promoting cell proliferation in the stiffer hydrogel. Additionally, cell viability was not impacted by the tested hydrogel stiffness range between 60 to 1160 Pa. Taken together, this PEG-based tuneable hydrogel system shows great promise as a 3D ECM mimic of cancer extracellular environments with controllable biophysical and biochemical properties. The ease of gelation and dissolution through salt concentration provides a way to quickly harvest cells for further analysis at any given time of interest without compromising cell viability.

Development of a bioactive dentin adhesive resin modified with magnesium-doped synthetic hydroxyapatite crystals.

The aim is to evaluate the development of an experimental multi-mode/Universal resin-based dentin adhesive modified with synthetic Mg2+ doped hydroxyapatite crystals (HAp) having self-remineralization and antibiofilm properties. HAp doped with Mg2+ was prepared by the precipitation method. Experimental adhesives were subjected to degree of conversion and X-ray diffraction test for size and crystal structure. Bond strength was tested, and electron microscopy (SEM/TEM) imaging of resin-dentin interface was done along with nanoleakage, nanoindentation, confocal and Raman analyses. S. mutans was analysed using CLSM images against modified adhesive specimens. Nucleating abilities within the resin-dentin specimens are determined by measuring Ca2+. Alkaline phosphatase, Runx2, and Ocn transcripts are amplified using quantitative polymerase chain reaction (q-PCR). A calcium assay is performed to quantify level of mineralisation. When compared to control adhesives, the 0.5% Hap/Mg2+ containing experimental dentin adhesive demonstrated improved interaction with dentin. The preservation of uniform intact hybrid layer with the absence of nanoleakage indicated dentin bond integrity with 0.5% HAP/Mg2+ modified adhesive. Self-remineralization and antibiofilm potentials are supported.

The conidial coin toss: A polarized conidial adhesive in Colletotrichum graminicola.

Colletotrichum graminicola is an economically significant fungal pathogen of maize. The primary infective conidia of the fungus, falcate conidia, are splash-dispersed during rain events. The adhesion of the falcate conidia triggers germination and is required for the development of infection structures. Falcate conidia are capable of immediate adhesion upon encountering the substrate. We report that rapid adhesion in C. graminicola is polarized, with a single-sided strip of adhesive material running the length of a single side (or face) of the conidium between the tips. This strip of adhesive is co-localized with dynamic transverse actin cables, and both the adhesive strip and actin cables are formed after liberation of the conidium from its conidiogenous cell but prior to adhesion to the infection court. Orientation of conidia upon contact with substrate determines whether they will rapidly adhere, and those which do not initially adhere can be induced to do so by applying force to reorient or "flip" the conidia. We propose that C. graminicola possesses an adhesive mechanism resulting in an adhesion efficiency of approximately 50% upon initial contact with substrata, and that an increase in adhesion efficiency can be induced by disturbance.

Effects of carbodiimide combined with ethanol-wet bonding pretreatment on dentin bonding properties: an in vitro study.

Purpose: This study evaluated the combined effects of Carbodiimide (EDC) and ethanol-wet bonding (EWB) pretreatment on the bond strength and resin-dentin surface. Methods: Phosphoric acid-etched dentin specimens were randomly divided into five groups based on the following pretreatments: deionized water (control), EWB, 0.3M EDC in water (EDCw), EDC water solution combined EWB (EDCw + EWB), and 0.3M EDC in ethanol (EDCe). A scanning electron microscope (SEM) was used to observe the morphology of collagen fibrils on the demineralized dentin matrix in each group after pretreatment. The adhesives Prime & Bond NT (PB) (Dentsply De trey, Konstanz, Germany) or Single bond 2 (SB) (3M ESPE, St. Paul, MN, USA) was applied after pretreatments, and a confocal laser scanning microscope (CLSM) was used to evaluate the quality of resin tags. The degree of conversion (DC) of the adhesive was investigated by Fourier transform infrared spectroscopy (ATR-FTIR). The dentin was first bonded with resin and bathed in water at 37 °C for 24 h. Half of them were subjected to 10, 000 cycles in a thermocycler between 5 °C and 55 °C before a microshear bond strength (µSBS) test. The statistical methods were Analysis of Variance (ANOVA) and a Tukey post hoc test at α = 0.05. Results: The µSBS was significantly affected by pretreatments (p < 0.001), adhesives (p < 0.001), and aging conditions (p < 0.001) as revealed by the three-way ANOVA. The EDCw, EDCw + EWB, and EDCe groups significantly increased the µSBS; the EDCw + EWB and EDCe groups produced the highest µSBS. In the EDC-containing groups, the SEM showed at the collagen fibrils in the dentin matrix formed a three-dimensional network structure in the tubules after cross-linking into sheets, and the hybrid layer formed thicker resin tags under a CLSM. In the EDC-containing groups, the CLSM observed an increase in the length of resin tags. PB showed a higher DC and bonding strength than SB, and the five pretreatment groups tested did not affect the DC of the two adhesives. Conclusions: In etch-and-rinse bonding system, EDC combined with EWB pretreatment can improve the quality of the hybrid layer and enhance the mechanical properties of demineralized dentin matrix. Pretreatment with EDC-ethanol solution may be a new clinically friendly option for enhancing dentin bonding durability.

Adhesive Bond Integrity of Experimental Zinc Oxide Nanoparticles Incorporated Dentin Adhesive: An SEM, EDX, µTBS, and Rheometric Analysis.

Objective: Our study is aimed at preparing an experimental adhesive (EA) and assessing the influence of adding 5-10 wt.% concentrations of zinc oxide (ZnO) nanoparticles on the adhesive's mechanical properties. Methods: Field emission scanning electron microscopy (FESEM) and energy dispersive X-ray (EDX) spectroscopy were employed to investigate the morphology and elemental distribution of the filler nanoparticles. To examine the adhesive properties, microtensile bond strength (µTBS) testing, an investigation of the rheological properties, degree of conversion (DC), and analysis of the interface between the adhesive and dentin were carried out. Results: The SEM micrographs of ZnO nanoparticles demonstrated spherical agglomerates. The EDX plotting confirmed the incidence of Zn and oxygen (O) in the ZnO nanoparticles. The highest µTBS was observed for nonthermocycled (NTC) 5 wt.% ZnO group (32.11 ± 3.60 MPa), followed by the NTC-10 wt.% ZnO group (30.04 ± 3.24 MPa). Most of the failures observed were adhesive in nature. A gradual reduction in the viscosity was observed at higher angular frequencies, and the addition of 5 and 10 wt.% ZnO to the composition of the EA lowered its viscosity. The 5 wt.% ZnO group demonstrated suitable dentin interaction by showing the formation of resin tags, while for the 10 wt.% ZnO group, compromised resin tag formation was detected. DC was significantly higher in the 0% ZnO (EA) group. Conclusion: The reinforcement of the EA with 5 and 10 wt.% concentrations of ZnO nanoparticles produced an improvement in the adhesive's µTBS. However, a reduced viscosity was observed for both nanoparticle-reinforced adhesives, and a negotiated dentin interaction was seen for 10 wt.% ZnO adhesive group. Further research exploring the influence of more filler concentrations on diverse adhesive properties is recommended.

Influence of Er:YAG laser irradiation settings on dentin-adhesive interfacial ultramorphology and dentin bond strength.

This study evaluated the effects of Erbium-doped yttrium aluminium garnet (Er:YAG) laser settings and dentin bonding agents on ultramorphological characteristics of resin-laser-irradiated dentin interfaces and dentin bond strength (BS) of these adhesive systems. Additionally, dentin depth affected by Er:YAG laser irradiations was measured. The experiments were performed on occlusal dentin surfaces of third molars that were flattened with 600-grit SiC sandpaper. Treated-dentin with laser settings (250 mJ/4 Hz and 160 mJ/10 Hz) were the experimental groups, while SiC abraded dentin was the control. These three dentin treatments and three adhesives (two self-etchings and one etch-&-rinse adhesive) formed nine groups for the ultramorphology of laser-ablated dentin-adhesives interfacial analysis, using a transmission electron microscope (TEM). For BS (n = 8), the same nine groups were tested with addition of the two evaluation times (24 h after sample preparation or 1 year). The depths of Er:YAG laser effects into the dentin were measured using a TEM (n = 10). Ablated-dentin depth and BS data were analyzed by one- and three-way ANOVA, respectively, and Tukey's test (α = 0.05). Hybrid layer formation was only observed for controls, while for laser-treated dentin, adhesives were bonded to dentin with resin tags formation. Laser settings reduced the BS for all adhesives at 24 h, while at 1 year, etch-&-rinse adhesive presented the highest BS, regardless treatment (control or laser settings). Dentin depth affected by laser settings was similar. The laser irradiation altered the bonding mechanism of the adhesives to dentin and reduced the BS for self-etching adhesives. Etch-&-rinse adhesive yielded the highest BS at 1 year. Laser settings similarly affected the dentin in depth. HIGHLIGHTS: Er:YAG laser irradiation settings produced similar effects on depth and bond strength to dentin. The etch-&-rinse adhesive yielded the highest dentin bond strength regardless of the type of dentin treatment at 1 year.

Location of MMPs in human radicular dentin and the effects of MMPs inhibitor on the bonding stability of fiber posts to radicular dentin.

This study explored the location of MMP-2, -3, -8 in human root dentin and the inhibition of EGCG/EGCG-3Me on dentin-originated collagen proteases activities. Also, the study evaluated EGCG/EGCG-3Me modified etch-and-rinse adhesives (Single Bond 2, SB 2) for their bonding stabilities to intraradicular dentin. Immunostaining and liquid chip analysis demonstrated that MMP-2 and MMP-8 are widely distributed in root dentin while MMP-3 shows a higher fluorescence intensity in the middle and apical third of the root. The contents of MMP-2, -3 and -8 varies in different locations of human tooth root and MMP-2 has the highest content than MMP-3 and MMP-8 at each third of teeth root. Both EGCG and EGCG-3Me showed an inhibitory effect on the root dentin-derived MMPs in a concentration dependent manner (P < 0.05) and the inhibitory activity of EGCG-3ME was stronger than that of EGCG at the same concentration (P < 0.05). EGCG and EGCG-3Me were incorporated separately into the adhesive SB 2 at concentrations of 200, and 400 µg/mL respectively. The immediate push-out strength of SB 2 was not compromised by EGCG/EGCG-3Me modification. EGCG/EGCG-3Me modified adhesive had higher push-out strength than SB 2 after thermocycling, showing no correlation with concentration.

Bonding Efficacy of Universal Adhesives to Fluorotic Enamel after Pre-conditioning with EDTA.

PURPOSE: To compare the effect of active pre-conditioning with 17% ethylenediaminetetraacetic acid (EDTA) vs 37% phosphoric acid (PA) on the resin-enamel microshear bond strength (µSBS), enamel-etching pattern, and in situ degree of conversion (in situ DC) of four universal adhesives on sound and fluorotic enamel. MATERIAL AND METHODS: In this study, 448 extracted human molars (224 without fluorosis and 224 with fluorosis) were sectioned into four parts and divided into 16 experimental groups based on the enamel surface (sound or fluorotic enamel), adhesive (Clearfil Universal Bond [CUB], Futurabond U [FBU], iBond Universal [IBU], or Scotchbond Universal [SBU]), and enamel conditioning agent (PA or EDTA). The specimens were stored for 24 h and tested under shear stress at 1.0 mm/min to determine the µSBS. The adhesive-enamel interfaces were evaluated for in situ DC using micro-Raman spectroscopy. The enamel-etching pattern was evaluated using a scanning electron microscope. The µSBS and in situ DC data were analyzed separately using three-way ANOVA and Tukey's post-hoc test (a = 0.05). RESULTS: Sound enamel showed higher µSBS and in situ DC compared to fluorotic enamel (p < 0.05). However, no significant difference was observed for µSBS, in situ DC (p > 0.05), or etching patterns when PA and EDTA etching were compared in sound and fluorotic enamel. Moreover, CUB and SBU showed higher mean µSBS than did FBU and IBU in both sound and fluorotic enamel (p < 0.05). CONCLUSIONS: Compared to PA, active pre-conditioning with EDTA showed similar µSBS and enamel etching patterns for all the adhesives in fluorotic enamel, without compromising the in situ DC.

Bonding performance and ultramorphology of the resin-dentine interface of contemporary universal adhesives.

OBJECTIVES: This study aimed at evaluating the microtensile bond strength (µTBS) and the resin-dentine ultramorphology (24 h and 10 months ageing) of contemporary universal adhesives applied in self-etch (SE) or etch-and-rinse (ER) mode. MATERIALS AND METHODS: Sixty-four sound human molars were collected and randomly allocated in 4 main experimental groups (n = 16) according to the adhesive system employed and subsequently divided into two subgroups depending on their application mode SE or ER (n = 8): ZipBond X (ZBX-SE; ZBX-ER), Prime and Bond Active (PBA-SE; PBA-ER), Clearfil Universal Bond Quick (CBQ-SE; CBQ-ER) or Scotchbond Universal (SCH-SE; SCH-ER). The specimens were cut into sticks with a cross-sectional area of approximately 0.9 mm2 and subjected to µTBS testing at 24 h or after 10 months of ageing in artificial saliva (AS). Five representative fractured specimens from each group were analysed using field-emission scanning electron microscopy (FE-SEM). Resin-dentine slabs (Ø 0.9mm2) from each experimental group were immersed in Rhodamine B and subsequently analysed using confocal microscopy analysis (CLSM). The µTBS results were analysed using a two-way ANOVA and Newman-Keuls multiple-comparison test (α = 0.05). RESULTS: ZBX, PBA and SCH exhibited greater µTBS values than CQB at 24 h in both SE and ER modes (p < 0.05). CQB showed a significant decrease in µTBS values after ageing both when used in SE and ER mode (p < 0.05). ZBX-ER exhibited no significant differences in the µTBS test after ageing (p > 0.05), while a significant drop in µTBS was seen in SCH-ER and APB-ER after 10-month ageing (p < 0.05). Clear signs of degradation were evident in the resin-dentine interface created with CQB regardless of the application mode or the ageing time. In APB-ER and SCH-ER groups, such signs of degradation were evident after ageing in AS. ZBX showed slight dye infiltration both when used in ER and SE mode. CONCLUSIONS: The long-term bonding performance of modern universal adhesives is usually influenced by the adhesive strategy employed; self-etching application should be prioritised during dentine bonding. Moreover, the use of shortened bonding protocols may compromise the quality of the resin-dentine interface and the bonding performance of most modern universal adhesives. CLINICAL RELEVANCE: The use of etch-and-rinse bonding procedures, as well as "shortened" application protocols should be eluded when using modern universal adhesives in dentine. However, new generation universal adhesives based on innovative chemical formulations may probably allow clinicians to achieve long-term bonding performance with such simplified system also when employed in ER mode.

Reverse engineering of a wool fibre to mimic the structural hierarchy of a gecko's foot.

The adhesion generated by a gecko's foot is realised by a structural hierarchy that is also present inside the cortex of a wool fibre. Both structures are based on the same fibril building blocks that belong to theα-keratin family. We show here that this hierarchical structure can be released from a Merino wool fibre with a combination of formic acid refluxing with agitation and trypsin digestion with ultrasonication. Thus, the cuticle scales are shown to be removed from wool yarns by mass-loss, FTIR spectroscopy and SEM followed by the breakdown of the cortex to release macrofibrils at the surface of the remaining yarn. SEM and AFM evidence are presented for the exposure of macrofibrils at the surface of cross-sections of descaled, fibrillated wool fibres. Adhesion measurements in the AFM show that regions of the treated wool have high adhesion, up to 58 nN, consistent with exposure of nanoscale macrofibrils. This exposure is not however homogeneous across the entirety of the cross-sectioned surface of a yarn and further digestion is required to optimise the depth profile of the exposure for direct comparison with the macroscale compliance and adhesion of a gecko's foot. Nonetheless, the current work has developed an experimental route to reserve engineer wool back to sub-unit macrofibrils, in order to replicate the format and to some extent the adhesive properties of a gecko's hierarchal foot structure.

Anti-adhesive effect of chondrocyte-derived extracellular matrix surface-modified with poly-L-lysine.

After an injury, soft tissue structures in the body undergo a natural healing process through specific phases of healing. Adhesions occur as abnormal attachments between tissues and organs through the formation of blood vessels and/or fibrinous adhesions during the regenerative repair process. In this study, we developed an adhesion-preventing membrane with an improved physical protection function by modifying the surface of chondrocyte-derived extracellular matrices (CECM) with anti-adhesion function. We attempted to change the negative charge of the CECM surface to neutral using poly-L-lysine (PLL) and investigated whether it blocked fibroblast adhesion to it and showed an improved anti-adhesion effect in animal models of tissue adhesion. The surface of the membrane was modified with PLL coating (PLL 10), which neutralized the surface charge. We confirmed that the surface characteristics except for the potential difference were maintained after the modification and tested cell attachment in vitro. Adhesion inhibition was identified in a peritoneal adhesion animal model at 1 week and in a subcutaneous adhesion model for 4 weeks. Neutralized CECM (N-CECM) suppressed fibroblast and endothelial cell adhesion in vitro and inhibited abdominal adhesions in vivo. The CECM appeared to actively inhibit the infiltration of endothelial cells into the injured site, thereby suppressing adhesion formation, which differed from conventional adhesion barriers in the mode of action. Furthermore, the N-CECM remained intact without degradation for more than 4 weeks in vivo and exerted anti-adhesion effects for a long time. This study demonstrated that PLL10 surface modification rendered a neutral charge to the polymer on the extracellular matrix surface, thereby inhibiting cell and tissue adhesion. Furthermore, this study suggests a means to modify extracellular matrix surfaces to meet the specific requirements of the target tissue in preventing post-surgical adhesions.

Physicochemical, structural and adhesion properties of walnut protein isolate-xanthan gum composite adhesives using walnut protein modified by ethanol.

Low-sugar and high-protein adhesives have broad market application prospects, while natural plant proteins have confronted technical bottlenecks due to their poor adhesion. In this study, the effects of ethanol with different concentrations (0-80%) on the adhesion properties of walnut protein isolate-xanthan gum (WNPI-XG) composite adhesives were investigated. Results showed the bonding strength of WNPI-XG treated with 40% ethanol reached 12.55 MPa, the denaturation temperature and the surface hydrophobicity increased to 87.91 and 185.07 respectively, displaying the best rheological and texture properties. It also indicated appropriate concentration of ethanol (40%) didn't change the molecular weight of WNPI-XG, but greatly strengthened the fluorescence intensity, leading changes in contents of reactive sulfhydryl groups, electrostatic forces, hydrophobic interactions, hydrogen bonds and disulfide bonds. Furthermore, the treatment also facilitated a conformation conversion of the secondary structures from ß-sheet to α-helix, promoting the full unfolding of protein molecules. The microstructure analysis showed after 40% ethanol treatment, the WNPI structure was uniform, the surface of WNPI-XG adhesive was flat and smooth, combined more closely with water molecules. By analyzing the influence of ethanol treatment on adhesion of WNPI-XG, the research laid a theoretical foundation for protein modification, providing good technical references for its development and utilization.

The application of ion mobility time of flight mass spectrometry to elucidate neo-formed compounds derived from polyurethane adhesives used in champagne cork stoppers.

Polyurethane adhesives are used to bond agglomerated cork and natural disk cork to produce cork stoppers that are used in champagne bottles. These adhesives are manufactured by reacting polyols with an excess of diisocyanates. Isocyanates are highly reactive compounds that have a propensity to form non-intentionally added substances (NIAS) in the end product. In this work, ion mobility-time of flight-mass spectrometry was used to elucidate such NIAS, through the comparison of accurate mass spectra with the fragmentation patterns of proposed candidates. Twelve neo-formed compounds, including amines, amides and urethanes, resulting from the reaction of isocyanates with acetic acid and ethanol used as food simulants, were identified. Additionally, markers from champagne vs. champagne after its exposure to the adhesive were investigated using the supervised multivariate analysis method of Orthogonal Projection to Latent Structures - Discriminant Analysis. Four neo-formed compounds, resulting from the reaction of diisocyanates with malic acid or tartaric acid contained in the champagne, were identified for the first time in this work. All of the compounds identified were subsequently quantified using ultra-high pressure liquid chromatography coupled to a triple quadrupole mass spectrometer. Limits of detection were below 5 µg/kg in the food simulants and below 30 µg/kg in champagne samples. Migration levels ranged from 70 to 721 µg/kg, with most of them exceeding the specific migration limit established for Cramer class III compound (90 µg/kg).

Nanofiller Particles and Bonding Durability, Water Sorption, and Solubility of Universal Adhesives.

The aim of this study was to evaluate the influence of nanofiller particles in simplified universal adhesive on the long-term microtensile bond strength and silver nitrate up-take, as well as water sorption and solubility. Commercial adhesives Ambar Universal (FGM) in nanofilled-containing version (filled) and same lot without fillers (unfilled) were donated and applied by means of etch-and-rinse strategy. Microtensile bond strength was surveyed after 24-hours or 1-year water storage. Silver nitrate uptake was assayed using scanning electron microscopy (SEM). Water sorption and solubility experiments were performed based on ISO 4049:2009. Statistical analysis was performed using two-way ANOVA and Tukey test (p<0.05). The bond strength of both the adhesives were statistically similar at 24 hours (p>0.05), but the filled group attained significant bond strength reduction after aging when compared to initial bond strength (p<0.001). Conversely, unfilled adhesive presented stable adhesion after 1-year storage (p=0.262). Silver nitrate uptake was similar for both adhesives, with little silver impregnation at the hybrid and adhesive layers. Water sorption was higher with filled adhesive compared to the unfilled one (p=0.01). Conversely, solubility was higher in unfilled in comparison to filled one (p=0.008). The presence of nanofillers in universal adhesive achieves higher water sorption and dentin bond degradation, which did not occur in the unfilled adhesive.

Green Wood Adhesives from One-Pot Coacervation of Folic Acid and Branched Poly(ethylene imine).

Adhesives are extensively used in furniture manufacture, and most currently utilized furniture glues are formaldehyde-based chemicals, which emit formaldehyde throughout the entire life of the furniture. With increasing concerns about formaldehyde emission effects on human health, formaldehyde-free and environmentally friendly wood adhesives from bio-based resources are highly desired. In this study, we developed an eco-friendly, high-strength, and water-based wood adhesive from one-pot coacervation of the hierarchical self-assembly of folic acid (FA, a biomolecule, vitamin B9) with a commercially available biocompatible polymer-branched poly(ethylene imine) (b-PEI). The coacervation is caused by multiple hydrogen bonds between b-PEI and the stacks of FA quartets, which demonstrates a continuous robust 3D network, thus realizing adhesion and cohesion behaviors. This coacervate has the strongest adhesion toward wood compared with other substrates. The long-lasting shear bonding strength is up to 3.68 MPa, which is much higher than that of commercial super glue, but without releasing any toxic components. Since all the fabrication and application processes are under ambient conditions without any heating and high-pressure procedures, this work provides a facile yet powerful strategy to develop formaldehyde-free, eco-friendly, and high-performance bio-based waterborne adhesives for wood bonding.

The 'flash' adhesive study: a randomized crossover trial using an additional adhesive patch to prolong freestyle libre sensor life among youth with type 1 diabetes mellitus.

AIMS: Although strategies to prevent premature sensor loss for flash glucose monitoring (FGM) systems may have substantial benefit, limited data are available. This study among youth with high-risk type 1 diabetes evaluated whether an additional adhesive patch over FGM sensors would reduce premature sensor loss frequency and not cause additional cutaneous adverse events (AEs). METHODS: This is a six-month, open-label, randomized crossover trial. Participants were recruited at completion of prior 'Managing Diabetes in a Flash' randomized controlled trial and allocated to three months of Freestyle Libre FGM sensors with either standard adhesive (control) or additional adhesive patches (RockaDex, New Zealand) (intervention), before crossing over to the opposite study arm. Participants self-reported patch use or non-use, premature sensor loss and cutaneous AEs fortnightly via an electronic questionnaire. RESULTS: Thirty-four participants were enrolled: mean age (± SD) 17.0 (± 2.2) years; mean HbA1c (± SD) 89 (± 16) mmol/mol (10.3% ± 1.4%). The response rate of questionnaires was 77% (314/408). Premature sensor loss was reported in 18% (58/314) of questionnaires: 20% (32/162) from intervention and 17% (26/152) from control (p = 0.56). Thirty-eight percent (118/314) of questionnaires were non-compliant to protocol allocation. However, per-protocol analysis showed similar findings. No significant difference in AEs was reported between compliant adhesive patch use and non-use (6% [5/78] and 3% [3/118], respectively, p = 0.27). CONCLUSIONS: The adhesive patch investigated in this study does not appear to prevent premature FGM sensor loss. However, the low risk of AEs and low cost of an adhesive patch suggest an individualized approach to their use may still be warranted. Further research is needed to explore alternative strategies to prevent sensor loss.