Injectable and Near-Infrared-Responsive Hydrogels Encapsulating Dopamine-Stabilized Gold Nanorods with Long Photothermal Activity Controlled for Tumor Therapy.

Gold nanorods (AuNRs) are confirmed to have excellent and repeated photothermal properties under near-infrared (NIR)-light irradiation above 780 nm. However, AuNRs easily leaked out from local pathological tissues and circulated in the body, reducing photothermal therapy (PTT) efficacy. By complexing AuNRs with a scaffold via interactions, AuNRs might be dispersed in the scaffold and fixed in the tumor site. Thus, based on the mussel-mimetic adhesion concept, AuNRs were designed to be coated with polydopamine (PDA), and then the prepared polydopamine-coated AuNRs (AuNR-PDA) were incorporated into a thermosensitive injectable hydrogel composed of ß-glycerophosphate-bound chitosan (CGP) and dopamine-modified alginate (Alg-DA) efficiently. Due to the strong interactions between PDA and polymers, AuNR-PDA could be immobilized stably and evenly into the obtained CGP/Alg-DA/AuNR composite hydrogel, which can avoid overheating locally or leaking out. The sol-gel transition temperature of the composite hydrogel was adjusted to the body temperature at around 37 °C to be conveniently injectable in vivo. With NIR irradiation at 808 nm of wavelength, the composite hydrogel was locally heated quickly to over 50 °C depending on controlling the irradiation powers and times. Moreover, the in vitro cytotoxicity test of the composite hydrogel showed good biocompatibility to normal cells but obvious suppression to tumor cells' growth under multiple times of photothermal therapy. Furthermore, the in vivo antitumor test demonstrated the obvious suppression to tumor growth of the CGP/Alg-DA/AuNR composite hydrogel under multiple PTTs. Therefore, the injectable CGP/Alg-DA/AuNR hydrogel could be a promising candidate for the long-term repeated photothermal treatment of tumors.

Application of functionalized nanoparticle for mass spectrometry.

We synthesized functionalized nanoparticles (NPs) by in mixing aqueous solutions of 3d transition metal (iron, or manganese) chlorides (MCl2 x nH2O) and (3-aminopropyl)triethoxysilane, and in this unique method, monodispersed NPs were obtained in a single step. The prepared NPs examined by X-ray diffraction, transmission electron microscope, Fourier transform infrared spectroscopy and zeta potential measurement. The synthesized NPs surround by amorphous SiO2 and possess amino and hydroxyl groups on NPs surface. The number-average diameter of the NPs was determined to be about 3 and 5 nm. The NPs worked as an ionization assisting reagent in mass spectrometry (MS) by means of what is called nanoparticle assisted laser desorption/ionization (nano-PALDI) MS has begun to be used to analyze low molecular compound. In this paper, we introduced analysis of the food product and pesticide as environmental pollutant by using nano-PALDI MS.

Metal-Assisted Injection Spinning of Ultra Strong Fibers from Megamolecular LC Polysaccharides.

The molecular orientation of liquid crystalline (LC) hydrogels has the potential to induce a range of functionalities that can deliver great mechanical strength. Sacran is a supergiant LC polysaccharide isolated from the cyanobacterium Aphanothece sacrum with a high amount of anionic functional groups such as sulfates and carboxylates. In this article, ultra-strong sacran hydrogels and their dried fibers were produced by cross-linking under injection flow with trivalent metal ions such as Al3+, Cr3+, Fe3+, In3+, and rare-earth metal ions such Er3+ and Sr3+. Crossed-polarizing microscopy and X-ray diffraction imaging revealed a uniaxial molecular orientation in the LC gel fiber, resulting in outstanding mechanical characteristics.

Anionic complexes of MWCNT with supergiant cyanobacterial polyanions.

Multi-walled carbon nanotubes (MWCNTs) were well dispersed in an aqueous solution of the cyanobacterial polysaccharide, sacran, with an ultra-high molecular weight >10 million g/mol. MWCNTs powder was put into aqueous solutions of various polysaccharides including sacran and was dispersed under sonication. As a result of the turbidity measurement of the supernatant, it was found that sacran showed the highest MWCNT-dispersion efficiency of all the polysaccharides used here. Cryogenic transmission electron microscopic (Cryo-TEM) studies directly demonstrated the existence of MWCNTs in the supernatant, and high-resolution TEM observation revealed that MWCNTs covered by sacran chains made their efficient dispersion in water. Raman spectroscopy demonstrated the existence of MWCNT in dried sample from supernatant and the interaction between MWCNT and sacran. The ζ-potential measurement of the dispersion indicated the negative surface charges of the sacran/MWCNT complexes. Then the MWCNT complexes were able to fabricate by ionic interaction; electrophoresis of the anionic complex formed the sacran/MWCNT gels on the anode while the droplet of sacran/MWCNT dispersion formed gel beads in the presence of the lanthanoid cations.

Hyperbranched polycoumarates with photofunctional multiple shape memory.

In good shape: The films of hyperbranched polycoumarate derivatives can undergo a reversible [2+2] cycloaddition under irradiation of UV light and behave like photomechanical elastomers. From a predetermined original shape A the photonically and thermally memorized shapes B and C were obtained. The original shape was recovered by photoirradiation (see picture; Tg =glass transition temperature).

Correction: One-step mild preparation of tough and thermo-reversible poly(vinyl alcohol) hydrogels induced by small molecules.

Correction for 'One-step mild preparation of tough and thermo-reversible poly(vinyl alcohol) hydrogels induced by small molecules' by Chuang Dong et al., Chem. Commun., 2021, 57, 3789-3792, https://doi.org/10.1039/D1CC00578B.

Oligonucleotide analysis by nanoparticle-assisted laser desorption/ionization mass spectrometry.

We analyzed oligonucleotides by nanoparticle-assisted laser desorption/ionization (nano-PALDI) mass spectrometry (MS). To this end, we prepared several kinds of nanoparticles (Cr-, Fe-, Mn-, Co-based) and optimized the nano-PALDI MS method to analyze the oligonucleotides. Iron oxide nanoparticles with diammonium hydrogen citrate were found to serve as an effective ionization-assisting reagent in MS. The mass spectra showed both [M - H](-) and [M + xMe(2+)- H](-) (Me: transition metal) peaks. The number of metal-adducted ion signals depended on the length of the oligonucleotide. This phenomenon was only observed using bivalent metal core nanoparticles, not with any other valency metal core nanoparticles. Our pilot study demonstrated that iron oxide nanoparticles could easily ionize samples such as chemical drugs and peptides as well as oligonucleotides without the aid of an oligonucleotide-specific chemical matrix (e.g., 3-hydroxypicolinic acid) used in conventional MS methods. These results suggested that iron-based nanoparticles may serve as the assisting material of ionization for genes and other biomolecules.

Bio-Based Hotmelt Adhesives with Well-Adhesion in Water.

We suggest a simple idea of bio-based adhesives with strong adhesion even under water. The adhesives simply prepared via polycondensation of 3,4-dihydroxyhydrocinnamic acid (DHHCA) and lactic acid (LA) in one pot polymerization. Poly(DHHCA-co-LA) has a hyperbranched structure and demonstrated strong dry and wet adhesion strength on diverse material surfaces. We found that their adhesion strength depended on the concentration of DHHCA. Poly(DHHCA-co-LA) with the lowest concentration of DHHCA showed the highest adhesion strength in water with a value of 2.7 MPa between glasses, while with the highest concentration of DHHCA it exhibited the highest dry adhesion strength with a value of 3.5 MPa, which was comparable to commercial instant super glue. Compared to underwater glues reported previously, our adhesives were able to spread rapidly under water with a low viscosity and worked strongly. Poly(DHHCA-co-LA) also showed long-term stability and kept wet adhesion strength of 2.2 MPa after steeping in water for 1 month at room temperature (initial strength was 2.4 MPa). In this paper, Poly(DHHCA-co-LA) with strong dry and wet adhesion properties and long-term stability was demonstrated for various kinds of applications, especially for wet conditions.

One-step mild preparation of tough and thermo-reversible poly(vinyl alcohol) hydrogels induced by small molecules.

To overcome shortcomings of the traditional freeze-thaw method for PVA hydrogel preparation, we develop a one-step mild method, which induces PVA crystallization to form hydrogels through small molecules containing hydroxyl and carboxyl groups. The obtained hydrogels showed high mechanical properties, untypical plasticity with short gelation time and repeatable sol-gel transformation.

Mussel-Inspired Epoxy Bioadhesive with Enhanced Interfacial Interactions for Wound Repair.

The balance between high mechanical properties and strong adhesion strength is crucial in designing and preparing a bio-based hydrogel adhesive for wound closure. Although the adhesion performance of bioadhesives has been remarkably improved by modification with catechol groups, their mechanical properties are yet to meet the biomedical requirements. In this study, mussel-inspired epoxy bioadhesives (CSD-PEG) were synthesized based on catechol-modified chitosan oligosaccharide (CSD) and polyethylene glycol diglycidyl ether (PEGDGE) through nucleophilic substitution. Notably, the CSD-PEG adhesive showed high mechanical and adhesion strengths, which were up to 50.7 kPa and 136.7 kPa, respectively. It was confirmed that a certain amount of the epoxy and catechol groups provided multiple interfacial interactions among the adhesives, substrates, and polymer chains for enhancing the performance of adhesives. The adhesives showed good binding and repairing effects for wound closure and favorable biocompatibility in vivo. The prepared CSD-PEG adhesives are expected to be a promising candidate for surgical tissue repair, wound closure, and tissue engineering fields. STATEMENT OF SIGNIFICANCE: Current reported adhesives composed of biopolymers generally suffer from poor mechanical properties or weak tissue adhesiveness. Therefore, to achieve simultaneously high mechanical and adhesion properties in a bio-based adhesive for wound closure is a big challenge. In this study, mussel-inspired adhesive hydrogels (CSD-PEG) were prepared based on catechol-modified chitosan oligosaccharide (CSD) and polyethylene glycol diglycidyl ether (PEGDGE). The tensile strength and adhesive strength of CSD-PEG on porcine skin reached 50.7 kPa and 136.7 kPa, respectively, which were higher than those for most reported biopolymeric adhesives, mainly due to the multiple interfacial interactions between the catechol and epoxy groups. The CSD-PEG bioadhesives also showed good binding and repairing effects for wound closure and tissue regeneration in vivo.

Gelation behavior by the lanthanoid adsorption of the cyanobacterial extracellular polysaccharide.

The self-organization behavior of an extracellular polysaccharide (sacran) extracted from the cyanobacterium Aphanothece sacrum in response to lanthanoid ion adsorption was investigated. Consequently, cryogenic TEM images revealed that sacran could be cross-linked by Nd(3+) trivalent ions and formed a fibrous nanostructural network containing water. Furthermore, sacran adsorbed trivalent metal ions at a 3:1 ratio, which was the theoretical ionic adsorption and showed more efficient adsorption than alginate based on electric conductivity titration. The critical gelation concentrations, Cg, where sacran formed tough gels upon metal ion binding were estimated. The Cg for trivalent metal ions was lower than that for divalent ions, and the Cg for lanthanoid ions was particularly low at 10(-3) to 10(-4) M, changing every four elemental numbers. The extracellular matrix of Aphanothece sacrum, sacran, may adsorb metal ions to create fibrous nanostructures that reinforce the jelly matrix.

Mussel inspired bio-adhesive with multi-interactions for tissue repair.

Bio-adhesives based on biopolymers have been widely researched for tissue repair. However, the adhesive properties are still insufficient to meet the practical applications. Introducing functional groups into the polymer chains that have multi-interactions among inter/intra-molecules and with substrates is an efficient way to increase cohesion force and further improve the adhesive properties. In this study, 3,4-dihydroxyphenyl propionic acid (DPA) and dopamine (DA) containing adhesion functional catechol groups were employed to modify chitosan (CS) and γ-polyglutamic acid (γPGA), respectively. The substituted degrees of the catechol groups were controlled by the catechol compositions. DPA modified chitosan/DA modified γPGA (CS-DPA/γPGA-DA) adhesives prepared by mixing CS-DPA and γPGA-DA. Effects of the substituted degrees and substrates on the adhesion strength were measured by tensile testing machine. The results showed good adhesion property of the CS-DPA/γPGA-DA adhesive on many surfaces of the substrates. Especially on the arthrodial cartilage, the adhesive strength reached around 150 kPa, much higher than commercially available tissue adhesives. The high adhesion property might be due to the adhesion interactions between the catechol groups and substrates and the high cohesion forces induced by the crosslinking interactions formation among the catechol groups and the electrostatic interactions between the CS and γPGA polymers. In vitro experiments demonstrated that the adhesive had good biocompatibility. These results suggested the catechol-based adhesive is a very suitable and promising biomaterial in the clinical medicine field.

Mass Spectrometry Imaging Analysis of Location of Procymidone in Cucumber Samples.

The localization of procymidone fungicide residue in cucumbers was investigated by mass spectrometry imaging (MSI). Cucumbers were grown, harvested, and then divided into two groups that were either sprayed or not sprayed with procymidone. The content of procymidone in the cucumbers was quantitatively determined by chromatographic techniques. Subsequently, the spatial distribution of procymidone was imaged by MSI. Procymidone reached the central part of the cucumbers following spraying compared with the control.

Mussel-mimetic, bioadhesive polymers from plant-derived materials.

AIM: Mussel-mimetic, bioadhesive polymers are synthesized from plant-derived sources. The strong adhesive action is caused by interactions between the catechol groups at the end of the polymer terminal chains and the substrate surface. Here, we present a preliminary study of the adhesion properties and a discussion of the adhesion mechanism. METHODS: Two bioadhesive polymers were synthesized from natural plant-derived monomers by the transesterification of: (a) caffeic acid (3,4-dihydroxycinnamic acid; DHCA) and p-coumaric acid (4-hydroxycinnamic acid; 4HCA) to produce poly(DHCA-co-4HCA); and (b) 4-dihydroxyhydrocinnamic acid (DHHCA) and 3-(3-hydroxyphenyl) propionic acid (3HPPA) to produce poly(DHHCA-co-3HPPA). Thermoplastic poly(DHCA-co-4HCA) or poly(DHHCA-co-3HPPA) was placed between glass, carbon, steel, or bovine dentin substrates, and a lap shear adhesion test was conducted to compare them using conventional cyanoacrylate glue and epoxy resin. RESULTS: The greatest adhesion for all tested substrates was exhibited by poly(DHHCA-co-3HPPA), followed by epoxy resin adhesive, poly(DHCA-co-4HCA), and cyanoacrylate adhesive. The adhesive strength of poly(DHHCA-co-3HPPA) was greater than 25.6 MPa for glass, 29.6 MPa for carbon, 15.7 MPa for steel, and 16.3 MPA for bovine dentin. CONCLUSION: The adhesion of poly(DHHCA-co-3HPPA) might be the strongest reported for a mussel-mimic adhesive system, and could be a feasible alternative to petroleum adhesives.

Mass spectrometry imaging: applications to food science.

Two-dimensional mass spectrometry (MS) analysis of biological samples by means of what is called MS imaging (MSI) is now being used to analyze analyte distribution because it facilitates determination of the existence (what is it?) and localization (where is it?) of biomolecules. Reconstruction of mass image by target signal is given after two-dimensional MS measurements on a sample section. From only one section, we can understand the existence and localization of many molecules without the need of an antibody or fluorescent reagent. In this review, we introduce the analysis of localization of functional constituents and nutrients in herbal medicine products via MSI. The ginsenosides were mainly distributed in the periderm and the tip region of the root of Panax ginseng. The capsaicin was found to be more dominantly localized in the placenta than the pericarp and seed in Capsicum fruits. We expect MSI will be a useful technique for optical quality assurance.

Dynamical visualization of "coffee stain phenomenon" in droplets of polymer solution via fluorescent microscopy.

In the drying process of polymer solution droplets, we propose an experimental procedure for visualizing the solute concentration profile by combining the fluorescent microscopy with the lateral profile observation. We have conducted a dynamical observation of the transport process of the solute polymer toward the edge that causes the "coffee stain phenomenon". We have found that the polymer concentration increases sharply near the edge, while it remains almost constant in the central region until the last stage of drying. The method is useful to understand the dynamical process that occurs near the contact line.

Contact dynamics in the adhesion process between spherical polydimethylsiloxane rubber and glass substrate.

The contact dynamics between a soft sphere and a rigid substrate on the micron scale was studied experimentally. The time evolution of the contact radius, contact angle, and the force acting on the sphere were measured simultaneously in the loading and the unloading cycle. There is little effect of repetition: the experimental results obtained in the second and third cycles agree completely with those of the first cycle. The contact angle changes dynamically in the loading and the unloading processes, and there are regions where the advancing angle and the receding angle remain constant. The experimental results were analyzed in terms of the extended Johnson-Kendall-Roberts theory, and it was found, to our surprise, that the theory works well: the theory predicts the force curve quite accurately if the apparent surface energy obtained from the contact radius is used. The apparent surface energy was experimentally obtained as a function of the contact line velocity, and it was found that (1) the curve agrees qualitatively with that predicted by Greenwood and Johnson, and (2) certain modification is needed when the velocity of the contact line changes the sign.

Influence of cyclohexane vapor on stick-slip friction between mica surfaces.

Stick-slip friction between mica surfaces under cyclohexane vapor has been investigated with the Surface Force Apparatus. The dynamic shear stress decreased from 60 to 10 MPa with increasing relative vapor pressure (rvp) from 5% to 50%. Between a rvp of 50% and 80%, the shear stress remained at approximately 10 MPa, with a slight decrease on increasing the rvp. At a rvp greater than 80%, the values of shear stress were below 5 MPa. The stick-slip behavior was observed in the rvp range of 20% to saturation. When the rvp reached 20%, stick-slip appeared but faded out with sliding time. At a rvp greater than 50%, the stick-slip pattern was stable without fading. By taking into account the size of the meniscus formed by capillary condensation of the liquid around the contact area and the Laplace pressure, the dependence of shear stress and the stick-slip modulation on rvp suggests that the origin of the stick-slip observed in cyclohexane vapor is as follows: At a rvp greater than 50%, where stable sick-slip is observed, the stick-slip caused by the cyclohexane layering in the contact area is of essentially the same origin as that observed with mica surfaces sliding in bulk cyclohexane liquid. As with the bulk liquid experiment, decreasing the layer thickness (or the number of the layers) between the surfaces increases the shear stress at the onset of slip. In the vapor phase experiments, the stick-slip is enhanced by the increase of the negative Laplace pressure in the capillary condensed liquid, thereby forcing the surfaces toward each other more strongly with decreasing rvp. In the rvp range between 20% and 50%, where the fading stick-slip is observed, the condensate liquid seeps into the contact area under the influence of the applied tangential force and thus triggers the slip motion. Due to the small condensation volume, the liquid condensed around the contact area is exhausted in the process of repeating stick-slip. As the slip length is limited to the meniscus size, the stick-slip amplitude becomes smaller, and eventually the surfaces start sliding without stick-slip.