Preparation and characterization of amidated pectin-gelatin-oxidized tannic acid hydrogel films supplemented with in-situ reduced silver nanoparticles for wound-dressing applications.

Wound dressings play a crucial role in protecting injured tissues and promoting the healing process. Traditional fabrication of antibacterial wound dressings can be complex and may involve toxic components. In this study, we developed an innovative hydrogel film (AP:GE@OTA/Ag) composed of amidated pectin (AP), gelatin (GE), oxidized tannic acid (OTA) at varying concentrations, and in-situ reduced silver nanoparticles (AgNPs). FTIR and XRD analyses confirmed that crosslinking occurs via interactions between OTA quinone groups and free amino groups in AP and GE. TEM imaging demonstrated the well-dispersed AgNPs with an average particle size of 58.64 nm, while the TG measurements indicated the enhancement of the thermal stability compared to AP:GE films. The AP:GE@OTA/Ag films exhibited superior fluid uptake ability (90.96 % at 2 h), water retention capacity (91.69 % at 2 h), and water vapor transmission rate (1903.29 g/m2/day), alongside improved tensile strength (38 MPa). Additionally, these films showed excellent cytocompatibility and sustained potent antimicrobial activity against S. aureus and E. coli with low AgNPs loadings of 1.02 ± 0.13 µg/cm2. NIT-1 mouse insulinoma cells demonstrated robust proliferation when cultured with the prepared dressings. These films significantly accelerated wound repair in a skin excision model, indicating their potential clinical applications for wound healing.

Chitosan based ethanolicAllium Sativumextract hydrogel film: a novel skin tissue regeneration platform for 2nd degree burn wound healing.

This study investigated the potential of ethanolic garlic extract-loaded chitosan hydrogel film for burn wound healing in an animal model. The ethanolic garlic extract was prepared by macerating fresh ground garlic cloves in ethanol for 24 h, followed by filtration and concentration using a rotary evaporator. Hydrogels were then prepared by casting a chitosan solution with garlic extract added at varying concentrations for optimization and, following drying, subjected to various characterization tests, including moisture adsorption (MA), water vapor transmission rate (WVTR), and water vapor permeability rate (WVPR), erosion, swelling, tensile strength, vibrational, and thermal analysis, and surface morphology. The optimized hydrogel (G2) was then analyzedin vivofor its potential for healing 2nd degree burn wounds in rats, and histological examination of skin samples on day 14 of the healing period. Results showed optimized hydrogel (G2; chitosan: 2 g, garlic extract: 1 g) had MA of 56.8% ± 2.7%, WVTR and WVPR of 0.00074 ± 0.0002, and 0.000 498 946 ± 0.0001, eroded up to 11.3% ± 0.05%, 80.7% ± 0.04% of swelling index, and tensile strength of 16.6 ± 0.9 MPa, which could be attributed to the formation of additional linkages between formulation ingredients and garlic extract constituents at OH/NH and C=O, translating into an increase in transition melting temperature and enthalpy (ΔT= 238.83 °C ± 1.2 °C, ΔH= 4.95 ± 0.8 J g-1) of the chitosan moieties compared with blank. Animal testing revealed G2 formulation significantly reduced the wound size within 14 d of the experiment (37.3 ± 6.8-187.5 ± 21.5 mm2) and had significantly higher reepithelization (86.3 ± 6.8-26.8 ± 21.5 and 38.2% ± 15.3%) compared to untreated and blank groups by hastening uniform and compact deposition of collagen fibers at the wound site, cementing developed formulation a promising platform for skin regeneration.

Citric acid cross-linked pomegranate peel extract-loaded pH-responsive ß-cyclodextrin/carboxymethyl tapioca starch hydrogel film for diabetic wound healing.

Pomegranate peel extract (PPE) hydrogel films filled with citric acid (CA) and ß-cyclodextrin-carboxymethyl tapioca starch (CMS) were designed mainly to prevent wound infections and speed up the healing process. FTIR and NMR studies corroborated the carboxymethylation of neat tapioca starch (NS). CMS exhibited superior swelling behavior than NS. The amount of CA and ß-CD controlled the physicochemical parameters of developed PPE/CA/ß-CD/CMS films. Optimized film (OF) exhibited acceptable swellability, wound fluid absorptivity, water vapor transmission rate, water contact angle, and mechanical properties. Biodegradable, biocompatible, and antibacterial films exhibited pH dependence in the release of ellagic acid for up to 24 h. In mice model, PPE/CA/ß-CD/CMS hydrogel film treatment showed promising wound healing effects, including increased collagen deposition, reduced inflammation, activation of the Wingless-related integration site (wnt) pathway leading to cell division, proliferation, and migration to the wound site. The expression of the WNT3A gene did not show any significant differences among all the studied groups. Developed PPE-loaded CA/ß-CD/CMS film promoted wound healing by epithelialization, granulation tissue thickness, collagen deposition, and angiogenesis, hence could be recommended as a biodegradable and antibacterial hydrogel platform to improve the cell proliferation during the healing of diabetic wounds.

Accelerated full-thickness skin wound tissue regeneration by self-crosslinked chitosan hydrogel films reinforced by oxidized CNC-AgNPs stabilized Pickering emulsion for quercetin delivery.

BACKGROUND: The non-toxic self-crosslinked hydrogel films designed from biocompatible materials allow for controlled drug release and have gathered remarkable attention from healthcare professionals as wound dressing materials. Thus, in the current study the chitosan (CS) film is infused with oil-in-water Pickering emulsion (PE) loaded with bioactive compound quercetin (Qu) and stabilized by dialdehyde cellulose nanocrystal-silver nanoparticles (DCNC-AgNPs). The DCNC-AgNPs play a dual role in stabilizing PE and are involved in the self-crosslinking with CS films. Also, this film could combine the advantage of the controlled release and synergistic wound-healing effect of Qu and AgNPs. RESULTS: The DCNC-AgNPs were synthesized using sodium periodate oxidation of CNC. The DCNC-AgNPs were used to stabilize oil-in-water PE loaded with Qu in its oil phase by high speed homogenization. Stable PEs were prepared by 20% v/v oil: water ratio with maximum encapsulation of Qu in the oil phase. The Qu-loaded PE was then added to CS solution (50% v/v) to prepare self-crosslinked films (CS-PE-Qu). After grafting CS films with PE, the surface and cross-sectional SEM images show an inter-penetrated network within the matrix between DCNC and CS due to the formation of a Schiff base bond between the reactive aldehyde groups of DCNC-AgNPs and amino groups of CS. Further, the addition of glycerol influenced the extensibility, swelling ratio, and drug release of the films. The fabricated CS-PE-Qu films were analyzed for their wound healing and tissue regeneration potential using cell scratch assay and full-thickness excisional skin wound model in mice. The as-fabricated CS-PE-Qu films showed great biocompatibility, increased HaCat cell migration, and promoted collagen synthesis in HDFa cells. In addition, the CS-PE-Qu films exhibited non-hemolysis and improved wound closure rate in mice compared to CS, CS-Qu, and CS-blank PE. The H&E staining of the wounded skin tissue indicated the wounded tissue regeneration in CS-PE-Qu films treated mice. CONCLUSION: Results obtained here confirm the wound healing benefits of CS-PE-Qu films and project them as promising biocompatible material and well suited for full-thickness wound healing in clinical applications.

Customized Hydrogel Films for MicroRNA Super-Resolution Imaging in Liquid Biopsies.

Tissue biopsy for early diagnosis and monitoring comes with several challenges, such as its invasiveness, and issues related to tissue heterogeneity in sampling. To address these issues, researchers have proposed a noninvasive approach called liquid biopsy, which uses blood samples to detect specific noncoding RNA (microRNA, miRNA). However, the current process of isolating and amplifying miRNA can be time-consuming and yield nonspecific results. In this study, a new super-resolution imaging tool is introduced that utilizes a thin, hydrogel-based liquid view (LV) film. This film can undergo a ninefold expansion and allows the analysis of cells obtained from liquid biopsy. The potential of the LV film is validated as a tool for early diagnosis and prognosis by testing biofluids derived from a variety of diseases. This method is confirmed to accurately analyze a greater number of miRNAs with higher sensitivity in a shorter time compared to other analytical methods. These findings suggest that the LV film provides high specificity, and multiplexing in detecting small amounts of miRNAs within cells, making it suitable for 3D implementation. It is proposed that liquid biopsy with LV films can be a solution to limitations related to the invasiveness, cost, and time-consuming nature of molecular analysis.

A Wearable Thin-Film Hydrogel Laser for Functional Sensing on Skin.

Flexible photonics offers the possibility of realizing wearable sensors by bridging the advantages of flexible materials and photonic sensing elements. Recently, optical resonators have emerged as a tool to improve their oversensitivity by integrating with flexible photonic sensors. However, direct monitoring of multiple psychological information on human skin remains challenging due to the subtle biological signals and complex tissue interface. To tackle the current challenges, here, we developed a functional thin film laser formed by encapsulating liquid crystal droplet lasers in a flexible hydrogel for monitoring metabolites in human sweat (lactate, glucose, and urea). The three-dimensional cross-linked hydrophilic polymer serves as the adhesive layer to allow small molecules to penetrate from human tissue to generate strong light--matter interactions on the interface of whispering gallery modes resonators. Both the hydrogel and cholesteric liquid crystal microdroplets were modified specifically to achieve high sensitivity and selectivity. As a proof of concept, wavelength-multiplexed sensing and a prototype were demonstrated on human skin to detect human metabolites from perspiration. These results present a significant advance in the fabrication and potential guidance for wearable and functional microlasers in healthcare.

Recoverable and degradable carboxymethyl chitosan polyelectrolyte hydrogel film for ultra stable encapsulation of curcumin.

Hydrogels have shown great potential for application in food science due to their diverse functionalities. However, most hydrogels inevitably contain toxic chemical cross-linking agent residues, posing serious food safety concerns. In this paper, a curcumin/sodium alginate/carboxymethyl chitosan hydrogels (CSCH) were prepared by self-assembly of two oppositely charged polysaccharides, carboxymethyl chitosan and sodium alginate, to form a three-dimensional network encapsulating curcumin for extending food shelf life. The network structure of the CSCH film confirmed by FTIR, XRD, and XPS was mainly formed by electrostatic interactions. The chemical stability of CSCH network encapsulated curcumin was 4.2 times greater than that of free curcumin, with excellent gas barrier, antimicrobial, antioxidant, and biosafety properties. It was found that CSCH films reduced dehydration, prevented nutrient loss, inhibited microbial growth, and lowered the respiration rate, which effectively maintained the quality of mango and prolonged its shelf-life up to 11 days. Notably, CSCH films possessed the properties of rapid recycling (10 mins) and biodegradability (53 days). This polysaccharide-based hydrogel film provides a viable strategy for the development of green and sustainable food packaging.

Smart Free-Standing Bilayer Polyacrylamide/DNA Hybrid Hydrogel Film-Based Sensing System Using Changes in Bending Angles as a Visual Signal Readout.

Stimuli-responsive DNA hydrogels have shown great potential in sensing applications due to their attractive properties such as programmable target responsiveness, excellent biocompatibility, and biodegradability. In contrast to the extensively developed DNA hydrogel sensing systems based on the stimuli-responsive hydrogel-to-solution phase transition of the hydrogel matrix, the quantitative sensing application of DNA hydrogels exhibiting smart shape deformations has rarely been explored. Moreover, bulk DNA hydrogel-based sensing systems also suffer from high material cost and slow response. Herein, free-standing bilayer polyacrylamide/DNA hybrid hydrogel films with programmable responsive properties directed by the sequence of functional DNA units have been constructed. Compared with bulk DNA hydrogels, these DNA hydrogel films with a thickness at the micrometer scale not only greatly reduce the consumption of DNA materials but also facilitate the mass transfer of biomacromolecular substances within the hydrogel network, thus favoring their sensing applications. Therefore, a target-responsive smart DNA hydrogel film-based sensor system is further demonstrated based on the large amplitude macroscopic shape deformation of the film as a visual signal readout. As a proof of concept, Pb2+ or UO22+ ion-responsive DNA units were introduced into the active layer of the bilayer hydrogel films. In the presence of Pb2+ or UO22+ ions, the occurrence of a cleavage reaction within the DNA units leads to the release of DNA segments from the hydrogel film, inducing a dramatic shape deformation of the film, and thus sensing of Pb2+ or UO22+ ions with high specificity is achieved based on measuring the bending angle changes of these smart free-standing films. These smart DNA hydrogel film sensors with target-programmable responsiveness, simple operation, and ease of storage may hold promise for future rapid on-site testing applications.

Conjugated Polymer-Based Hydrogel Film for a Fast and Sensitive Detection of Fe(â ¢) in Vegetables.

Fluorescent film sensors are ideal for the real-time outdoor detection of heavy metal ions of Fe3+, but they are limited because of their low sensitivity and long response time due to their special structure. In this work, we constructed a fluorescent hydrogel for the specific detection of Fe3+, utilizing poly(9-fluorenecarboxylic acid) (PFCA) as the sensing moiety and sodium alginate (SA) as the cross-linking substrate, which exhibited a rapid and selective recognition of Fe3+ among a panel of 16 anions and 21 cations. It can sense Fe3+ at 0.1 nM immediately owing to the porous network structure of the PFCA-SA film that provided enhanced ion transport channels and active sites, and the "molecular line effect" of polymer PFCA. Moreover, we successfully applied this platform to detect Fe3+ in four different vegetable samples. This work provides an innovative and effective strategy for fabricating green and sustainable fluorescent sensors.

Fluorescent carbon dots in situ polymerized biodegradable semi-interpenetrating tough hydrogel films with antioxidant and antibacterial activity for applications in food industry.

A flexible, antioxidant, biodegradable, and UV-resistant polymeric nanocomposite hydrogel with heteroatom-doped carbon dots (CDs) has been fabricated using a simple one-step in situ free radical gelation process. The hydrogel formation and their physico-mehcanical characteristics have been assessed by rheology, uniaxial tensile and compression testing. The water uptake behaviour of the hydrogels is controlled by the CDs by manipulating their internal morphology and porosity. The porous nature of the hydrogels has been found from their scanning electron microscopic images which are also supported by their anomalous diffusion-based transport mechanism. The rheological signatures of the hydrogels show delayed network rupturing due to the secondary physical crosslinking alleviated by CDs. Moreover, CDs are directly influencing the permeabilites (oxygen and moisture) by lowering the values compared to their neat hydrogel films which are essential for a packing material. The biodegradability of the hydrogel films showed gradual weight loss (<75 %) within 3 weeks. The hydrogel films also have been qualified to be acted as antibacterial and antioxidant material. The shelf-life and non-leaching of CDs from gel matrices are also performed which shows its excellent capability to be used as a potential antibacterial, biodegradable, antioxidant alternative packaging material in food sectors.

Gelatin/Polyacrylamide-Based Antimicrobial and Self-Healing Hydrogel Film for Wound Healing Application.

In this study, a self-healing, adhesive, and superabsorbent film made of gelatin, poly(acrylamide), and boric acid (GelAA) was successfully synthesized using a free radical reaction mechanism. The optimized film showed a remarkable 2865 ± 42% water absorptivity and also exhibited excellent self-healing behavior. The GelAA films were further loaded with silver nanoclusters (AgNCs) and ursodeoxycholic acid (UDC) (loading efficiency = 10%) to develop UDC/Ag/GelAA films. The loading of AgNCs in UDC/Ag/GelAA films helped in exhibiting 99.99 ± 0.01% antibacterial activity against both Gram-positive and Gram-negative bacteria, making them very effective against bacterial infections. Additionally, UDC/Ag/GelAA films had 77.19 ± 0.52% porosity and showed 90% of UDC release in 30 h, which helps in improving the cell proliferation. Our research provides an easy but highly effective process for synthesizing a hydrogel film, which is an intriguing choice for wound healing applications without the use of antibiotics.

Visualized sensing of erythritol using a simple enzyme-free catechol-based hydrogel film.

Based on the versatile properties of bio-derived materials, non-enzymatic assays in combination with electronic devices have attracted increasing interest. Here, we report a novel enzyme-free visualization approach for the detection of erythritol, which is a zero-calorie natural sweetener and serves as an ideal sucrose substitute for diabetics or overweight people who need sugar control. The recognition element of the electrochemical biosensor was constructed by catechol modification on a chitosan-based hydrogel film. The signal transduction was achieved by the competitive binding assay of sweeteners. The results show that 2-fluorophenylboronic acid (FPBA) can form a cyclic boronate ester with the ortho-hydroxyls of both reduced catechol and oxidized quinone, impeding the electron transfer and leading to redox signal attenuation. The addition of sweeteners caused a competitive reaction resulting in bonding between the 1,2-diols and FPBA moieties, and in the recovery of the redox signals. Importantly, the pattern of redox signal changes of catechol can be detected optically, as the oxidized quinone state is darker in color than the reduced catechol state. Using a simple cell phone imaging application, we demonstrate that erythritol can be distinguished from other sweeteners in real samples using the oxidized catechol-Chit0/agarose hydrogel film. Thus, we envision that this method could allow diabetics and people who need to control their sugar intake to detect whether the product contains only erythritol in the field or at home. In addition, this work further illustrates the potential of bio-derived materials for performing redox-based functions and enzyme-free visualization assays.

In Situ Fabrication of Photoluminescent Hydrogen-Bonded Organic Framework-Functionalized Ca (II) Hydrogel Film for the Tetracyclines Visual Sensor and Information Security.

A facilely in situ fabricated hydrogen-bonded organic framework (HOF) hydrogel film with perfect photoluminescent performance was designed for visual sensing of tetracycline antibiotics (TCs) and information security. Luminescent HOF (MA-IPA) was combined with sodium alginate (SA) through hydrogen bonding actions and electrostatic interactions, then cross-linked with Ca2+ ions to form HOF hydrogel film (Ca@MA-IPA@SA). The HOF hydrogel film exhibited exceptional mechanical robustness along with stable blue fluorescence and ultralong green phosphorescence. After exposure to TCs, Ca2+ was combined with TCs to generate a new green fluorescence exciplex (TC-Ca2+) in hydrogel films. Due to fluorescence resonance energy transfer, the fluorescence of MA-IPA was quenched, and the fluorescent color of the HOF hydrogel film was changed from blue to green. This dichromatic fluorescent response is convenient for the visual and rapid detection of TCs. The detection limits of tetracycline (TC), oxytetracycline (OTC), and chlortetracycline (CTC) were 5.1, 7.7, and 32.7 ng mL-1, respectively. Importantly, this hydrogel sensing platform was free of tedious operation and enabled the ultrasensitive and selective detection of TCs within 6 min. It has been successfully applied to TC detection in pork and milk samples. Based on the stable photoluminescence performance of HOF hydrogel films and fluorescent-responsive properties to TCs, two types of anticounterfeiting arrays were fabricated for information encryption and decryption. This work provides a novel approach for on-site detection of TCs and offers valuable insights into information security.

Enzyme-functionalized hydrogel film for extracorporeal uric acid reduction.

Enzyme replacement therapy for hyperuricemia treatment has been proven effective for critical state hyperuricemia patients. Still, direct administration of recombinant uricase can induce several fatal side effects. To circumvent this drawback, hydrogel protein carriers can be used in platforms for extracorporeal treatment such as microscale-based devices. In this work, calcium alginate and poly-(vinyl alcohol) hydrogel films were studied for their urate oxidase immobilization and uric acid reduction, which could be implemented in microscale-based extracorporeal devices. A mathematical model was developed in conjunction with uric acid reduction experiments to evaluate the influence of mass transfer and reaction parameters in the Michaelis-Menten kinetic expression. Alginate hydrogels prepared with crosslinker 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and N-(hydroxysuccinimide) offered superior diffusivity of uric acid in the gel matrix at the maximum value of D g , UA ≈ $$ {D}_{\mathrm{g},\mathrm{UA}}\approx $$ 1.98 × 10-11 m2 /s compared with alginate prepared solely from ionic crosslinking with D g , UA ≈ $$ {D}_{\mathrm{g},\mathrm{UA}}\approx $$ 5.31 × 10-12 m2 /s at the same alginate concentration. The maximum value of νmax was experimentally determined at 7.78 × 10-5 mol/(m3 s). A 3% sodium alginate hydrogel with crosslinkers yielded the highest reduction of uric acid at 92.70%. The mathematical model demonstrated an excellent prediction of uric acid conversion suggesting potential use of the model for formulation and maximizing the therapeutic performance of functionalized hydrogels.

Ln-MOF-Based Hydrogel Films with Tunable Luminescence and Afterglow Behavior for Visual Detection of Ofloxacin and Anti-Counterfeiting Applications.

Highly selective and sensitive quantitative detection of ofloxacin (OFX) at ultralow concentrations in aqueous media and development of new afterglow materials remains a challenge. Herein, a new 2D water-stable lanthanide metal-organic framework (NIIC-2-Tb) is proposed, which exhibits high selectivity towards OFX through the luminescence quenching with the lowest detection limit (1.1 × 10-9 M) reported to date and a fast response within 6 s. In addition, the luminescent detection of OFX by NIIC-2-Tb is not affected by typical components of blood plasma and urine. The excellent sensing effect of NIIC-2-Tb is further utilized to prepare a composite functional sensing carrageenan hydrogel material for the rapid detection of OFX in meat in real time and the first discovery of impressive afterglow in MOF-based hydrogels. This study not only presents novel Ln-MOF materials and Ln-MOF-based hydrogel films for luminescent sensing of OFX, but also demonstrates color-tunable luminescent films with afterglow, which expands the application of composite luminescent materials for detection and anti-counterfeiting.

Structural characterization, chain conformation and immunomodulatory activity of a heteropolysaccharide from Inonotus hispidus.

A new polysaccharide (IHP-1aa) was isolated from the fruiting body of Inonotus hispidus by hot water extraction, ethanol precipitation and column chromatography. The molecular weight of IHP-1aa was 26.9 kDa. Structural analysis showed that IHP-1aa consisted of glucose (Glc), galactose (Gal), fucose (Fuc), mannose (Man) and contained a certain amount of 3-O-methylgalactose (3-O-Me-Gal). The structure was mainly composed of →6)-α/ß-D-Glcp-(1→, →6)-α-D-Galp-(1→, →6)-(3-O-Me)-α-D-Galp-(1→, →6)-α-D-Manp-(1 â†’ and →2, 6)-α-D-Galp-(1 â†’ as the main chain. Branched at O-2 with single ß-L-Fucp-(1 â†’ 6)-α-D-Galp-(1 â†’ 6)-α-D-Glcp-(1 â†’ as major the side chain. The results of SEM, XRD and AFM combined with Congo red indicated that IHP-1aa may be amorphous granular chain conformation. In addition, IHP-1aa stimulated macrophage function and improved phagocytic ability of RAW264.7, as well as promoted the secretion of NO, TNF-α and IL-6. IHP-1aa, a 3-O-methylgalactose-containing heteropolysaccharide, was isolated for the first time from the I. hispidus, which may be used as a potential immunomodulator in functional foods.

Unveiling the effect of molecular weight of vanillic acid grafted chitosan hydrogel films on physical, antioxidant, and antimicrobial properties for application in food packaging.

Till now, a wide range of chitosan (CHS)-based food packaging films have been developed. Yet, the role of molecular weight (MW), which is an important physical property of CHS, in determining the physicochemical and biochemical properties of vanillic acid (VA)-grafted CHS hydrogel films synthesized using CHS with different MWs has not been investigated until now. Three kinds of CHS including low, medium, and high MWs were grafted separately with VA through a carbodiimide mediated coupling reaction. No significant difference in water resistance properties was observed with increasing MW of CHS, in contrast to obvious decrease in light transmittance and opacity. The VA-g-CHS hydrogel films exhibited significantly improved light blocking capacity. A significant improvement in antioxidant (~6-fold) and antimicrobial (~1.2-fold) activity was observed after grafting with VA. In contrast, the free radical scavenging and antimicrobial activity decreased with increasing MW of CHS. Most importantly, VA-g-CHS hydrogel films could maintain the freshness of cherry tomatoes for up to 10 days at ~25 °C. However, no significant difference was observed depending on the MW value of CHS. This pioneering work is of great importance in guiding the selection of MW of CHS biomacromolecule to design hydrogel films with desired physicochemical and biochemical properties.

An elaborate biomolecular keypad lock based on electrochromism of viologen derivatives and bioelectrocatalytic reduction of CO2 at supramolecular hydrogel film electrodes.

Herein, the short peptide N-fluorenemethoxycarbonyl diphenylalanine (Fmoc-FF) was used to immobilize both diallyl viologen (DAV) and the enzyme formate dehydrogenase (FDH) to form Fmoc-FF/DAV/FDH supramolecular hydrogel films on an electrode surface by a simple solvent-controlled self-assembly method. The DAV component in the films exhibited multiple properties, such as electrochromism and electrofluorochromism, and acted as an electrochemical mediator. A high efficiency of bioelectrocatalytic reduction of CO2 to formate (HCOO-) was obtained by the natural FDH enzyme and the artificial coenzyme factor DAV both immobilized in the same films. The supramolecular hydrogel films with CO2, voltage and light as stimulating factors and current, fluorescence and UV-vis extinction as responsive signals, were further applied for the construction of complex biomolecular logic systems and information encryption. A 3-input/7-output biomolecular logic gate and several logic devices, including an encoder/decoder, a parity checker, and a keypad lock, were constructed. Especially, the biomolecular keypad lock with 3 types of signals as outputs significantly enhanced the security level of information encryption. In this work, a supramolecular self-assembly interface was simply fabricated with complex biomolecular computational functions using immobilized molecules as the computational core, greatly broadening the application range of supramolecular hydrogel films and providing an idea for new designs of bioinformation encryption through the use of a simple film system.

The cell walls of different Chara species are characterized by branched galactans rich in 3-O-methylgalactose and absence of AGPs.

Streptophyte algae are the closest relatives to land plants; their latest common ancestor performed the most drastic adaptation in plant evolution around 500 million years ago: the conquest of land. Besides other adaptations, this step required changes in cell wall composition. Current knowledge on the cell walls of streptophyte algae and especially on the presence of arabinogalactan-proteins (AGPs), important signalling molecules in all land plants, is limited. To get deeper insights into the cell walls of streptophyte algae, especially in Charophyceae, we performed sequential cell wall extractions of four Chara species. The three species Chara globularis, Chara subspinosa and Chara tomentosa revealed comparable cell wall compositions, with pectins, xylans and xyloglucans, whereas Chara aspera stood out with higher amounts of uronic acids in the pectic fractions and lack of reactivity with antibodies binding to xylan- and xyloglucan epitopes. Search for AGPs in the four Chara species and in Nitellopsis obtusa revealed the presence of galactans with pyranosidic galactose in 1,3-, 1,6- and 1,3,6-linkage, which are typical galactan motifs in land plant AGPs. A unique feature of these branched galactans was high portions of 3-O-methylgalactose. Only Nitellopsis contained substantial amounts of arabinose A bioinformatic search for prolyl-4-hydroxylases, involved in the biosynthesis of AGPs, revealed one possible functional sequence in the genome of Chara braunii, but no hydroxyproline could be detected in the four Chara species or in Nitellopsis obtusa. We conclude that AGPs that is typical for land plants are absent, at least in these members of the Charophyceae.

Exo I signal amplification of a DNA hydrogel film combined with capillary self-driven action for EpCAM detection.

Target-responsive aptamer hydrogels are increasingly used in the field of analytical sensing with different morphologies developed by various strategies. Herein, we developed a DNA hydrogel film combined with capillary self-driven action for the specific detection of the tumor marker EpCAM and further introduced Exo I for signal amplification. EpCAM aptamer was used as a crosslinking agent to construct the DNA hydrogel film. When EpCAM was present, it competed for binding with the EpCAM aptamer, resulting in a permeability change of the DNA hydrogel film attached to one end of the capillary, and leading to different solution flow rates through the capillaries that can be utilized for the quantitative detection of EpCAM. This method did not require any instrument and was easy to use. The distance the solution travelled through the capillary was quantified as the concentration of EpCAM, and only a small amount of DNA hydrogel was required for each detection. The detection limit of EpCAM was as low as 0.018 ng mL-1, while offering the advantages of good stability and specificity, and showing great potential in point-of-care testing.