Nanofilamentous Virus-Based Dynamic Hydrogels with Tunable Internal Structures, Injectability, Self-Healing, and Sugar Responsiveness at Physiological pH.

With expanding applications of hydrogels in diverse fields ranging from biomaterials to sensors, actuators, and soft robotics, there is an urgent need to endow one single gel with multiple physicochemical properties, such as stimuli-responsiveness, injectability, self-healing, and tunable internal structures. However, it is challenging to simultaneously incorporate these highly sought-after properties into one single gel. Herein, a conceptual hydrogel system with all of these properties is presented via combining bioconjugate chemistry, filamentous viruses, and dynamic covalent bonds. Nanofilamentous bioconjugates with diol affinity were prepared by coupling a tailor-synthesized low-p Ka phenylboronic acid (PBA) derivative to a well-defined green nanofiber the M13 virus with a high aspect ratio (PBA-M13). Dynamic hydrogels with tunable mechanical strength were prepared by using multiple diol-containing agents such as poly(vinyl alcohol) to cross-link such PBA-M13 via the classic boronic-diol dynamic bonds. The as-prepared hydrogels exhibit excellent injectability and self-healing behaviors as well as easy chemical accessibility of the PBA moieties on the virus backbone inside the gel matrix. Ordered internal structures were imparted into virus-based hydrogels by simple shear-induced alignment of the virus nanofibers. Furthermore, unique hydrogels with chiral internal structures were fabricated through in situ gelation induced by diffusion of diol-containing molecules to fix the chiral liquid crystal phase of the PBA-M13 virus. Sugar responsiveness of this gel leads to a glucose-regulated release behavior of payloads such as insulin. All of these properties have been implemented at physiological pH, which will facilitate future applications of these hydrogels as biomaterials.

Tracking and imaging nano-plastics in fresh plant using cryogenic laser ablation inductively coupled plasma mass spectrometry.

Tracking and imaging of nano-plastics are extremely challenging, especially in fresh biological samples. Here, we propose a new strategy in which polystyrene (PS) was doped with the europium chelate Eu (DBM)3bpy to quantify, track, and in situ image nano-plastics in fresh cucumber based on inherent metals using cryogenic laser ablation inductively coupled plasma mass spectrometry (cryo-LA-ICP-MS). The cryogenic conditions provide a stable condition for imaging fresh cucumber, suppressing the evaporation of water in fresh plants, and maintaining the original structure of plants with respect to room temperature imaging in LA-ICP-MS. The plants were cultivated in two types of nano-plastics solutions with low (50 mg/L) and high (200 mg/L) concentrations for 9 days. The results showed that nano-plastics mainly enrich the roots and have negative effects, which decrease the trace elements of Zn, Mn, and Cu in cucumber. Smaller PS particles are able to penetrate the plant more easily and inflict serious damage. Novel imaging method provides a novel insight into the tracking and imaging of nano-plastics in fresh plant samples. The results illustrated that nano-plastics deposition on plants has the potential to have direct ecological effects as well as consequences for potential health.

Preparation of doxycycline-imprinted magnetic microspheres by inverse-emulsion suspension polymerization for magnetic dispersion extraction of tetracyclines from milk samples.

A magnetic dispersion extraction method was developed based on a molecularly imprinted magnetic microsphere (MIMM) for the selective clean-up and enrichment of tetracycline antibiotics from milk samples. The MIMMs were prepared by inverse-emulsion suspension polymerization, using doxycycline, trimethylolpropane trimethacrylate, acrylamide, methacrylic acid, and surface-modified Fe3 O4 as a template molecule, crosslinker, functional monomer, and magnetic component, respectively. Synthesis and extraction conditions were optimized for obtaining excellent affinity and high selectivity. The magnetism, covering amount, and selectivity of the magnetic microspheres were characterized by a vibrating sample magnetometer, thermogravimetric analysis, and a competitive recognition experiment. The MIMMs were applied to separate tetracycline antibiotics from milk samples by magnetic dispersion extraction, and an enrichment factor of 9.28 and a good sample clean-up were obtained. The average recoveries of four tetracycline antibiotics were obtained in the range of 74.5-93.8% with a precision of 1.2-5.2%. The LODs and LOQs of the proposed method were in the range of 7.4-19.4 and 24.7-64.7 µg/kg, respectively. The results indicated that magnetic dispersion extraction using MIMMs is a powerful tool for food-sample pretreatment with high selectivity and a simplified procedure.

Adsorption equilibria and kinetics for the adsorption of p-nitrophenol on a phenoxy groups modified hypercrosslinked polystyrene resin.

Adsorption equilibria and kinetics of p-nitrophenol adsorbed on HJ-01 were investigated in this study. The result indicated that phenoxy groups were uploaded on the skeleton of HJ-01 successfully, the Friedel-Crafts reaction brought on prodigious changes for the Brunauer-Emmett-Teller (BET) specific surface area and pore structure while the nucleophilic substitution reaction had few effects. The adsorption experiments revealed that the acidic solution was suitable for p-nitrophenol adsorption, the adsorption isotherms could be characterized by the Freundlich isotherm equation and the adsorption thermodynamic parameters were all negative, the adsorption kinetic curves obeyed the pseudo-second-order rate equation.

Polysaccharide-based biopolymer hydrogels for heavy metal detection and adsorption.

BACKGROUND: With rapid development in agriculture and industry, water polluted with heavy metallic ions has come to be a serious problem. Adsorption-based methods are simple, efficient, and broadly used to eliminate heavy metals. Conventional adsorption materials have the problems of secondary environmental contamination. Hydrogels are considered effective adsorbents, and those prepared from biopolymers are biocompatible, biodegradable, non-toxic, safe to handle, and increasingly used to adsorb heavy metal ions. AIM OF REVIEW: The natural origin and easy degradability of biopolymer hydrogels make them potential for development in environmental remediation. Its water absorption capacity enables it to efficiently adsorb various pollutants in the aqueous environment, and its internal pore channels increase the specific surface area for adsorption, which can provide abundant active binding sites for heavy metal ions through chemical modification. KEY SCIENTIFIC CONCEPT OF REVIEW: As the most representative of biopolymer hydrogels, polysaccharide-based hydrogels are diverse, physically and chemically stable, and can undergo complex chemical modifications to enhance their performance, thus exhibiting superior ability to remove contaminants. This review summarizes the preparation methods of hydrogels, followed by a discussion of the main categories and applications of polysaccharide-based biopolymer hydrogels.

Acquiring structural and mechanical information of a fibrous network through deep learning.

Fibrous networks play an essential role in the structure and properties of a variety of biological and engineered materials, such as cytoskeletons, protein filament-based hydrogels, and entangled or crosslinked polymer chains. Therefore, insight into the structural features of these fibrous networks and their constituent filaments is critical for discovering the structure-property-function relationships of these material systems. In this paper, a fibrous network-deep learning system (FN-DLS) is established to extract fibrous network structure information from atomic force microscopy images. FN-DLS accurately assesses the structural and mechanical characteristics of fibrous networks, such as contour length, number of nodes, persistence length, mesh size and fractal dimension. As an open-source system, FN-DLS is expected to serve a vast community of scientists working on very diverse disciplines and pave the way for new approaches on the study of biological and synthetic polymer and filament networks found in current applied and fundamental sciences.

Europium-Pyridinedicarboxylate-Adenine Light-Up Fluorescence Nanoprobes for Selective Detection of Phosphate in Biological Fluids.

Phosphate (Pi) plays important roles in various physiological processes. Its quantification in biological fluids is highly crucial for timely warning of Pi accumulation. Herein, an europium (Eu)-based coordination polymer nanoprobe (Eu/DPA/Ade) is prepared by coordinating 2,6-pyridinedicarboxylic acid (2,6-DPA) and adenine (Ade) with Eu3+. Eu/DPA/Ade exhibits light-up fluorescence response to Pi. The strong coordinating interaction between Eu3+ and O atoms in the Pi group not only shortens the Eu3+-ligand distance to improve the energy transfer from 2,6-DPA to Eu3+ but also attenuates the fluorescence quenching from water molecules in the coordinating sphere of Eu3+. Eu/DPA/Ade produces red emission at λem 618 nm via the "antenna effect". The coligand Ade further promotes the fluorescent emission. The selective recognition of Pi within 10-60 µM is achieved with a detection limit of 4.65 µM. In addition, a certain level of Pi (100-170 µM) causes an exponential increment on the fluorescence of Eu/DPA/Ade and makes it feasible for visual estimation of Pi under irradiation by an ultraviolet lamp at 254 nm. The quantitative detection and visual estimation of Pi in human urine and saliva have been demonstrated.

Electrospun reduced graphene oxide/TiO2/poly(acrylonitrile-co-maleic acid) composite nanofibers for efficient adsorption and photocatalytic removal of malachite green and leucomalachite green.

Electrospun reduced graphene oxide/TiO2/poly(acrylonitrile-co-maleic acid) composite nanofibers (E-spun RGO/TiO2/PANCMA NFs) were fabricated using electrospinning of the dispersive solution of PANCMA, GO and TiO2 followed by post-chemical reduction. The obtained composite nanofibers were compressed in a dialyzer and then used to absorb and degrade malachite green (MG) and leucomalachite green (LMG) from aqueous solution. Compared to the E-spun TiO2/PANCMA and GO/TiO2/PANCMA NFs, the E-spun RGO/TiO2/PANCMA NFs exhibited higher adsorption capacity and photocatalytic degradation ability. Under optimized conditions, 90.6% of MG and 93.7% of LMG from 50 mL aqueous sample solution were adsorbed on the RGO/TiO2/PANMA NFs (3.0 mg fibers) in 2.0 min, and subsequent the 91.4% and 95.2% of MG and LMG adsorbed on the NFs were degradated in 60 min under UV irradiation, respectively. In addition, the E-spun RGO/TiO2/PANMA NFs exhibited good reusability and could be reused in multiple cycles of operations for adsorption and photocatalytic degradation of MG and LMG. This work demonstrated that the electrospun composite nanofibers are promising materials for removal of pollutants from environmental water samples.

A portable dual-mode sensor based on a TiO2 nanotube membrane for the evaluation of telomerase activity.

A portable dual-mode sensing platform based on a self-standing TiO2 nanotube membrane is developed for simultaneously performing both qualitative analysis by the naked eye and quantitative analysis by ionic current. This dual-mode diagnosis strategy exhibits a high performance in telomerase detection in urine specimens from patients with bladder cancer.

Protein Shell-Encapsulated Pt Clusters as Continuous O2-Supplied Biocoats for Photodynamic Therapy in Hypoxic Cancer Cells.

As a highly oxygen-dependent process, the effect of photodynamic therapy is often obstructed by the premature leakage of photosensitizers and the lack of oxygen in hypoxic cancer cells. To overcome these limitations, this study designs bovine serum albumin protein (BSA)-encapsulated Pt nanoclusters (PtBSA) as O2-supplied biocoats and further incorporates them with mesoporous silica nanospheres to develop intelligent nanoaggregates for achieving improved therapeutic outcomes against hypoxic tumors. The large number of amino groups on BSA can provide sufficient functional groups to anchor tumor targeting agents and thus enhance the selective cellular uptake efficiency. Owing to the outstanding biocompatibility features of BSA and the state-of-the-art catalytic activity of Pt nanoclusters, the nanocomposites have lower dark cytotoxicity, and O2 continuously evolves via the decomposition of H2O2 in a tumor microenvironment. Both in vivo and in vitro experiments indicate that the resulting nanocomposites can effectively relieve hypoxic conditions, specifically induce necrotic cell apoptosis, and remarkably hinder tumor growth. Our results illuminate the great potential of BSA-encapsulated Pt nanoclusters as versatile biocoats in designing intelligent nanocarriers for hypoxic-resistant photodynamic therapy.

Effects of irradiation and pH on fluorescence properties and flocculation of extracellular polymeric substances from the cyanobacterium Chroococcus minutus.

Microbial extracellular polymeric substances (EPS) may flocculate or be decomposed when environmental factors change, which significantly influences nutrient cycling and transport of heavy metals. However, little information is available on the stability of EPS in natural environments. Fluorescence and flocculation properties of EPS from Chroococcus minutus under different irradiation and pH conditions were studied. Two aromatic protein-like fluorescence peaks and one tyrosine protein-like peak were identified from the excitation-emission-matrix (EEM) fluorescence spectra of EPS. UVB (ultraviolet B) and solar irradiation increased the fluorescence intensity of all the three peaks while UVC (ultraviolet C) irradiation had little effect. EPS formed unstable flocs after exposure to UV (ultraviolet) irradiation and formed stable flocs under solar irradiation. EPS were prone to flocculation under highly acidic conditions and minimal fluorescence of peaks was observed. The fluorophores in EPS were relatively stable under neutral and alkaline conditions. These findings are helpful for understanding the behavior of EPS in aquatic environments and their role in biogeochemical cycles of the elements.

Synthesis and application of molecularly imprinted poly(methacrylic acid)-silica hybrid composite material for selective solid-phase extraction and high-performance liquid chromatography determination of oxytetracycline residues in milk.

A novel molecularly imprinted organic-inorganic hybrid composite material (MIP-HCM) was developed based on molecular imprinting technique in combination with hybrid composite synthesis and sol-gel technology for selective solid-phase extraction (SPE) of tetracyclines residues in milk. The MIP-HCM was prepared using oxytetracycline as the template, methacrylic acid as organic functional monomer, tetraethoxysilane as inorganic precursor and methacryloxypropyltrimethoxysilane as the coupling agent. Synthesis conditions are optimized by changing some factors to obtain sorbent with the controllable adsorption capacity, selectivity, hardness and toughness. Binding study demonstrated that the imprinted hybrid composites showed excellent affinity and high selectivity to oxytetracycline. An enrichment factor of 18.8 along with a good sample clean-up was obtained under the optimized SPE conditions. The average recoveries of three tetracyclines antibiotics spiked milk at 0.1, 0.2 and 0.5 mg kg⁻¹ were in the range of 80.9-104.3% with the precision of 1.5-5.0%. The limits of detection and quantitation of the proposed method were in a range of 4.8-12.7 µg kg⁻¹ and 16.0-42.3 µg kg⁻¹, respectively.