Introduction to Bionanocomposites.

Sabu Thomas, Maya John and Aji Mathew introduce the Nanoscale Advances themed issue on Bionanocomposites.

Three-Dimensional Printing of Cellulose/Covalent Organic Frameworks (CelloCOFs) for CO2 Adsorption and Water Treatment.

The development of porous organic polymers, specifically covalent organic frameworks (COFs), has facilitated the advancement of numerous applications. Nevertheless, the limited availability of COFs solely in powder form imposes constraints on their potential applications. Furthermore, it is worth noting that COFs tend to undergo aggregation, leading to a decrease in the number of active sites available within the material. This work presents a comprehensive methodology for the transformation of a COF into three-dimensional (3D) scaffolds using the technique of 3D printing. As part of the 3D printing process, a composite material called CelloCOF was created by combining cellulose nanofibrils (CNF), sodium alginate, and COF materials (i.e., COF-1 and COF-2). The intervention successfully mitigated the agglomeration of the COF nanoparticles, resulting in the creation of abundant active sites that can be effectively utilized for adsorption purposes. The method of 3D printing can be described as a simple and basic procedure that can be adapted to accommodate hierarchical porous materials with distinct micro- and macropore regimes. This technology demonstrates versatility in its use across a range of COF materials. The adsorption capacities of 3D CelloCOF materials were evaluated for three different adsorbates: carbon dioxide (CO2), heavy metal ions, and perfluorooctanesulfonic acid (PFOS). The results showed that the materials exhibited adsorption capabilities of 19.9, 7.4-34, and 118.5-410.8 mg/g for CO2, PFOS, and heavy metals, respectively. The adsorption properties of the material were found to be outstanding, exhibiting a high degree of recyclability and exceptional selectivity. Based on our research findings, it is conceivable that the utilization of custom-designed composites based on COFs could present new opportunities in the realm of water and air purification.

In situ modified nanocellulose/alginate hydrogel composite beads for purifying mining effluents.

Biobased adsorbents and membranes offer advantages related to resource efficiency, safety, and fast kinetics but have challenges related to their reusability and water flux. Nanocellulose/alginate composite hydrogel beads were successfully prepared with a diameter of about 3-4 mm and porosity as high as 99%. The beads were further modified with in situ TEMPO-mediated oxidation to functionalize the hydroxyl groups of cellulose and facilitate the removal of cationic pollutants from aqueous samples at low pressure, driven by electrostatic interactions. The increased number of carboxyl groups in the bead matrix improved the removal efficiency of the adsorbent without compromising the water throughput rate; being as high as 17 000 L h-1 m-2 bar-1. The absorptivity of the beads was evaluated with UV-vis for the removal of the dye Methylene Blue (91% removal) from spiked water and energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) elemental analyses for the removal of Cd2+ from industrial mining effluents. The modified beads showed a 3-fold increase in ion adsorption and pose as excellent candidates for the manufacturing of three-dimensional (3-D) column filters for large-volume, high flux water treatment under atmospheric pressure.

3D printing of cellulose/leaf-like zeolitic imidazolate frameworks (CelloZIF-L) for adsorption of carbon dioxide (CO2) and heavy metal ions.

Metal-organic frameworks (MOFs) have advanced several technologies. However, it is difficult to market MOFs without processing them into a commercialized structure, causing an unnecessary delay in the material's use. Herein, three-dimensional (3D) printing of cellulose/leaf-like zeolitic imidazolate frameworks (ZIF-L), denoted as CelloZIF-L, is reported via direct ink writing (DIW, robocasting). Formulating CelloZIF-L into 3D objects can dramatically affect the material's properties and, consequently, its adsorption efficiency. The 3D printing process of CelloZIF-L is simple and can be applied via direct printing into a solution of calcium chloride. The synthesis procedure enables the formation of CelloZIF-L with a ZIF content of 84%. 3D printing enables the integration of macroscopic assembly with microscopic properties, i.e., the formation of the hierarchical structure of CelloZIF-L with different shapes, such as cubes and filaments, with 84% loading of ZIF-L. The materials adsorb carbon dioxide (CO2) and heavy metals. 3D CelloZIF-L exhibited a CO2 adsorption capacity of 0.64-1.15 mmol g-1 at 1 bar (0 °C). The materials showed Cu2+ adsorption capacities of 389.8 ± 14-554.8 ± 15 mg g-1. They displayed selectivities of 86.8%, 6.7%, 2.4%, 0.93%, 0.61%, and 0.19% toward Fe3+, Al3+, Co2+, Cu2+, Na+, and Ca2+, respectively. The simple 3D printing procedure and the high adsorption efficiencies reveal the promising potential of our materials for industrial applications.

Effect of decoration route on the nanomechanical, adhesive, and force response of nanocelluloses-An in situ force spectroscopy study.

Although cellulose derivatives are widely applied in high-tech materials, the relation between their force responses and their surface chemical properties in a biological environment as a function of pH is unknown. Here, interaction forces of surface modified cellulose nanocrystals (CNCs), lignin residual cellulose nanocrystals (LCNCs), and 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose nanofibres (TCNFs) with OSO3-, COO- and lignin chemical groups were measured using in situ peak force quantitative nanomechanical mapping and force spectroscopy in salt solution at two pH values. We found that the forces acting between the tip and CNC or LCNC are steric dominated showing long range and slow decay as a result of their low surface charge density. High Mw lignin contributed to the increased repulsion range for LCNCs compared to CNCs. The repulsion measured for TCNFs at the very short range was electrostatic force dominating showing a steep decay attributed to its high surface charge density. In the case of TCNFs, electrostatic double layer force was also evidenced by the attraction measured at secondary minima. In all the three cases the electro steric interactions are pH dependent. Dissipation maps verified that the force behavior for each material was related to structural conformation restriction of the groups at compression. The slow decayed repulsion of CNCs or LCNCs is related to a weak restriction of conformational change due to small surface groups or high molecular weight bound polymers forming flat layers, whereas the steep repulsion of TCNFs is attributed to a strong conformation restriction of carboxylic groups occurred by forming extended structure. Our results suggest that the force responses of the materials were dominated by surface charges and structural differences. TCNFs showed superior nanomechanical and repulsion properties over CNCs or LCNCs at neutral pH.

The Design of 3D-Printed Polylactic Acid-Bioglass Composite Scaffold: A Potential Implant Material for Bone Tissue Engineering.

Bio-based and patient-specific three-dimensional (3D) scaffolds can present next generation strategies for bone tissue engineering (BTE) to treat critical bone size defects. In the present study, a composite filament of poly lactic acid (PLA) and 45S5 bioglass (BG) were used to 3D print scaffolds intended for bone tissue regeneration. The thermally induced phase separation (TIPS) technique was used to produce composite spheres that were extruded into a continuous filament to 3D print a variety of composite scaffolds. These scaffolds were analyzed for their macro- and microstructures, mechanical properties, in vitro cytotoxicity and in vivo biocompatibility. The results show that the BG particles were homogeneously distributed within the PLA matrix and contributed to an 80% increase in the mechanical strength of the scaffolds. The in vitro cytotoxicity analysis of PLA-BG scaffolds using L929 mouse fibroblast cells confirmed their biocompatibility. During the in vivo studies, the population of the cells showed an elevated level of macrophages and active fibroblasts that are involved in collagen extracellular matrix synthesis. This study demonstrates successful processing of PLA-BG 3D-printed composite scaffolds and their potential as an implant material with a tunable pore structure and mechanical properties for regenerative bone tissue engineering.

Plant biomechanics and resilience to environmental changes are controlled by specific lignin chemistries in each vascular cell type and morphotype.

The biopolymer lignin is deposited in the cell walls of vascular cells and is essential for long-distance water conduction and structural support in plants. Different vascular cell types contain distinct and conserved lignin chemistries, each with specific aromatic and aliphatic substitutions. Yet, the biological role of this conserved and specific lignin chemistry in each cell type remains unclear. Here, we investigated the roles of this lignin biochemical specificity for cellular functions by producing single cell analyses for three cell morphotypes of tracheary elements, which all allow sap conduction but differ in their morphology. We determined that specific lignin chemistries accumulate in each cell type. Moreover, lignin accumulated dynamically, increasing in quantity and changing in composition, to alter the cell wall biomechanics during cell maturation. For similar aromatic substitutions, residues with alcohol aliphatic functions increased stiffness whereas aldehydes increased flexibility of the cell wall. Modifying this lignin biochemical specificity and the sequence of its formation impaired the cell wall biomechanics of each morphotype and consequently hindered sap conduction and drought recovery. Together, our results demonstrate that each sap-conducting vascular cell type distinctly controls their lignin biochemistry to adjust their biomechanics and hydraulic properties to face developmental and environmental constraints.

Cellulose-Based Nanomaterials Advance Biomedicine: A Review.

There are various biomaterials, but none fulfills all requirements. Cellulose biopolymers have advanced biomedicine to satisfy high market demand and circumvent many ecological concerns. This review aims to present an overview of cellulose knowledge and technical biomedical applications such as antibacterial agents, antifouling, wound healing, drug delivery, tissue engineering, and bone regeneration. It includes an extensive bibliography of recent research findings from fundamental and applied investigations. Cellulose-based materials are tailorable to obtain suitable chemical, mechanical, and physical properties required for biomedical applications. The chemical structure of cellulose allows modifications and simple conjugation with several materials, including nanoparticles, without tedious efforts. They render the applications cheap, biocompatible, biodegradable, and easy to shape and process.

A New Family of Renewable Thermosets: Kraft Lignin Poly-adipates.

Thermosetting polymeric materials have advantageous properties and are therefore used in numerous applications. In this study, it was hypothesized and ultimately shown that thermosets could be derived from comparably sustainable sub-components. A two-step procedure to produce a thermoset comprising of Kraft lignin (KL) and the cross-linker adipic acid (AdA) was developed. The cross-linking was activated by means of an acetylating agent comprising isopropenyl acetate (IPA) to form a cross-linking mixture (CLM). The cross-linking was confirmed by FTIR and solid-state NMR spectroscopy, and the esterification reactions were further studied using model compounds. When the KL lignin was mixed with the CLM, partial esterification occurred to yield a homogeneous viscous liquid that could easily be poured into a mold, as the first step in the procedure. Without any additions, the mold was heated and the material transformed into a thermoset by reaction of the two carboxylic acid-derivatives of AdA and KL in the second step.

In-situ growth of zeolitic imidazolate frameworks into a cellulosic filter paper for the reduction of 4-nitrophenol.

Whatman® cellulosic filter paper was used as a substrate for the synthesis of two zeolitic imidazolate frameworks (ZIFs); ZIF-8 and ZIF-67 with and without 2,2,6,6-tetramethyl-1-piperidine oxoammonium salt (TEMPO)-oxidized cellulose nanofibril (TOCNF). All synthesis procedures take place at room temperature via a one-pot procedure. The synthesis steps were followed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transforms infrared (FT-IR). Data indicated the formation of metal oxide that converted to a pure phase of ZIFs after the addition of the organic linker i.e. 2-methyl imidazole (Hmim). The materials were characterized using XRD, FT-IR, SEM, energy dispersive X-ray (EDX), nitrogen adsorption-desorption isotherms, and X-ray photoelectron microscope (XPS). Data analysis confirms the synthesis of ZIFs into Whatman® filter paper. The materials were used for the reduction of pollutants such as 4-nitrophenol (4-NP) compound to 4-aminophenol (4-AP). The materials exhibit high potential for water treatment and may open new exploration for hybrid materials consisting of cellulose and ZIFs.

A Rare Case of Pediatric Central Venous Catheter-Related Bloodstream Infection With Kocuria Varians.

Cases of central line blood infections caused by Kocuria spp. are limited in the literature. Most of those infections have been detected in hospitalized patients with severe underlying disease or those with implanted catheters or with suppressed immunity. They are usually non-pathogenic in humans, but few cases of opportunistic infections in adult and pediatric populations have been reported. They can be serious in certain occasions. So treating physicians should not underestimate or ignore the significance of the infection with these bacteria. We report a rare case of central venous catheter (CVC) infection associated with Kocuria varians, which was successfully treated with CVC salvage.

Water Filtration Membranes Based on Non-Woven Cellulose Fabrics: Effect of Nanopolysaccharide Coatings on Selective Particle Rejection, Antifouling, and Antibacterial Properties.

This article presents a comparative study of the surface characteristics and water purification performance of commercially available cellulose nonwoven fabrics modified, via cast coating, with different nano-dimensioned bio-based carbohydrate polymers, viz. cellulose nanocrystals (CNC), TEMPO-oxidized cellulose nanofibers (T-CNF), and chitin nanocrystals (ChNC). The surface-modified nonwoven fabrics showed an improvement in wettability, surface charge modification, and a slight decrease of maximum pore size. The modification improved the water permeance in most of the cases, enhanced the particle separation performance in a wide range of sizes, upgraded the mechanical properties in dry conditions, and showed abiotic antifouling capability against proteins. In addition, T-CNF and ChNC coatings proved to be harmful to the bacteria colonizing on the membranes. This simple surface impregnation approach based on green nanotechnology resulted in highly efficient and fully bio-based high-flux water filtration membranes based on commercially available nonwoven fabrics, with distinct performance for particle rejection, antifouling and antibacterial properties.

Isolation and modification of nano-scale cellulose from organosolv-treated birch through the synergistic activity of LPMO and endoglucanases.

Nanocellulose isolation from lignocellulose is a tedious and expensive process with high energy and harsh chemical requirements, primarily due to the recalcitrance of the substrate, which otherwise would have been cost-effective due to its abundance. Replacing the chemical steps with biocatalytic processes offers opportunities to solve this bottleneck to a certain extent due to the enzymes substrate specificity and mild reaction chemistry. In this work, we demonstrate the isolation of sulphate-free nanocellulose from organosolv pretreated birch biomass using different glycosyl-hydrolases, along with accessory oxidative enzymes including a lytic polysaccharide monooxygenase (LPMO). The suggested process produced colloidal nanocellulose suspensions (ζ-potential -19.4 mV) with particles of 7-20 nm diameter, high carboxylate content and improved thermostability (To = 301 °C, Tmax = 337 °C). Nanocelluloses were subjected to post-modification using LPMOs of different regioselectivity. The sample from chemical route was the least favorable for LPMO to enhance the carboxylate content, while that from the C1-specific LPMO treatment showed the highest increase in carboxylate content.

Safety and Cost-Effectiveness of Interscalene Brachial Plexus Block With Sedation in Reverse Total Shoulder Replacement.

Aims To investigate the safety and cost-effectiveness of interscalene brachial plexus block/regional anaesthesia (ISB-RA) in patients undergoing reverse total shoulder replacement. Patients and methods This retrospective study included 15 patients with symptomatic rotator cuff arthropathy who underwent reverse total shoulder arthroplasty (rTSA) under ISB-RA without general anaesthesia in the beach chair position from 2010 to 2018. The mean patient age was 77 years (range 59-82 years). Patients had associated medical comorbidities: American Society of Anesthesiologists (ASA) grade 2-4. Assessed parameters were: duration of anaesthesia, intra-operative systolic blood pressure variation, sedation and vasopressor use, duration of post-operative recovery, recovery scores, length of stay, and complications. A robust cost analysis was also performed. Results The mean (range) duration of anaesthesia was 38.66 (20-60) min. Maximum and minimum intra-operative systolic blood pressure ranges were 130-210 and 75-145 mmHg, respectively (mean [range] drop, 74.13 [33-125] mmHg). Mean (range) propofol dose was 1.74 (1-3.0) mg/kg/h. The Median (interquartile range) post-operative recovery time was 30 (20-50) min. The mean (range) postoperative recovery score (local scale, range 5-28 where lower values are superior) was 5.2 (5-8). The mean (range) length of stay was 8 (1-20 days); the two included patients with ASA grade 2 were both discharged within 24 hours. One patient with predisposing history developed pneumonia; however, there were no complications related to ISB-RA. The mean (range) cost per patient was £101.36 (£59.80-£132.20). Conclusions Our data demonstrate that rTSA under ISB-RA is safe, comfortable, and cost-effective. Notably, patients with ASA grade 2 who underwent rTSA under ISB-RA had a reduced length of stay and were discharged within 24 hours. Clinical relevance  rTSA under ISB-RA is potentially a safe, cost-effective, and viable alternative for patients with multiple comorbidities.

All-cellulose functional membranes for water treatment: Adsorption of metal ions and catalytic decolorization of dyes.

In this study, we present a facile, one-step method for the manufacturing of all-cellulose, layered membranes containing cellulose nanocrystals (CNC), TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidized cellulose nanofibers (TO-CNF), or zwitterionic polymer grafted cellulose nanocrystals (CNC-g-PCysMA) as functional entities in combination with cellulose fibers and commercial grade microfibrillated cellulose. The presence of active sites such as hydroxyl, carbonyl, thioethers, and amines, gave the membranes high adsorption capacities for the metal ions Au (III), Co (II), and Fe (III), as well as the cationic organic dye methylene blue (MB). Furthermore, the membranes served as excellent metal-free catalysts for the decolorization of dyes via hydrogenation. A 3-fold increase of the hydrogenation efficiency for cationic dyes such as rhodamine B (RhB) and methylene blue was obtained in the presence of membranes compared to NaBH4 alone. Water-based processing, the abundance of the component materials, and the multifunctional characteristics of the membranes ensure their potential as excellent candidates for water purification systems.

A Rare Cystic Fibrosis Transmembrane Conductance Regulator (CFTR) Mutation Associated With Typical Cystic Fibrosis in an Arab Child.

Cystic fibrosis (CF) is a progressive genetic disorder, inherited by the autosomal recessive mode of inheritance and more frequently seen in the Caucasian population with a carrier rate of 1:29 in Caucasian-Americans. Over 1800 cystic fibrosis transmembrane conductance regulator (CFTR) gene mutations have been identified so far and the delta F 508 del mutation is the most common mutation. Gene sequencing and deletion/duplication analysis can detect mutations in 99% of people with a clinical diagnosis of CF. However, diagnostic testing can be challenging, as screening tests may be inconclusive and the routine gene mutation panel analysis may be negative due to some rare or undocumented mutations. We report a case of a two-year-old boy of Palestinian-Lebanese descent, with a history of raised immunoreactive trypsin test (IRT), positive sweat test, and phenotypical CF manifestations, found to have rare CF apparent homozygous CFTR (NM_000492.3) variant, c.3623del (p.Gly1208AlafsX3). In our case, genetic testing for 139 mutations done in Germany could not identify any defect. Only CFTR gene sequencing identified the above pathogenic variant. This reinforces the practice for a broad range of CFTR mutation analyses to detect ethnic-specific rare variants. This is the second case of this particular genetic mutation identified and the first to be reported in detail.

Charged ultrafiltration membranes based on TEMPO-oxidized cellulose nanofibrils/poly(vinyl alcohol) antifouling coating.

This study reports the potential of TEMPO-oxidized cellulose nanofibrils (T-CNF)/poly(vinyl alcohol) (PVA) coatings to develop functionalized membranes in the ultrafiltration regime with outstanding antifouling performance and dimensional/pH stability. PVA acts as an anchoring phase interacting with the polyethersulfone (PES) substrate and stabilizing for the hygroscopic T-CNF via crosslinking. The T-CNF/PVA coated PES membranes showed a nano-textured surface, a change in the surface charge, and improved mechanical properties compared to the original PES substrate. A low reduction (4%) in permeance was observed for the coated membranes, attributable to the nanometric coating thickness, surface charge, and hydrophilic nature of the coated layer. The coated membranes exhibited charge specific adsorption driven by electrostatic interaction combined with rejection due to size exclusion (MWCO 530 kDa that correspond to a size of ∼35-40 nm). Furthermore, a significant reduction in organic fouling and biofouling was found for T-CNF/PVA coated membranes when exposed to BSA and E. coli. The results demonstrate the potential of simple modifications using nanocellulose to manipulate the pore structure and surface chemistry of commercially available membranes without compromising on permeability and mechanical stability.

3D-printed monolithic biofilters based on a polylactic acid (PLA) - hydroxyapatite (HAp) composite for heavy metal removal from an aqueous medium.

High flux, monolithic water purification filters based on polylactic acid (PLA) functionalised with fish scale extracted hydroxyapatite (HAp) were prepared by solvent-assisted blending and thermally induced phase separation (TIPS), followed by twin-screw extrusion into filaments and processed via three-dimensional (3D) printing. The printed filters with consistent pore geometry and channel interconnectivity as well as homogenous distribution of HAp in the PLA matrix showed adsorption capabilities towards heavy metals i.e. cadmium (Cd) and lead (Pb) with maximum adsorption capacity of 112.1 mg gHAp -1 and 360.5 mg gHAp -1 for the metal salt of Pb and Cd, respectively. The adsorption was found to be driven by a combination of ion exchange, dissolution and precipitation on HAp and surface complexation.

Holistic Valorization of Hemp through Reductive Catalytic Fractionation.

Despite the increased use of hemp fiber, negligible attention has been given to upgrade the hemp hurd, which constitutes up to 70 wt % of the hemp stalk and is currently considered a low-value byproduct. In this work, valorization of hemp hurd was performed by reductive catalytic fractionation (RCF) in the presence of a metal catalyst. We found an unexpectedly high yield of monophenolic compounds (38.3 wt %) corresponding to above 95% of the theoretical maximum yield. The high yield is explained by both a thin cell wall and high S-lignin content. In addition, organosolv pulping was performed to generate a pulp that was bleached to produce dissolving-grade pulp suitable for textile fiber production (viscosity, 898 mL/g; ISO-brightness, 90.2%) and nanocellulose. Thus, we have demonstrated a novel value chain from a low-value side stream of hemp fiber manufacture that has the potential to increase textile fiber production with 100% yield and also give bio-oil for green chemicals.

CelluPhot: Hybrid Cellulose-Bismuth Oxybromide Membrane for Pollutant Removal.

The simultaneous removal of organic and inorganic pollutants from wastewater is a complex challenge and requires usually several sequential processes. Here, we demonstrate the fabrication of a hybrid material that can fulfill both tasks: (i) the adsorption of metal ions due to the negative surface charge, and (ii) photocatalytic decomposition of organic compounds. The bioinorganic hybrid membrane consists of cellulose fibers to ensure mechanical stability and of Bi4O5Br2/BiOBr nanosheets. The composite is synthesized at low temperature of 115 °C directly on the cellulose membrane (CM) in order to maintain the carboxylic and hydroxyl groups on the surface that are responsible for the adsorption of metal ions. The composite can adsorb both Co(II) and Ni(II) ions and the kinetic study confirmed a good agreement of experimental data with the pseudo-second-order equation kinetic model. CM/Bi4O5Br2/BiOBr showed higher affinity to Co(II) ions than to Ni(II) ions from diluted aqueous solutions. The bioinorganic composite demonstrates a synergistic effect in the photocatalytic degradation of rhodamine B (RhB) by exceeding the removal efficiency of single components. The fabrication of the biologic-inorganic interface was confirmed by various analytical techniques including scanning electron microscopy (SEM), scanning transmission electron microscopy with energy dispersive X-ray spectroscopy (STEM EDX) mapping, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The presented approach for controlled formation of the bioinorganic interface between natural material (cellulose) and nanoscopic inorganic materials of tailored morphology (Bi-O-Br system) enables the significant enhancement of materials functionality.