Isolation, purification, and structural elucidation of a water-soluble polysaccharide derived from Phellinus baumii Pilát mycelia.

This study involved the successful production of mycelial polysaccharides by optimizing submerged culture conditions of Phellinus baumii Pilát. Then, the investigation focused on the composition and chemical structure of the water-soluble polysaccharide from P. baumii Pilát mycelia (PBMP) by extraction and purification. Specifically, this study indicated that a water-soluble PBMP fraction 1 (PBMP1) was isolated from PBMP. Moreover, this study discovered a PBMP1 isolated from PBMP, which was found to have the monosaccharide compositions comprised of fucose (Fuc), glucose (Glc), and galactose (Gal) despite the absence of proteins. Subsequently, the composition and structure of PBMP1 were characterized using Fourier transform infrared (FT-IR) spectroscopy, periodate oxidation, Smith degradation, methylation reaction, gas chromatography-mass spectrometer (GC-MS), and Nuclear magnetic resonance (NMR). The composition and structure of PBMP1 were characterized in this study, revealing an α-glycosidic bond conformational linkage with 1,4-Glc residues and 1,6-Gal residues forming the backbone. Additionally, a highly branched hetero-polysaccharide was identified with a non-reducing terminus of Fuc containing 1,3,4- and 1,4,6-Glc branching. The findings of this study offer valuable insights and information that can be utilized by researchers, manufacturers, and other stakeholders to advance the field of P. baumii Pilát product development. Moreover, these results have significant implications for future large-scale mass production and functional applications of PBMP1 products.

Oxidized ionic polysaccharide hydrogels: Review on derived scaffolds characteristics and tissue engineering applications.

Polysaccharide-based hydrogels have gained prominence due to their non-toxicity, biocompatibility, and structural adaptability for constructing tissue engineering scaffolds. Polysaccharide crosslinking is necessary for hydrogel stability in vivo. The periodate oxidation enables the modification of native polysaccharide characteristics for wound healing and tissue engineering applications. It produces dialdehydes, which are used to crosslink biocompatible amine-containing macromolecules such as chitosan, gelatin, adipic acid dihydrazide, silk fibroin, and peptides via imine/hydrazone linkages. Crosslinked oxidized ionic polysaccharide hydrogels have been studied for wound healing, cardiac and liver tissue engineering, bone, cartilage, corneal tissue regeneration, abdominal wall repair, nucleus pulposus regeneration, and osteoarthritis. Several modified hydrogel systems have been synthesized using antibiotics and inorganic substances to improve porosity, mechanical and viscoelastic properties, desired swelling propensity, and antibacterial efficacy. Thus, the injectable hydrogels provide a host-tissue-mimetic environment with high cell adhesion and viability, making them appropriate for scarless wound healing and tissue engineering applications. This review describes the oxidation procedure for alginate, hyaluronic acid, gellan gum, pectin, xanthan gum and chitosan, as well as the characteristics of the resulting materials. Furthermore, a critical review of scientific advances in wound healing and tissue engineering applications has been provided.

Periodate oxidation-mediated nanocelluloses: Preparation, functionalization, structural design, and applications.

In recent years, the remarkable progress in nanotechnology has ignited considerable interest in investigating nanocelluloses, an environmentally friendly and sustainable nanomaterial derived from cellulosic feedstocks. Current research primarily focuses on the preparation and applications of nanocelluloses. However, to enhance the efficiency of nanofibrillation, reduce energy consumption, and expand nanocellulose applications, chemical pre-treatments of cellulose fibers have attracted substantial interest and extensive exploration. Various chemical pre-treatment methods yield nanocelluloses with diverse functional groups. Among these methods, periodate oxidation has garnered significant attention recently, due to the formation of dialdehyde cellulose derived nanocellulose, which exhibits great promise for further modification with various functional groups. This review seeks to provide a comprehensive and in-depth examination of periodate oxidation-mediated nanocelluloses (PONCs), including their preparation, functionalization, hierarchical structural design, and applications. We believe that PONCs stand as highly promising candidates for the development of novel nano-cellulosic materials.

Characteristics of Dialdehyde Cellulose Nanofibrils Derived from Cotton Linter Fibers and Wood Fibers.

Two types of cellulose nanofibrils (CNFs) were isolated from cotton linter fibers and hardwood fibers through mechanical fibrillation methods. The dialdehyde cellulose nanofibrils (DACNFs) were prepared through the periodate oxidation method, and their morphological and structural properties were investigated. The characteristics of the DACNFs during the concentration process were also explored. The AFM analysis results showed that the mean diameters of wood fiber-based CNFs and cotton fiber-based CNFs were about 52.03 nm and 69.51 nm, respectively. However, the periodate oxidation treatment process obviously reduced the nanofibril size and destroyed the crystalline region of the nanofibrils. Due to the high crystallinity of cotton fibers, the cotton fiber-based DACNFs exhibited a lower aldehyde content and suspension stability compared to the wood fiber-based DACNFs. For the concentration process of the DACNF suspension, the bound water content of the concentrated cotton fiber-based DACNFs was lowered to 0.41 g/g, which indicated that the cotton fiber-based DACNFs could have good redispersibility. Both the wood fiber-based and cotton fiber-based DACNF films showed relatively good transmittance and mechanical strength. In addition, to the cotton fiber-based DACNF films had a very low swelling ratio, and the barrier water vapor and oxygen properties of the redispersed cotton fiber-based DACNF films decreased by very little. In sum, this study has demonstrated that cotton fibers could serve as an effective alternative to wood fibers for preparing CNFs, and that cotton fiber-based DACNFs have huge application prospects in the field of packaging film materials due to their stable properties during the concentration process.

Periodate oxidation of nanofibrillated cellulose films for active packaging applications.

An alternative packaging material based on cellulose that possesses excellent barrier properties and is potentially useful for active packaging has been developed. Cellulose nanofibril was efficiently and selectively oxidized with sodium periodate generating reactive aldehyde groups. These groups formed hemiacetal and hemialdal bonds during film formation and, consequently, highly transparent, elastic and strong films were created even under moisture saturation conditions. The periodate oxidation treatment additionally decreased the polarity of the films and considerably enhanced their water barrier properties. Thus, the water contact angle of films treated for 3 and 6 h was 97° and 102°, their water drop test value was higher than in untreated film (viz., 138 and 141 min with 3 and 6 h of treatment) and their water vapour transmission rate was substantially better (3.31 and 0.78 g m-2 day-1 with 3 and 6 h, respectively). The presence of aldehyde groups facilitated immobilization of the enzyme laccase, which efficiently captures oxygen and prevents food decay as a result. Laccase-containing films oxidized 80 % of Methylene Blue colorant and retained their enzymatic activity after storage for 1 month and 12 reuse cycles, opening the door to the possible creation of a reusable packaging to replace the single-use packaging.

Towards Tailored Dialdehyde Cellulose Derivatives: A Strategy for Tuning the Glass Transition Temperature.

The derivatization of dialdehyde cellulose (DAC) has received increasing attention in the development of sustainable thermoplastics. In this study, a series of dialcohol celluloses were generated by borohydride reduction, which exhibited glass transition temperature (Tg ) values ranging from 23 to 109 °C, depending on the initial degree of oxidation (DO) of the DAC intermediate. However, the DAC derivatives did not exhibit thermoplastic behavior when the DO of the modified DAC was below 26 %. The influence of introduced side chains was highlighted by comparing DAC-based thermoplastic materials obtained by either oximation or borohydride reduction. Our results provide insights into the generation of DAC-based thermoplastics and highlight a strategy for tailoring the Tg by adjusting the DO during the periodate oxidation step and selecting appropriate substituents in subsequent modifications.

Introduction of Carbonyl Groups into Antibodies.

Antibodies and their derivatives (scFv, Fabs, etc.) represent a unique class of biomolecules that combine selectivity with the ability to target drug delivery. Currently, one of the most promising endeavors in this field is the development of molecular diagnostic tools and antibody-based therapeutic agents, including antibody-drug conjugates (ADCs). To meet this challenge, it is imperative to advance methods for modifying antibodies. A particularly promising strategy involves the introduction of carbonyl groups into the antibody that are amenable to further modification by biorthogonal reactions, namely aliphatic, aromatic, and α-oxo aldehydes, as well as aliphatic and aryl-alkyl ketones. In this review, we summarize the preparation methods and applications of site-specific antibody conjugates that are synthesized using this approach.

Oxidation Treatments Using Hydrogen Peroxide to Convert Paper-Grade Eucalyptus Kraft Pulp into Dissolving-Grade Pulp.

Converting paper-grade bleached Kraft pulp into dissolving pulp using eco-friendly chemicals on-site at the mill is a challenge for the pulp industry. In this study, two oxidation systems are evaluated: the first one is based on the use of hydrogen peroxide at various levels of alkalinity; the second one investigates the use of sodium periodate followed by hydrogen peroxide to convert aldehydes into carboxyls and enhance their hemicelluloses removal. Our results have shown that when using only peroxide, the removal of hemicelluloses was not sufficient to improve the pulp's dissolving ability. Conversely, the periodate-peroxide system proved to be more efficient. Results regarding the pulp purity, solubility, degradation (pulp viscosity and cellulose molecular mass distribution), brightness, and its potential applications were discussed.

Direct ink writing of multifunctional nanocellulose and allyl-modified gelatin biomaterial inks for the fabrication of mechanically and functionally graded constructs.

Recreating the intricate mechanical and functional gradients found in natural tissues through additive manufacturing poses significant challenges, including the need for precise control over time and space and the availability of versatile biomaterial inks. In this proof-of-concept study, we developed a new biomaterial ink for direct ink writing, allowing the creation of 3D structures with tailorable functional and mechanical gradients. Our ink formulation combined multifunctional cellulose nanofibrils (CNFs), allyl-functionalized gelatin (0.8-2.0 wt%), and polyethylene glycol dithiol (3.0-7.5 wt%). The CNF served as a rheology modifier, whereas a concentration of 1.8 w/v % in the inks was chosen for optimal printability and shape fidelity. In addition, CNFs were functionalized with azido groups, enabling the spatial distribution of functional moieties within a 3D structure. These functional groups were further modified using a spontaneous click chemistry reaction. Through additive manufacturing and a readily available static mixer, we successfully demonstrated the fabrication of mechanical gradients - ranging from 3 to 6 kPa in indentation strength - and functional gradients. Additionally, we introduced dual gradients by combining gradient printing with an anisotropic photocrosslinking step. The developed biomaterial ink opens up possibilities for printing intricate multigradient structures, resembling the complex hierarchical organization seen in living tissues.

Extracting dialdehyde cellulose nanocrystals using choline chloride/urea-based deep eutectic solvents: A comparative study in NaIO4 pre-oxidation and synchronous oxidation.

Dialdehyde cellulose nanocrystals (DCNC) are defined as C2 and C3 aldehyde nanocellulose, which can be used as raw materials for nanocellulose derivatization, owing to the high activity of aldehyde groups. Herein, a comparative study in NaIO4 pre-oxidation and synchronous oxidation is investigated for DCNC extraction via choline chloride (ChCl)/urea-based deep eutectic solvent (DES). Ring-liked DCNC with an average particle size of 118 ± 11 nm, a yield of 49.25 %, an aldehyde group content of 6.29 mmol/g, a crystallinity of 69 %, and rod-liked DCNC with an average particle size of 109 ± 9 nm, a yield of 39.40 %, an aldehyde group content of 3.14 mmol/g, a crystallinity of 75 % can be extracted via optimized DES treatment combined with pre-oxidation and synchronous oxidation, respectively. In addition, the average particle size, size distribution, and aldehyde group content of DCNC were involved. TEM, FTIR, XRD, and TGA results reveal the variation of microstructure, chemical structure, crystalline structure, and thermostability of two kinds of DCNC during extraction even though the obtained DCNC exhibiting different micromorphology, pre-oxidation, or synchronous oxidation during ChCl/urea-based DES treatment can be considered as an efficient approach for DCNC extraction.

Autologous endothelialisation by the stromal vascular fraction on laminin-bioconjugated nanocellulose-alginate scaffolds.

Establishing a vascular network in biofabricated tissue grafts is essential for ensuring graft survival. Such networks are dependent on the ability of the scaffold material to facilitate endothelial cell adhesion; however, the clinical translation potential of tissue-engineered scaffolds is hindered by the lack of available autologous sources of vascular cells. Here, we present a novel approach to achieving autologous endothelialisation in nanocellulose-based scaffolds by using adipose tissue-derived vascular cells on nanocellulose-based scaffolds. We used sodium periodate-mediated bioconjugation to covalently bind laminin to the scaffold surface and isolated the stromal vascular fraction and endothelial progenitor cells (EPCs; CD31+CD45-) from human lipoaspirate. Additionally, we assessed the adhesive capacity of scaffold bioconjugationin vitrousing both adipose tissue-derived cell populations and human umbilical vein endothelial cells. The results showed that the bioconjugated scaffold exhibited remarkably higher cell viability and scaffold surface coverage by adhesion regardless of cell type, whereas control groups comprising cells on non-bioconjugated scaffolds exhibited minimal cell adhesion across all cell types. Furthermore, on culture day 3, EPCs seeded on laminin-bioconjugated scaffolds showed positive immunofluorescence staining for the endothelial markers CD31 and CD34, suggesting that the scaffolds promoted progenitor differentiation into mature endothelial cells. These findings present a possible strategy for generating autologous vasculature and thereby increase the clinical relevance of 3D-bioprinted nanocellulose-based constructs.

Tailoring Functionality of Nanocellulose: Current Status and Critical Challenges.

Nanocellulose (NC) isolated from natural cellulose resources, which mainly includes cellulose nanofibril (CNF) and cellulose nanocrystal (CNC), has garnered increased attention in recent decades due to its outstanding physical and chemical properties. Various chemical modifications have been developed with the aim of surface-modifying NC for highly sophisticated applications. This review comprehensively summarizes the chemical modifications applied to NC so far in order to introduce new functionalities to the material, such as silanization, esterification, oxidation, etherification, grafting, coating, and others. The new functionalities obtained through such surface-modification methods include hydrophobicity, conductivity, antibacterial properties, and absorbability. In addition, the incorporation of NC in some functional materials, such as films, wearable sensors, cellulose nanospheres, aerogel, hydrogels, and nanocomposites, is discussed in relation to the tailoring of the functionality of NC. It should be pointed out that some issues need to be addressed during the preparation of NC and NC-based materials, such as the low reactivity of these raw materials, the difficulties involved in their scale-up, and their high energy and water consumption. Over the past decades, some methods have been developed, such as the use of pretreatment methods, the adaptation of low-cost starting raw materials, and the use of environmentally friendly chemicals, which support the practical application of NC and NC-based materials. Overall, it is believed that as a green, sustainable, and renewable nanomaterial, NC is will be suitable for large-scale applications in the future.

The effect of periodate oxidation of basil seed gum and its addition on protein binding.

This study attempted to determine the best point of basil seed oxidation by applying response surface methodology (RSM) with 3 factors of temperature (35-45 °C), pH (3-7) as well as time (3-7 h), at 3 levels. The produced dialdehyde basil seed gum (DBSG) was collected and its physicochemical properties were determined. Fitting of quadratic, linear polynomial equations was subsequently done by considering the insignificant lack of fit, as well as highly considerable R2, in order to probe the probable relationship existing between these considered variables as well as the obtained responses. So the considered optimal related test conditions, which included pH = 3, T = 45 °C as well as Time = 3 h, were specified to produce the highest percentage of aldehyde (DBSG32), optimal (DBSG34) and the (DBSG74) samples with the highest viscosity. The results obtained by FTIR and aldehyde content determination provided the indication that dialdehyde groups were formed in a way that was in equilibrium with the considered the hemiacetal form which was dominant. Furthermore, AFM investigation related to the considered DBSG34 sample displayed over-oxidation as well as depolymerization; this might be due to the enhanced hydrophobic qualities, as well as the decreased viscosity. While the DBSG34 sample had the most dialdehyde factor group with a particular tendency for the combination having the proteins' amino group, DBSG32 and DBSG74 samples could be desirable for industrial uses owing to no overoxidation.

Aminooxy Click Modification of a Periodate-Oxidized Immunoglobulin G: A General Approach to Antibody-Drug Conjugates with Dye-Mediated Expeditious Stoichiometry Control.

A universal approach to the construction of antibody-drug conjugates (ADCs) has been developed. It relies on periodate oxidation of naturally present glycans of immunoglobulin G, followed by oxime ligation and, optionally, copper(I)-catalyzed alkyne-azide cycloaddition for conjugation with a toxic payload. The introduction of highly absorbing cyanine dyes into the linker allows for facile determination of the drug-antibody ratio. We applied this methodology to the synthesis of cytotoxic conjugates of an antibody against the tumor-associated antigen PRAME with doxorubicin and monomethyl auristatin E (MMAE). The resultant conjugates retained their affinity to a large extent, yet their cytotoxicity in vitro varied dramatically: while the doxorubicin-based conjugate did not produce any effect on cells, the MMAE-based one demonstrated specific activity against PRAME-expressing cancer cell lines. Importantly, the latter conjugate constitutes the first reported example of a PRAME-targeting ADC.

Debugging periodate oxidation of cellulose: Why following the common protocol of quenching excess periodate with glycol is a bad idea.

Periodate oxidation of cellulose to produce "dialdehyde cellulose" (DAC) has lately received increasing attention in sustainable materials development. Despite the longstanding research interest and numerous reported studies, there is still an enormous variation in the proposed preparation and work-up protocols. This apparently reduces comparability and causes reproducibility problems in DAC research. Two simple but prevalent work-up protocols, namely glycol quenching and filtration/washing, were critically examined and compared, resulting in this cautionary note. Various analytical techniques were applied to quantify residual iodine species and organic contaminations from quenching side reactions. The commonly practiced glycol addition cannot remove all oxidising iodine compounds. Both glycol and the formed formaldehyde are incorporated into DAC's polymeric structure. Quenching of excess periodate with glycol can thus clearly be discouraged. Instead, simple washing protocols are recommended which do not bear the risk of side reactions with organic contaminants. While simple washing was sufficient for mildly oxidised celluloses, higher oxidised samples were more likely to trap residual (per)iodate, as determined by thiosulfate titration. For work-up, simple washing with water is proposed while determining potential iodine contaminations after washing with a simple colorimetric test and, if needed, removal of residual periodate by washing with an aqueous sodium thiosulfate solution.

Branched Linkers for Site-Specific Fluorescent Labeling of Antibodies.

Fluorescent antibodies have proved to be an invaluable tool for molecular biology and diagnostics. They are routinely produced by modification of lysine residues, which leads to high heterogeneity. As such, their affinity may be compromised if the antigen-binding site is affected, the probability of which increases along with the degree of labeling. In this work, we propose a methodology for the synthesis of site-specific antibody-dye conjugates with a high degree of labeling. To this end, we synthesized two oxyamine-based branched triazide linkers and coupled them with a periodate-oxidized anti-PRAME antibody 6H8; two oxyamine-based linear monoazide linkers of similar structure were used as controls. The azide-labeled antibodies were subsequently conjugated with fluorescent dyes via SPAAC, a copper-free click reaction. Compared to their counterparts made with linear linkers, the branched conjugates possessed a higher degree of labeling. The utility of the methodology was demonstrated in the detection of the PRAME protein on the surface of the cell by flow cytometry.

Single-base resolution mapping of 2'-O-methylation sites by an exoribonuclease-enriched chemical method.

2'-O-methylation (Nm) is one of the most abundant RNA epigenetic modifications and plays a vital role in the post-transcriptional regulation of gene expression. Current Nm mapping approaches are normally limited to highly abundant RNAs and have significant technical hurdles in mRNAs or relatively rare non-coding RNAs (ncRNAs). Here, we developed a new method for enriching Nm sites by using RNA exoribonuclease and periodate oxidation reactivity to eliminate 2'-hydroxylated (2'-OH) nucleosides, coupled with sequencing (Nm-REP-seq). We revealed several novel classes of Nm-containing ncRNAs as well as mRNAs in humans, mice, and drosophila. We found that some novel Nm sites are present at fixed positions in different tRNAs and are potential substrates of fibrillarin (FBL) methyltransferase mediated by snoRNAs. Importantly, we discovered, for the first time, that Nm located at the 3'-end of various types of ncRNAs and fragments derived from them. Our approach precisely redefines the genome-wide distribution of Nm and provides new technologies for functional studies of Nm-mediated gene regulation.

Chitosan Schiff-Base Hydrogels-A Critical Perspective Review.

Chitosan is quite a unique polysaccharide due to the presence of the amine groups naturally occurring in its structure. This feature renders it into a polycation which makes it appealing for preparing polyelectrolyte complexes or imine bonds gels. Therefore, the vast majority of hydrogels prepared using Schiff base chemistry have chitosan as one component. Usually, the counterpart is a low molecular weight aldehyde or a macromolecular periodate-oxidized polysaccharide, i.e., cellulose, pullulan, starch, alginate, hyaluronic acid, etc. Indisputable advantages of hydrogels include their quick gelation, no need for crosslinking agents, and self-healing and injectability properties. This gives grounds for further research, both fundamental in materials science and applicative in various domains. This article is a critical assessment of the most relevant aspects of this topic. It also provides a short review of some of the most interesting research reported in the literature supporting the main observations of this perspective.

Oxidation treatments to convert paper-grade Eucalyptus kraft pulp into microfibrillated cellulose.

Microfibrillated cellulose (MFC) is an emerging cellulosic material that has shown enormous potential in various industrial sectors such as food packaging, cosmetics, pharmaceuticals, filler for cement and paper, and others. Yet, there is still the need to improve its processing in order to reach its full potential. Despite research efforts for the production of MFC, the production volumes remain low because the costs of these products are hardly competitive with synthetic polymers. The present study investigates the conversion of bleached Kraft pulp into MFC using three different oxidative treatments: (1) oxidation with sodium periodate followed by oxidation with hydrogen peroxide to enrich the pulp with carboxyl groups; (2) activation of hydrogen peroxide with copper to produce hydroxyl radicals; and (3) use of hydrogen peroxide alone in alkaline medium. Treatments (1) and (2) allowed producing interesting MFC with reduced energy consumption.

Dialdehyde sodium alginate bonded dicyandiamide for formaldehyde-free leather production with enhanced properties.

Dialdehyde sodium alginate (DSA) is an eco-crosslinker attracting extensive interest while undergoing limited large-scale applications. Herein, we employed DSA to react with dicyandiamide (DA) for engineering a biomass-derived retanning agent (BDR) towards addressing the long-term toxicity of residual formaldehyde (FA) in leather caused by amino resins. Results confirmed that BDR reserved the structural features of DSA by grafting DA onto DSA molecules. Owing to the suitable molecular weight (main components, 1424-1462 g/mol) and abundant oxygen-containing groups of BDR endowed by DSA, BDR-treated chrome-free leather showed higher hydrothermal stability (82.4 °C), thickening ratio (13.93 %), mechanical strengths (17.2 N/mm2 for tensile strength and 120 N/mm for tear strength), and fullness compared with industrial dicyandiamide-FA-resin (DFR)-treated leather. The FA-free feature of DSA led to BDR-treated leather containing no FA, while FA in DFR-treated leather reached 591.5 mg/kg. This work provided new insights into broadening the large-scale application scopes of DSA.