Cellulose Ester Research Articles

Preface

It is both an honor and a privilege to introduce this inaugural issue of Biomaterials Connect. Biomaterials Connect is a newly established journal that intends to be an inclusive forum for all researchers, scientists, engineers, and professionals working within the various fields of biomaterials science. The purpose is to encourage the contribution to multi-disciplinary interaction, the diffusion of new ideas, and contributing to biomaterials research and applications, but in particular those related to medicine and dentistry. Biomaterials Connect is based on the belief that biomaterials would continue to form the foundation of healthcare advances. In collaboration with Scifiniti, we are committed to delivering a premier, peer-reviewed journal to fulfill the multi-faceted and changing biomaterials community needs. Now more than ever, it is critical to remove the barriers among disciplines and provide the fertile ground on which cutting-edge research will flourish to enhance health and improve quality of life. It is a matter of great pride to present a collection of articles that really highlights the breadth and depth of biomaterial research. This issue features two state-of-the-art review articles; one focused on the biofunctional applications of chitosan in dentistry, and another examining the role of MEMS and nanomaterials in the advancement of diagnostics and therapeutics in healthcare. In addition, this issue presents three experimental studies addressing current challenges in medicine and dentistry. These include an investigation into the effects of surface treatment of hemp fibers on the properties of polyethylene composites, a study on the synthesis and characterization of laurate ester of acetate cellulose, and research on the translucency and polymerization efficiency of contemporary resin composites. Finally, we shortly discuss the disruptive potential of 3D printing in the biomaterials field. Biomaterials Connect will cover a broad scope including, but not limited to, tissue engineering, medical devices, dental implants, biocompatibility, nanotechnology, and 3D printing. Original research articles, reviews, perspectives, and commentaries that contribute to the development of biomaterials science are invited. We aim to create a forum for an interactive and creative community that challenges established dogma through facilitating research across disciplinary boundaries. I feel very privileged to stand as Editor-in-Chief of this journal, having such an enthusiastic Editorial Board and such an extended network of renowned reviewers. We have one common goal, which is to maintain standards of scientific stringency and integrity as high as possible. I now call on all researchers from the international community to join this exciting journey and share valuable inputs and results with Biomaterials Connect. Thank you for your support, and I hope you find this first issue both informative and inspiring.

Characterization of biodegradable films based on carboxymethyl cellulose and citrus pectin films enriched with bee bread oil and thyme oil

Films based on polysaccharides (e.g., cellulose esters, pectin) are often utilized as bio-packaging for food products. In this study, films were developed by casting method using carboxymethyl cellulose (CMC), pectin (P), and glycerol incorporated with two essential oils (EOs), bee bread oil (BBO) and thyme oil (TO) in different concentrations (1, 2, and 3%). The formulated films were described in terms of physicochemical properties, as well as through FT-IR spectroscopy, morphological, and thermogravimetric analysis, and with a focus on biodegradation degree. The addition of BBO to CMC films enhanced mechanical properties (77.22–81.96 MPa for tensile strength and 380.5–629.5 MPa for Young's modulus) and reduced barrier characteristics (0.46–0.74 g × mm/kPa × h × m2 and 0.69–0.84 cc × mm/m2 × atm × day for water vapor and oxygen permeabilities, respectively). The EOs decreased the films' opacity and increased their transparency. Considerably, films incorporating 2% and 3% of BBO and TO were completely degraded after 20 days of burial. Furthermore, principal functional groups and interaction between polymers and EOs were observed by FT-IR spectroscopy and morphological analysis of films.

Gelation during Ring-Opening Reactions of Cellulosics with Cyclic Anhydrides: Phenomena and Mechanisms.

Cellulose esters are used in Food and Drug Administration-approved oral formulations, including in amorphous solid dispersions (ASDs). Some bear substituents with terminal carboxyl moieties (e.g., hydroxypropyl methyl cellulose acetate succinate (HPMCAS)); these ω-carboxy ester substituents enhance interactions with drug molecules in solid and solution phases and enable pH-responsive drug release. However, the synthesis of carboxyl-pendent cellulose esters is challenging, partly due to competing reactions between introduced carboxyl groups and residual hydroxyls on different chains, forming either physically or covalently cross-linked systems. As we explored ring-opening reactions of cyclic anhydrides with cellulose and its esters to prepare polymers designed for high ASD performance, we became concerned upon encountering gelation. Herein, we probe the complexity of such ring-opening reactions in detail, for the first time, utilizing rheometry and solid-state 13C NMR spectroscopy. Gelation in these ring-opening reactions was caused predominantly by physical interactions, progressing in some cases to covalent cross-links over time.

Bright and long-lasting aqueous peroxyoxalate chemiluminescence in cellulose microspheres.

Water decreases the brightness of the peroxyoxalate chemiluminescence partially due to the hydrolysis of the oxalate reagent. Here, we show that encapsulation of an oxalate ester and the fluorescent activator in microspheres of cellulose esters increases the emission intensity 30 times compared to the same reaction in water without encapsulation, whereas the emission intensity decay rate constants are considerably lower. Emission intensities, rate constants and chemiluminescence quantum yields increase with increasing hydrogen peroxide concentrations. These results expand the potential of application of chemiluminescence, contributing for the development of ultrasensitive analytical methods.

Extraction of Lignocellulose from Rice Straw and Its Carboxymethylation When Activated by Microwave Radiation.

The paper presents the process of cellulose extraction from rice straw using water-alkaline solution treatment and the subsequent process of carboxymethylation of the obtained product when activated by microwave radiation. After mercerization of rice straw, the obtained product contained 89.2% cellulose and 6.7% lignin. The X-ray diffraction pattern of the obtained lignocellulose shows three diffraction peaks in the region typical for the polymorphic modification of cellulose Iβ (2θ = 15.50(78), 21.70(145), 34.70(52)). The degree of crystallinity was 65%. The product was heat-stable up to 247 °C. The synthesis of carboxymethylcellulose (CMC) based on the obtained product included successive processes of thermostating in alcohol-alkali solution and cellulose esterification reaction using monochloroacetic acid. To activate the carboxymethylation process, microwave radiation was used (350 W for 90 s), which made it possible to reduce the reaction time by more than 100 times. Functional group analysis of the carboxylated lignocellulose from rice straw was carried out using an FTIR spectrometer. In the IR spectra, a band with a maximum of 1742 cm-1 was recorded, corresponding to stretching vibrations of >C(O)OH groups. The degree of polymerization was recorded by mass spectrometry.

Preparation and Charcterisation of Acetate Cellulose Laurate Ester in Sodium Acetate/Zinc Chloride Systems

The objective of this study was to explore the preparation and characterisation of acetate cellulose laurate ester in sodium acetate/zinc chloride systems. The cellulose used in the study was obtained from oil palm empty fruit bunch and oil palm frond. The characterization of both the isolated cellulose and the acetate cellulose laurate ester was carried out using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Differential thermogravimetric (DTG), and Thermogravimetric analysis (TGA). The FT-IR analysis of the acetate cellulose laurate ester revealed the presence of C=O, confirming its modification. The crystallinity of the isolated cellulose and the acetate cellulose laurate ester was found to be 67-72% and 51-54%, respectively. The thermal stability of the isolated and modified cellulose esters was found to be 360-340 ℃ and 380-365 ℃, respectively. The solubility test showed that the prepared acetate cellulose laurate esters were soluble in different solvents. However, this study found that the synthesis of acetate cellulose laurate ester in an aqueous medium is not feasible. The improved hydrophobic character, good thermal stability, water retention value, and excellent solubility in different solvents of the acetate cellulose laurate ester reported in this study make it a potential material for applications in bioplastics, and packaging materials.

Using syringe filtration after lab-scale adsorption processes potentially overestimates PFAS adsorption removal efficiency from non-conventional irrigation water.

The adsorption process, known for its cost-effectiveness and high efficiency, has been extensively investigated at the laboratory scale for removing per- and polyfluoroalkyl substances (PFAS) from non-conventional irrigation water. However, a syringe filtration step is commonly used when quantifying PFAS removal during this adsorption process, potentially leading to PFAS retention onto the filters and an overestimate of adsorption removal efficiency. Here, we assessed the retention of three prevalent PFAS (i.e., perfluorooctanoic acid [PFOA], perfluorooctane sulfonic acid [PFOS], and perfluorobutanoic acid [PFBA]) on six syringe filters. When filtering distilled deionized water spiked with 1µg/L and 100µg/L of each PFAS, we observed the highest and lowest PFAS recovery percentages by mixed cellulose ester (MCE) (0.20µm, 25mm; 97±11%, 101±4.8%) and polytetrafluoroethylene (0.45µm, 13mm; 61±37%, 80±28%), respectively. Under the initial concentration of 1µg/L and 100µg/L, PFOS had recovery percentages of 55±25% and 68±24%, significantly lower than 96±12% and 99±5% for PFOA and 95±8% and 97±4% for PFBA, highlighting the importance of PFAS functional groups. PFAS recovery percentage increased with filtration volume in the order of 80±28% (1mL)<85±21% (5mL)<90±18% (10mL). Using MCE to filter treated municipal wastewater spiked with 1µg/L and 100µg/L of each PFAS, we found recovery percentages>90% for all three PFAS. Our study underscores the significance of syringe filter selection and potential overestimate of PFAS removal efficacy by the lab-scale adsorption processes.

Synthetic membrane selection for in vitro release testing (IVRT): A case study of topical mometasone furoate semi-solid dosage forms

In vitro release testing (IVRT) is extensively used to develop the formulation of topical semi-solid products, to evaluate the quality and consistency of the product after scale-up and post-approval changes, and more recently to aid the evaluation of topical generic products’ equivalency. The selection of synthetic membrane is one of the most critical parameters of the method development part of IVRT. It is well known that the membrane features namely its polymer matrices, porosity, pore size, thickness can have a substantial effect on the IVRT data. However, there is no detailed information available in the literature regarding the membrane selection for different types of topical dosage forms. Therefore, we aimed to investigate whether difference topical semi-solid dosage forms of the same drug molecule would cause to variation in the membrane selection. Within this framework, rheological behaviour of commercially available three different types of topical semi-solid dosage forms (ointment, cream, and lotion) of mometasone furoate (0.1%) were primarily characterized. Then, the membrane inertness test was conducted using a series of synthetic hydrophilic membranes (regenerated cellulose, cellulose acetate, cellulose nitrate, mixed cellulose ester membranes) and hydrophobic membranes (polyether sulfone, polypropylene, polytetrafluoroethylene membranes) after identifying of an appropriate receptor medium that ensures sink condition for mometasone furoate. Lastly, IVRT studies from the topical semi-solid products were performed utilizing Franz-type diffusion cells. The membrane inertness and in vitro release data demonstrated that the cellulose acetate membrane showed superior diffusion properties in general while the other synthetic membranes exhibited varying outcomes for different semi-solid dosage forms of mometasone furoate. Overall, the results indicated that the release rate and the cumulative drug released amount of drug after 6 h through the different synthetic membranes might vary depending on the semi-solid dosage form. In order to select the synthetic membrane for IVRT, it should also be considered potential interactions between the polymer matrices and the chemical structure of drug molecule as well as formulation components prior to conducting membrane inertness test and IVRT studies.

Reactive extrusion of cellulose esters in ionic liquid: exploring properties and performance across different cellulose types and degrees of polymerization

Reactive extrusion of cellulose esters in ionic liquid: exploring properties and performance across different cellulose types and degrees of polymerization

Surface treatment optimization of mixed cellulose ester membrane by cold plasma treatment to improve apple juice clarification

This study aimed to determine the optimal conditions for the surface modification of mixed cellulose ester (MCE) microfiltration membrane by cold plasma (CP) for apple juice clarification. Response surface method using central cubic design (CCD) was employed for the optimization of the membrane surface modification process. Plasma gas type (oxygen, carbon dioxide, and air), power (10, 15, and 20 W), and exposure time (120, 180, and 240 s) were used as the factors for cold plasma surface modification. The results revealed the surface modification of the MCE membrane using air as plasma gas with plasma power and exposure time equal to 10 W and 180 s resulted in the maximum permeate flux in apple juice clarification. The results of scanning electron microscope, and atomic force microscope confirm the effect of CP treatment on the membrane surface roughness. Fourier transform infrared spectroscopy showed the incorporation of the hydroxyl group into the membrane surface due to CP treatment which affected the surface contact angle and hydrophilicity. The CP treatment of the membrane significantly affects the membrane resistances. Also, the surface modification of the MCE membrane using the CP treatment process in optimal conditions is an effective method for clarifying apple juice.

ω-Carboxyl terminated cellulose esters are effective crystallization inhibitors for challenging drugs

Polymeric additives are widely used to delay drug crystallization from supersaturated solutions, which is critical for enhancing oral bioavailability by amorphous solid dispersion (ASD). The efficacy of these polymers relies on their capacity to inhibit nucleation and subsequent crystal growth. Drug nucleation is pivotal to crystallization; therefore, effective polymers are essential for suppressing nucleation from supersaturated solutions. We studied the performance of cellulose ω-carboxyalkanoates designed as crystallization inhibitors by measuring their influence on nucleation induction times of poorly soluble drugs celecoxib, posaconazole, and enzalutamide, from supersaturated solutions. In the absence of polymers, crystallization occurred within 5 to 15 minutes for all three drugs. Polymer hydrophobicity strongly influenced effectiveness in crystallization inhibition. Hydrophobic polymers prolonged induction times for up to 8 hours, while hydrophilic polymers were less effective, except for cellulose acetate glutarate (CA1.18-GA1.21; degrees of substitution acetate 1.18, glutarate 1.21). The cellulose ω-carboxyalkanoates had glass transition temperatures well above 100 °C, outstanding for ASD stability requirements. We investigated the impact of these designed polymers on surface tension and found that it only weakly influenced crystallization inhibition. Among the nine crafted cellulose derivatives, water-soluble CA1.18-GA1.21 emerged as a highly promising ASD polymer, preventing crystallization for 2-8 hours for all fast-crystallizing model compounds.

Microencapsulation of &lt;i&gt;Chromolaena odorata&lt;/i&gt; Leaf Extract with Cellulose Esters for the Application as an Eco-Friendly Antibacterial Agent

The aim of this work is to develop an eco-friendly antibacterial agent in the form of microcapsules containing extract from Chromolaena odorata leaves using the solvent evaporation method. The wall materials for encapsulating were tested with various cellulose esters including cellulose acetate (CA), cellulose acetate butyrate (CAB), and cellulose acetate propionate (CAP). The evaluation of microcapsules containing C. odorata leaf extract was focused on their encapsulation efficiency, size, shape, thermal stability, and antimicrobial activities. The results showed that CAB was a suitable wall material for the encapsulation of C. odorata leaf extract. The CAB microcapsules exhibited the highest encapsulation efficiency, which was 65.82 ± 3.07. The size of CAB microcapsules was the smallest, at 1013.3 ± 66.5 nm. According to the thermogravimetric analysis, the prepared microcapsules were able to protect the extract of C. odorata leaves from the environment. Moreover, the CAB microcapsules containing C. odorata leaf extract showed the best antibacterial activities against Escherichia coli ATCC 25922 and Stapphylococcus aureus ATCC 25923. The minimum bactericidal concentration of the microcapsules was 25.6 mg/mL in both bacteria. This study proved the potential application of C. odorata leaf extract as a biomaterial in diverse industries in the future.

Design of ternary GO@AgNPs@g-C3N4 membranes for efficient dye removals in integrated photocatalysis-filtration reactors

Photocatalytic composite membranes (PCMs), which integrate the high degradation efficiency of photocatalysts and the physical separation properties of membranes, have emerged as a promising technology for wastewater treatment. Herein, the ternary GO@AgNPs@g-C3N4 PCM was fabricated through a facile vacuum-filtration assembly of graphene oxide (GO), graphitic phase carbon nitride (g-C3N4), and silver nanoparticles (AgNPs) onto commercial mixed cellulose ester (MCE) substrates. The effects of g-C3N4 synthesized from different precursors and various metal nanoparticles on the performance of PCM were systematically investigated. Interestingly, results show the addition of AgNPs not only significantly improves the photocatalytic performance of PCMs but also enhances the mechanical adhesion between the active layer and the MCE substrate. The resultant PCMs exhibit outstanding photocatalytic performance, maintaining dye removal above 89% even after 25 consecutive cycles. Moreover, dye degradation pathways over the PCMs were investigated through free radical scavenging experiments and electron spin resonance characterizations. This simple assembly method results in a 3–12 times increase in flux compared to the layer-by-layer assembly method. Accordingly, our designed PCMs exhibit significant potential for wastewater treatment and water purification applications.

Sulfur-containing cellulose esters for selectively anchoring gold for water catalytic decontamination

The facile preparation of sustainable sulfur-containing polymer functional materials has been obtained great attention due to their chemical reactivity and metal complexing ability. In this study, taking the solution properties advantages of the newly developed cellulose solvent system of DBU/DMSO/CO2, thiol and disulfide bond functionalized cellulose ester (TDSCE) was facilely prepared via in-situ tandem transesterification and oxidation reaction by using methyl 3-mercaptopropionate, without adding any external catalyst. The synthetic protocol was featured by that the DBU not only acted as reagent for the dissolution of cellulose, but also catalysts for the transesterification of cellulose with methyl 3-mercaptopropionate to yield cellulose 3-mercaptopropionate (Cell-MP) with maximum degrees of substitution (DS) of 0.77, and an oxidant for the partial oxidation of Cell-MP to produce a cellulose methyl 3,3′-disulfanediyldipropionate (Cell-MDSP) with maximum DS of 0.36 mixed ester, respectively. With successful introduction of thiol and disulfide bond into the cellulose backbone, the TDSCEs indicated desirable selective absorption of Au3+ from mimic heavy mental ions waste water due to the sulfur-Au chemistry with maximal adsorption capacity for Au3+ of 415.2 mg/g. The subsequent reduction of Au3+ into gold nanoparticles (Au NPs) fabricated a robust TDSCE-2@Au NPs composite catalyst with high catalytic activity for the hydrogenation treatment of water pollutes, such as 4-nitrophenol (4-NP)and azo dyes.

Optimization of iron flocculation for enrichment of CyHV-2 in aquaculture water

Cyprinid herpesvirus 2 (CyHV-2) is an important infectious virus endangering the farmed Carassius species industry. The enrichment and identification of CyHV-2 in the water is a vital means of early warning diagnostics, which is helpful to aquatic diseases prevention and control. In this study, we employed and optimized iron flocculation to enrich the concentrations of CyHV-2 in aquaculture water. Different Fe3+ concentrations (0.5, 1.0, and 10.0 mg/L), various membrane filters (mixed cellulose ester, glass fiber, nylon microporous filter membrane), different elution buffers containing reductants (ascorbate, citrate, DL-malate, and their combinations with EDTA or TE buffer) were compared to check the recovery yield of CyHV-2. Viral genome quantitation was determined using quantitative real-time PCR. The results showed that Fe3+ concentration of 1.0 mg/L, the glass fiber and citrate-TE were determined to have high efficiency and stable recovery yield. To evaluate infectious CyHV-2 viral titres, crucian carps (Carassius auratus) were intraperitoneally injected with CyHV-2. The mortality rate was 100 % at 9 days postinoculation (dpi) with the 96.7 % detection of CyHV-2 in the pooled tissues. The histopathological phenotype showed necrotic cell death in the liver, spleen and kidney. The CyHV-2 genome was ranging from 101.1 to 107.5 copies/μl in the deceased fish, and 101.4 to 103.0 copies/μl in the feeding water at various stages from latent infection to onset of disease. The field samples from Huzhou, Zhejiang Province on June 4th and 7th had higher detection rates, 87.5 % and 100 % respectively, corresponding to higher CyHV-2 detected in the aquaculture water. CyHV-2 viral load in cultured waters tends to increase prior to fish death, which provides a new indicator for the prediction of fish diseases. In summary, we have established a unified operational standard for enrichment of CyHV-2 in the aqueous environment by iron flocculation.

Fabrication and evaluation of PVDF membranes modified with cellulose and cellulose esters from peanut (Arachis hypogea L.) shell for application in methylene blue filtration

Polyvinylidene fluoride (PVDF) membrane is frequently employed for filtration due to its excellent properties. The hydrophobicity of PVDF membrane causes easy fouling; therefore, hydrophilic polymer materials are required to increase hydrophilicity. This study applies cellulose and cellulose esters as fillers for PVDF membranes to solve the fouling problem. Cellulose esters, such as cellulose acetate (PSCA), cellulose benzoate (PSCB), and cellulose citrate (PSCC), were successfully synthesized from peanut shell cellulose (PSC) using Fischer and non-Fischer reactions. The phase inversion method was successfully used to fabricate PVDF membranes with cellulose or cellulose esters as fillers. The fabricated membranes have been applied for methylene blue (MB) filtration. Adding PSC fillers improved the hydrophilicity and performance of the PVDF membranes up to 23.49 ± 2.40 L m−2 h−1 for water flux and 95.75 ± 0.78 % for rejection of MB. Regarding cellulose esters, cellulose acetate gave the highest value of 77.63 L m−2 h−1 for water flux, and cellulose citrate gave the highest value of 86.88 ± 3.54 % for MB rejection. Hence, cellulose or cellulose esters from peanut shells are suitable fillers for MB filtration in PVDF membranes.

Methodology Approach for Microplastics Isolation from Samples Containing Sucrose.

The growing production and use of plastics significantly contribute to microplastics (MPs) contamination in the environment. Humans are exposed to MPs primarily through the gastrointestinal route, as these particles are present in beverages and food, e.g., sugar. Effective isolation and identification of MPs from food is essential for their elimination. This study aimed to evaluate factors influencing the isolation of MPs from sucrose solutions to determine optimal conditions for the process. Polyethylene particles were used to test separation methods involving chemical digestion with acids and filtration through membrane filters made of nylon, mixed cellulose ester, and cellulose acetate with pore sizes of 0.8 and 10 µm. The effects of temperature and acid type and its concentration on plastic particles were examined using scanning electron microscopy and µ-Raman spectroscopy. The results indicate that increased temperature reduces solution viscosity and sucrose adherence to MPs' particles, while higher acid concentrations accelerate sucrose hydrolysis. The optimal conditions for MPs' isolation were found to be 5% HCl at 70 °C for 5 min, followed by filtration using an efficient membrane system. These conditions ensure a high recovery and fast filtration without altering MPs' surface properties, providing a reliable basis for further analysis of MPs in food.

Smart Lanceolate Surface with Fast Fog-Digesting Performance for Triboelectric Energy Harvesting.

Utilizing the ubiquitous fog in nature to create decentralized energy-harvesting devices, free from geographical and hydrological constraints, presents an opportunity to foster sustainable power generation. Extracting electrical energy from fog relies heavily on fog-digesting performance. Improving the efficiency of fogwater utilization remains a formidable challenge for existing fogwater energy-harvesting technologies. Inspired by the water-harvesting behavior of Tillandsia leaves, a smart lanceolate surface is developed to harvest triboelectric energy by rapidly digesting fog. Such a surface exhibits capabilities in fog management, encompassing precise fog capture, transportation, and critical droplet separation. Specifically, fog droplets condense at hydrophilic sites of acylated cellulose ester, subsequently migrating toward the rear under Laplace pressure, thereby producing energy as they traverse through the tail end. Such architecture yields a brief voltage restoration period (with an average of 9.36 s), can rush the capacitor to 11.59 V within 20 s, and achieves a water-digestion rate of up to 71.05 kg/m2 h. This biomimetic approach enhances the water-digestion efficacy of the atmospheric water energy apparatus and offers perspectives on mitigating deficiencies in power resources.

Study of heat effects of topochemical esterification of cellulose

Study of heat effects of topochemical esterification of cellulose

Band gap engineering of g-C3N4/CuS and its application in Solar Still

Interfacial solar steam generation is considered as economical and more effective implementation of Solar steam generation (SSG) where solar energy is concentrated at the liquid surface via the utilization of heat localization materials (HLM). Herein we report the fabrication of an HLM constituted of a nanocomposite absorber of graphitic carbon nitride (g-C3N4) and covellite copper sulfide (CuS) supported on a mixed cellulose ester membrane, with a substrate of air laid paper-wrapped polystyrene foam. This structure allowed for strong broad-spectrum absorbance, increased hydrophilic character and minimal thermal losses. The HLM system absorbed 98% of the material and had an evaporation rate of 2.58 kgs per square meter per hour. This is twice the evaporation rate of water tested under the same conditions. Moreover, as fabricated HLM was also incorporated in a solar still in order to assess its practical performance in solar distillation. Initial studies proved that HLM modified solar still was more effective than conventional solar stills.