Colloidal Engineering of Microplastic Capture with Biodegradable Soft Dendritic "Microcleaners".

The introduction of colloidal principles that enable efficient microplastic collection from aquatic environments is a goal of great environmental importance. Here, we present a novel method of microplastic (MP) collection using biodegradable hydrogel soft dendritic colloids (hSDCs). These dendritic colloids have abundant nanofibrils and a large surface area, which provide an abundance of interfacial interactions and excellent networking capabilities, allowing for the capture of plastic particles and other contaminants. Here, we show how the polymer composition and morphology of the hSDCs can impact the capture of microplastics modeled by latex microbeads. Additionally, we use colloidal DLVO theory to interpret the capture efficiencies of microbeads of different sizes and surface functional groups. The results demonstrate the microplastic remediation efficiency of hydrogel dendricolloids and highlight the primary factors involved in the microbead interactions and adsorption. On a practical level, the results show that the development of environmentally benign microcleaners based on naturally sourced materials could present a sustainable solution for microplastic cleanup.

Elucidation of temperature-induced water structuring on cellulose surfaces for environmental and energy sustainability.

Optimizing drying energy in the forest products industry is critical for integrating lignocellulosic feedstocks across all manufacturing sectors. Despite substantial efforts to reduce thermal energy consumption during drying, further enhancements are possible. Cellulose, the main component of forest products, is Earth's most abundant biopolymer and a promising renewable feedstock. This study employs all-atom molecular dynamics (MD) simulations to explore the structural dynamics of a small Iß-cellulose microcrystallite and surrounding water layers during drying. Molecular and atomistic profiles revealed localized water near the cellulose surface, with water structuring extending beyond 8 Å into the water bulk, influencing solvent-accessible surface area and solvation energy. With increasing temperature, there was a ∼20 % reduction in the cellulose surface available for interaction with water molecules, and a ∼22 % reduction in solvation energy. The number of hydrogen bonds increased with thicker water layers, facilitated by a "bridging" effect. Electrostatic interactions dominated the intermolecular interactions at all temperatures, creating an energetic barrier that hinders water removal, slowing the drying processes. Understanding temperature-dependent cellulose-water interactions at the molecular level will help in designing novel strategies to address drying energy consumption, advancing the adoption of lignocellulosics as viable manufacturing feedstocks.

Comparison and assessment of methods for cellulose crystallinity determination.

The degree of crystallinity in cellulose significantly affects the physical, mechanical, and chemical properties of cellulosic materials, their processing, and their final application. Measuring the crystalline structures of cellulose is a challenging task due to inadequate consistency among the variety of analytical techniques available and the lack of absolute crystalline and amorphous standards. Our article reviews the primary methods for estimating the crystallinity of cellulose, namely, X-ray diffraction (XRD), nuclear magnetic resonance (NMR), Raman and Fourier-transform infrared (FTIR) spectroscopy, sum-frequency generation vibrational spectroscopy (SFG), as well as differential scanning calorimetry (DSC), and evolving biochemical methods using cellulose binding molecules (CBMs). The techniques are compared to better interrogate not only the requirements of each method, but also their differences, synergies, and limitations. The article highlights fundamental principles to guide the general community to initiate studies of the crystallinity of cellulosic materials.

Polymer Color Intelligence: Effect of Materials, Instruments, and Measurement Techniques - A Review.

Transparent polymers and plastics are used to create molded parts and films for many applications. The colors of these products are of great importance for the suppliers, manufacturers, and end-users. However, for simplicity of the processing, the plastics are produced in the form of small pellets or granules. The predictive measurement of the color of such materials is a challenging process and needs consideration of a complex set of factors. A combination of color measurement systems in transmittance and reflectance modes need to be used for such materials, along with the techniques for minimizing the artifacts based on surface texture and particle sizes. This article provides an extensive overview and discussion of the various factors that can affect the perceptive colors and the methods used for the characterization of the colors and minimizing the measuring artifacts.

Innovation in lignocellulosics dewatering and drying for energy sustainability and enhanced utilization of forestry, agriculture, and marine resources - A review.

Efficient utilization of forestry, agriculture, and marine resources in various manufacturing sectors requires optimizing fiber transformation, dewatering, and drying energy consumption. These processes play a crucial role in reducing the carbon footprint and boosting sustainability within the circular bioeconomy framework. Despite efforts made in the paper industry to enhance productivity while conserving resources and energy through lower grammage and higher machine speeds, reducing thermal energy consumption during papermaking remains a significant challenge. A key approach to address this challenge lies in increasing dewatering of the fiber web before entering the dryer section of the paper machine. Similarly, the production of high-value-added products derived from alternative lignocellulosic feedstocks, such as nanocellulose and microalgae, requires advanced dewatering techniques for techno-economic viability. This critical and systematic review aims to comprehensively explore the intricate interactions between water and lignocellulosic surfaces, as well as the leading technologies used to enhance dewatering and drying. Recent developments in technologies to reduce water content during papermaking, and advanced dewatering techniques for nanocellulosic and microalgal feedstocks are addressed. Existing research highlights several fundamental and technical challenges spanning from the nano- to macroscopic scales that must be addressed to make lignocellulosics a suitable feedstock option for industry. By identifying alternative strategies to improve water removal, this review intends to accelerate the widespread adoption of lignocellulosics as feasible manufacturing feedstocks. Moreover, this review aims to provide a fundamental understanding of the interactions, associations, and bonding mechanisms between water and cellulose fibers, nanocellulosic materials, and microalgal feedstocks. The findings of this review shed light on critical research directions necessary for advancing the efficient utilization of lignocellulosic resources and accelerating the transition towards sustainable manufacturing practices.

Plant-biomass-based hybrid seed wraps mitigate yield and post-harvest losses among smallholder farmers in sub-Saharan Africa.

Sustainable practices that reduce food loss are essential for enhancing global food security. We report a 'wrap and plant' seed treatment platform to protect crops from soil-borne pathogens. Developed from the abundantly available wastes of banana harvest and recycled old, corrugated cardboard boxes via chemical-free pulping, these paper-like biodegradable seed wraps exhibit tunable integrity and bioavailability of loaded moieties. These wraps were used for nematode control on yam (Dioscorea cayenensis-rotundata) seed pieces in Benin, a major producer of this staple crop in the sub-Saharan African 'yam belt'. Our seed wraps loaded with ultra-low-volume abamectin (1/100 ≤ commercial formulation) consistently controlled yam nematode (Scutellonema bradys) populations while considerably increasing the yield at various locations over 2015-2018. Substantial reduction in post-harvest tuber weight loss and cracking was observed after 3 and 5 months of storage, contributing to increased value, nutrition and stakeholders' preference for the wrap and plant treatment.

Surface Mechanical Properties and Topological Characteristics of Thermoplastic Copolyesters after Precisely Controlled Abrasion.

Due to the high probability of surface-to-surface contact of materials during routine applications, surface abrasion remains one of the most challenging factors governing the long-term performance of polymeric materials due to their broad range of tunable mechanical properties, as well as the varied conditions of abrasion (regarding, e.g., rate, load, and contact area). While this concept is empirically mature, a fundamental understanding of mechanical abrasion regarding thermoplastics remains lacking even though polymer abrasion can inadvertently lead to the formation of nano-/microplastics. In the present study, we introduce the concept of precision polymer abrasion (PPA) in conjunction with nanoindentation to elucidate the extent to which controlled wear is experienced by three chemically related thermoplastics under systematically varied abrasion conditions. While depth profiling of one polymer reveals a probe-dependent change in modulus, complementary results from positron annihilation lifetime spectroscopy confirm that the polymer density changes measurably, but not appreciably, with depth over the depth range explored. After a single PPA pass, the surface moduli of the polymers noticeably increase, whereas the corresponding increase in hardness is modest. The dependence of wear volume on the number of PPA passes is observed to reach limiting values for two of the thermoplastics, and application of an empirical model to the data yields estimates of these values for all three thermoplastics. These results suggest that the metrics commonly employed to describe the surface abrasion of polymers requires careful consideration of a host of underlying factors.

A systematic examination of the dynamics of water-cellulose interactions on capillary force-induced fiber collapse.

Cellulosic fiber collapse is a phenomenon of fundamental importance for many technologies that include tissue/hygiene to packaging because it governs their essential materials properties such as tensile strength, softness, and water absorption; therefore, we elaborate cellulose fiber collapse from water interactions. This is the first attempt to directly correlate fiber collapse and entrapped or hard-to-remove (HR) water content through DSC, TGA and SEM. Freeze-drying and oven drying were individually investigated for influence on collapse. SEM of the fibers at different moisture contents show that irreversible collapsing begins as entrapped water departs the fiber surface. The removal of HR water pulls cell walls closer due to strong capillary action which overwhelms the elastic force of the fiber lumen which results in partially or fully irreversible collapse. The initial moisture content and refining intensity were found to regulate HR water content and consequently played a vital role in fiber collapsing.

A Critical Review of the Performance and Soil Biodegradability Profiles of Biobased Natural and Chemically Synthesized Polymers in Industrial Applications.

This review explores biobased polymers for industrial applications, their end fate, and most importantly, origin and key aspects enabling soil biodegradation. The physicochemical properties of biobased synthetic and natural polymers and the primary factors governing degradation are explored. Current and future biobased systems and factors allowing for equivalent comparisons of degradation and possible sources for engineering improved biodegradation are reviewed. Factors impacting ultraviolet (UV) stability of biopolymers have been described including methods to enhance photoresistance and impact on biodegradation. It discusses end-fate of biopolymers in soil and impact of residues on soil health. A limited number of studies examine side effects (e.g., microbial toxicity) from soil biodegradation of composites and biopolymers. Currently available standards for biodegradation and composting have been described with limitations and scope for improvements. Finally, design considerations and implications for sustainable polymers used, under consideration, and to be considered within the context of a rational biodegradable strategy are elaborated.

Study of tobacco-derived proteins in paper coatings.

Replacing synthetic polymers with renewable alternatives is a critical challenge for the packaging industry. This research investigated the use of leaf-based proteins as a sustainable co-binder in the coating formulations for paper-based packaging and other applications. Protein isolates from tobacco leaf and alfalfa concentrates were characterized using the Pierce protein assay, Kjeldahl nitrogen, and gel electrophoresis. The proteins were tested as co-binders in a typical latex-based paper coating formulation. The rheology and water retention properties of the wet coating and the surface, optical, structural, and strength properties of coated papers were measured. The coating performance was affected by the purity, solubility, and molecular weight of the tobacco protein and exhibited a shear-thinning behavior with lower water retention than soy protein. Analysis by scanning electron microscopy and time of flight secondary ion mass spectroscopy on the dried coating layer containing tobacco protein showed enhanced porosity (advantageous for package glueability) relative to the control latex coating. The tobacco protein offers adequate coverage and coating pigment distribution, indicating that this protein can be a suitable option in coatings for packaging applications.

Lignocellulosic Fibers from Renewable Resources Using Green Chemistry for a Circular Economy.

The sustainable development of lignocellulose fibers exhibits significant potential to supplant synthetic polymer feedstocks and offers a global platform for generating sustainable packaging, bioplastics, sanitary towels, wipes, and related products. The current research explores the dynamics of fiber production from wood, non-wood, and agro-residues using carbonate hydrolysis and a mild kraft process without bleaching agents. With respect to carbonate hydrolysis, high yield, and good coarseness fibers are attained using a simple, low-cost, and ecofriendly process. Fibers produced using a mild kraft process have lower Klason lignin, carboxyl content, surface charges, and higher fiber length, and crystallinity. Eucalyptus fibers show the highest crystallinity while softwood carbonate fibers show the lowest crystallinity. Hemp hurd fibers contain the highest concentration of hard-to-remove water, and thus, suffer maximum flattening visualized by the microscopic images. The relatively high yield sustainable fibers with versatile properties can provide a significant economic benefit since fiber is the dominant cost for producing various bioproducts to meet society's current and future needs.

Hydrogel-Based Sensor Networks: Compositions, Properties, and Applications-A Review.

Hydrogels are three-dimensional porous polymeric networks prepared by physical or chemical cross-linking of hydrophilic molecules, which can be made into smart materials through judicious chemical modifications to recognize external stimuli; more specifically, this can be accomplished by the integration with stimuli-responsive polymers or sensing molecules that has drawn considerable attention in their possible roles as sensors and diagnostic tools. They can be tailored in different structures and integrated into systems, depending on their chemical and physical structure, sensitivity to the external stimuli and biocompatibility. A panoramic overview of the sensing advances in the field of hydrogels over the past several decades focusing on a variety protocols of hydrogel preparations is provided, with a major focus on natural polymers. The modifications of hydrogel composites by incorporating inorganic nanoparticles and organic polymeric compounds for sensor applications and their mechanisms are also discussed.

Crude Wood Rosin and Its Derivatives as Hydrophobic Surface Treatment Additives for Paper and Packaging.

The aim of this work is to obtain better water resistance properties with additives to starch at the size press. A further goal is to replace petroleum-based additives with environmentally friendly hydrophobic agents obtained by derivatization of wood rosin. A crude wood rosin (CWR) sample was methylated and analyzed with gas chromatography-mass spectrometry (GC-MS). Methyl abietate, dehydroabietic acid, and abietic acid were the main constituents of the sample. The crude wood rosin samples were fortified with fumaric acid and then esterified with pentaerythritol. Fortified and esterified wood rosin samples were dissolved in ethanol and emulsified with cationic starch to make them suitable as hydrophobic additives for surface treatment formulations in mixtures with starch. These hydrophobic agents (2% on a dry weight basis in a cationic starch solution) were applied to paperboard, bleached kraft paper, and test liner paper using a rod coater with a target pickup of 3-5 gsm. The solution pickup was controlled by varying the rod number. The amounts of hydrophobic material applied in the preparation of the paper samples were 32.2, 48.6, and 35.1 lb/ton pickup compared to three types of base papers. Basic surface features of fortified and fortified and esterified rosin-treated paper were compared with base paper and paper treated with starch alone. Lower Cobb60 values were obtained for fortified and esterified samples than for linerboard samples that had been surface-sized just by starch. Thus, as novel hydrophobic additive agents, derivatives of CWR can be a green way to increase hydrophobicity while reducing starch consumption in papermaking.

Recent advances in biodegradable matrices for active ingredient release in crop protection: Towards attaining sustainability in agriculture.

Climate changes, emerging species of plant pests, and deficits of clean water and arable land have made availability of food to the ever-increasing global population a challenge. Excessive use of synthetic pesticides to meet ever-increasing production needs has resulted in development of resistance in pest populations, as well as significant ecotoxicity, which has directly and indirectly impacted all life-forms on earth. To meet the goal of providing safe, sufficient, and high-quality food globally with minimal environmental impact, one strategy is to focus on targeted delivery of pesticides using eco-friendly and biodegradable carriers that are derived from naturally available materials. Herein, we discuss some of the recent approaches to use biodegradable matrices in crop protection, while exploring their design and efficiency. We summarize by discussing associated challenges with the existing approaches and future trends that can lead the world to more sustainable agricultural practices.

Tailored Lignocellulose-Based Biodegradable Matrices with Effective Cargo Delivery for Crop Protection.

Controlled release and targeted delivery of agrochemicals are crucial for achieving effective crop protection with minimal damage to the environment. This work presents an innovative and cost-effective approach to fabricate lignocellulose-based biodegradable porous matrices capable of slow and sustained release of the loaded molecules for effective crop protection. The matrix exhibits tunable physicochemical properties which, when coupled with our unique "wrap-and-plant" concept, help to utilize it as a defense against soil-borne pests while providing controlled release of crop protection moieties. The tailored matrix is produced by mechanical treatment of the lignocellulosic fibers obtained from banana plants. The effect of different extents of mechanical treatments of the lignocellulosic fibers on the protective properties of the developed matrices is systematically investigated. While variation in mechanical treatment affects the morphology, strength, and porosity of the matrices, the specific composition and structure of the fibers are also capable of influencing their release profile. To corroborate this hypothesis, the effect of morphology and lignin content changes on the release of rhodamine B and abamectin as model cargos is investigated. These results, compared with those of the matrices developed from non-banana fibrous sources, reveal a unique release profile of the matrices developed from banana fibers, thereby making them strong candidates for crop protection applications.

Highly tunable bioadhesion and optics of 3D printable PNIPAm/cellulose nanofibrils hydrogels.

A hybrid poly(N-isopropylacrylamide) (PNIPAm)/cellulose nanofibrils (CNFs) hydrogel composite was fabricated by inverted stereolithography 3D printing to provide a new platform for regulating lower critical solution temperature (LCST) properties and thus tuning optical and bioadhesive properties. The phenomena of interest in the as-printed PNIPAm/CNF hydrogels may be attributed to the fiber-reinforced composite system between crosslinked PNIPAm and CNFs. The optical tunability was found to be correlated to the micro/nano structures of the PNIPAm/CNF hydrogel films. It was found that PNIPAm/CNF hydrogels exhibit switchable bioadhesivity to bacteria in response to CNF distribution in the hydrogels. After 2.0 wt% CNF was incorporated, it was found that a remarkable 8°C reduction of the LCST was achieved relative to PNIPAm hydrogel crosslinked by TEGDMA without CNF. The prepared PNIPAm/CNF hydrogels possessed highly reversible optical, bioadhesion, and thermal performance, making them suitable to be used as durable temperature-sensitive sensors and functional biomedical devices.

3D Photoinduced Spatiotemporal Resolution of Cellulose-Based Hydrogels for Fabrication of Biomedical Devices.

Rational spatiotemporal irradiation of cellulose-based hydrogels (carboxymethylcellulose (CMC), citric acid, and riboflavin) using a laser diode stereolithography 3D printer obtained architectures referred to as photodegradation addressable hydrogels (PAHs). Under irradiation, these PAHs engage in an unprecedented spatially resolved zonal swelling illustrating marked but controllable changes in swelling and thickness while concomitantly obtaining improved oxygen transmission rate values by 5 times. XPS, carboxyl content, and swelling data comparisons of hydrogel formulations show that photodegradation and ablation of the material occur, where hydroxyl sites of CMC are converted to aldehydes and ketones. XRD data show that the total number of crystalline aggregates in the material are lowered after photoablation. The spatially tuned (photoablated) hydrogel films can thus be shaped into a lens form. The energy required for the lens tuning process can be lowered up to 30 times by incorporation of riboflavin in the films. The method demonstrated here enables the processing of a material that is difficult to be machined or cast by popular contact lens making methods.

Highly conductive carbon nanotubes and flexible cellulose nanofibers composite membranes with semi-interpenetrating networks structure.

Highly conductive multi-walled carbon nanotubes (MWCNTs) and flexible cellulose nanofibers (CNF) membranes with semi-interpenetrating networks structure were fabricated using the typical paper-making method, which was simple and cost-effective. The Scanning electron microscope (SEM), Fourier-transform infrared (FT-IR), and thermal gravimetric analysis (TGA) were used to estimate the morphology, chemical structure, and thermal stability of the membranes. The mechanical, optical, and electrical properties of the membranes were characterized with a uniaxial tensile testing machine, ultraviolet visible spectroscope, and digital multimeter, respectively. The results indicated that the membranes containing 10 wt% of MWCNTs showed a high conductivity value of 37.6 S/m, and the sheet resistances of the membranes were stable at different bending states. Furthermore, we demonstrated the electrical features of membrane-based capacitive pressure sensors based on CNF/MWCNTs. The proposed method for fabricating CNF/MWCNTs membranes can simplify the production process and have great practical potential in various electronics applications such as touch screens.

Unique thermo-responsivity and tunable optical performance of poly(N-isopropylacrylamide)-cellulose nanocrystal hydrogel films.

A hybrid materials system to modulate lower critical solution temperature (LCST) and moisture content for thermo-responsivity and optical tunability was strategically developed by incorporating cellulose nanocrystals (CNCs) into a poly(N-isopropylacrylamide) (PNIPAm) hydrogel matrix. The PNIPAm/CNC hydrogel films exhibit tunable optical properties and wavelength bandpass selectivity as characterized by PROBE Spectroscopy and Dynamic Light Scattering (DLS). Importantly, the micro/nano structures of the PNIPAm/CNC hydrogel films were completely different when dried below and above the LCST. Below the LCST, PNIPAm/CNC hydrogel films exhibit transparency or semi-transparency due to the uniform bonding of hydrophilic PNIPAm and CNC through hydrogen bonds. Above the LCST, the hydrogel films engage in both hydrophobic PNIPAm and hydrophilic CNC interactions due to changes in PNIPAm conformation which lead to light scattering effects and hence opacity. Furthermore, the incorporation of CNC induces a ∼ 15 °C reduction of the LCST relative to pure PNIPAm hydrogel films.

High-Strength Antibacterial Chitosan-Cellulose Nanocrystal Composite Tissue Paper.

A heightened need to control the spread of infectious diseases prompted the current work in which functionalized and innovative antimicrobial tissue paper was developed with a hydrophobic spray-coating of chitosan (Ch) and cellulose nanocrystals (CNCs) composite. It was hypothesized that the hydrophobic nature of chitosan could be counterbalanced by the addition of CNC to maintain fiber formation and water absorbency. Light-weight tissue handsheets were prepared, spray-coated with Ch, CNC, and their composite coating (ChCNC), and tested for antimicrobial activity against Gram-negative bacteria Escherichia coli and a microbial sample from a human hand after using the rest room. Water absorption and strength properties were also analyzed. To activate the surface of cationized tissue paper, an oxygen/helium gas atmospheric plasma treatment was employed on the best performing antimicrobial tissue papers. The highest bactericidal activity was observed with ChCNC-coated tissue paper, inhibiting up to 98% microbial growth. Plasma treatment further improved the antimicrobial activity of the coatings. Water absorption properties were reduced with Ch but increased with CNC. This "self-disinfecting" bactericidal tissue has the potential to be one of the most innovative products for the hygiene industry because it can dry, clean, and resist the infection of surfaces simultaneously, providing significant societal benefits.