Physicochemical Modifications Research Articles

The application of dairy products and their derivatives as edible inks in 3D printing technology: A review

SummaryThree‐dimensional (3D) printing technology digitally designs and manufactures objects through computer‐controlled processes. It requires raw materials with specific rheological properties for extrusion and shape retention. Dairy products hold promise for 3D printing due to their ability to form structures and their nutritional value. However, the quality of 3D printing with dairy products relies on the properties of the printing ink and printer parameters, presenting challenges for practical applications. This work provided a summary of the suitability of dairy‐based 3D printed products, discussing physicochemical modifications and additives to enhance their suitability and nutritional properties. The internal structure and composition of printing inks derived from dairy products are closely linked to their printing performance. Physicochemical modifications and additives effectively improve printability and the nutritional aspects of dairy inks. The 3D printing suitability of dairy inks can be enhanced through physical, chemical or enzymatic treatments. The gel properties of dairy products can be improved by mixing them with hydrophilic gels, introducing calcium, and incorporating lipids to enhance the 3D printing performance of dairy products. 3D printing technology enables the customisation of dairy products with personalised control of nutritional content, meeting the increasing consumer and market demand for healthier foods. In the future, 3D printed dairy products are expected to constitute convenient and quick nutritious food and enter home kitchens.

Effect of amylose partial extraction on citrate esterification of potato starch and its role in structure and physicochemical modification

This study examines the impact and influence of amylose on the starch esterification reaction through partial extraction of amylose. Citric acid was added for the esterification reaction, and then the esterified starches' multiscale structure, physicochemical, and functional properties were evaluated. As the extraction time of amylose increased, the amylose content in the starch decreased. Higher concentrations of citric acid will lead to samples with a higher degree of substitution, with DS rising from 0.203 % (0 h) to 0.231 % (3.5 h) at CA3 treatment. While removing amylose had minimal effects on the crystal structure of starch granules, it did decrease the ratio of A and B1 chains and the molecular weight of amylose. Acid hydrolysis exacerbated these changes upon the addition of citric acid. Furthermore, removing amylose followed by citrate esterification resulted in lower pasting viscosity, enthalpy of gelatinization (from 13.37 J to 2.83 J), and degree of short-range ordering. Also, digestion shows a decrease caused by the increasing content of slow-digesting starch. The presence of amylose in starch granules does affect the formation of starch esters, and removing it before esterification modification may improve production efficiency and reduce costs to some extent.

Starch digestibility: How single, double, and multiple physicochemical modifications change nutritional attributes of starch?

AbstractThe ever‐increasing ranges of starch applications have been restricted by some of its inherent adverse characteristics like retrogradability, gel opacity, low resistibility to variations of pH, and elevated shear/temperatures. Starch modification through various physical, chemical, and enzymatic methods has been proposed as the most mature platform to tackle such drawbacks. Along with their outstanding potential in enhancing the starch's technofunctional characteristics, physicochemical modifications could remarkably customize starch nutritional/digestibility attributes. For instance, physical modifications could remarkably change starch digestibility by manipulating the granular architecture while chemical approaches change it by altering the chemical structure of starch molecules, making them unrecognizable to digestive enzymes. Such alterations could even be more challenging upon applying a combination of starch modifications. The changes in starch digestibility through its modification via single, double, and multiple modifications have been overviewed in this review.

Synchronous Front-Face Fluorescence Spectra: A Review of Milk Fluorophores.

Milk is subjected to different industrial processes, provoking significant physicochemical modifications that impact milk's functional properties. As a rapid and in-line method, front-face fluorescence can be used to characterize milk instead of conventional analytical tests. However, when applying fluorescence spectroscopy for any application, it is not always necessary to determine which compound is responsible for each fluorescent response. In complex matrixes such as milk where several variables are interdependent, the unique identification of compounds can be challenging. Thus, few efforts have been made on the chemical characterization of milk' fluorescent spectrum and the current information is dispersed. This review aims to organize research findings by dividing the milk spectra into areas and concatenating each area with at least one fluorophore. Designations are discussed by providing specific information on the fluorescent properties of each compound. In addition, a summary table of all fluorophores and references cited in this work by area is provided. This review provides a solid foundation for further research and could serve as a central reference.

Development of Novel Nanocarriers by Ultrasound and Ethanol-Assisted Soy Protein Isolate: Enhancing the Resistance of Lutein to Environmental Stress.

The aim of this work was to investigate the effects of the processing sequence of ultrasound and ethanol on the physicochemical properties of soy protein isolate (SPI), which were further evaluated for the morphology and stability of SPI-lutein coassembled nanoparticles. The results showed that the sequence of ultrasound followed by ethanol treatment was the optimal one. The samples were subjected to ultrasonication followed by subunit disassembly and reassembly induced by 40% (v/v) ethanol, with the resulting molecular unfolding and subsequent aggregation being attributed to intramolecular hydrogen bonds. The recombined nanoparticles had smaller particle size (142.43 ± 2.91 nm) and turbidity (0.16 ± 0.01), and the exposure of more hydrophobic groups (H0 = 6221.00 ± 130.20) induced a shift of SPI structure toward a more ordered direction. The homogeneous and stable particle provided excellent stability for the loading of lutein. The bioaccessibility (from 25.48 ± 2.35 to 65.85 ± 1.78%) and release rate of lutein were modulated in gastrointestinal digestion experiments. Our discoveries provide a new perspective for the development of combined physicochemical modification of proteins as nanocarriers in functional foods.

Argon plasma-modified bacterial nanocellulose: Cell-specific differences in the interaction with fibroblasts and endothelial cells

Unique properties of bacterial nanocelullose (BNC), such as high purity, water retention, nanofibrillar structure and non-cytotoxicity, allow its application in regenerative medicine, particularly for active wound healing and for skin tissue engineering. However, its biological activity is not fully sufficient to be considered a good cell scaffold. This can be enhanced by physicochemical modifications, particularly plasma treatment. In this work, air-dried (AD) or lyophilized (L) BNC samples were modified in a direct current Ar+ plasma discharge (PM). BNC_AD samples showed higher surface roughness, tensile strength and Young's modulus but a lower swelling ratio than BNC_L samples. The swelling ratio of BNC_L samples further increased after PM. The samples were subjected to six-day in vitro cell culture tests with normal human dermal fibroblasts (NHDFs) or human umbilical vein endothelial cells (HUVECs), i.e. cell types important for skin defect healing. NHDFs adhered in higher numbers, by a larger cell spreading area and reached higher cell population densities on PM samples than on unmodified samples. However, in HUVECs, this effect of PM on cell growth was less pronounced or even opposite, especially on mechanically weaker and more swellable BNC_L. At the same time, both cell types preferred mechanically stronger BNC_AD for their adhesion and growth, which was more apparent in HUVECs. The expression of mRNA for markers of cell adhesion and phenotypic maturation in NHDFs (talin, vinculin, CD90) was generally similar on BNC_PM and on tissue culture polystyrene. In HUVECs, the expression of vinculin and PECAM-1 on all BNC samples was lower than on polystyrene, but the expression of KDR (VEGF receptor 2) was higher, especially on BNC_PM. These results indicate cell type-specific differences in the response to various BNC modifications, which must be properly balanced to accommodate various cell types needed for wound healing and skin tissue engineering.

Consolidation of Spray-Dried Amorphous Calcium Phosphate by Ultrafast Compression: Chemical and Structural Overview.

A large amount of research in orthopedic and maxillofacial domains is dedicated to the development of bioactive 3D scaffolds. This includes the search for highly resorbable compounds, capable of triggering cell activity and favoring bone regeneration. Considering the phosphocalcic nature of bone mineral, these aims can be achieved by the choice of amorphous calcium phosphates (ACPs). Because of their metastable property, these compounds are however to-date seldom used in bulk form. In this work, we used a non-conventional "cold sintering" approach based on ultrafast low-pressure RT compaction to successfully consolidate ACP pellets while preserving their amorphous nature (XRD). Complementary spectroscopic analyses (FTIR, Raman, solid-state NMR) and thermal analyses showed that the starting powder underwent slight physicochemical modifications, with a partial loss of water and local change in the HPO42- ion environment. The creation of an open porous structure, which is especially adapted for non-load bearing bone defects, was also observed. Moreover, the pellets obtained exhibited sufficient mechanical resistance allowing for manipulation, surgical placement and eventual cutting/reshaping in the operation room. Three-dimensional porous scaffolds of cold-sintered reactive ACP, fabricated through this low-energy, ultrafast consolidation process, show promise toward the development of highly bioactive and tailorable biomaterials for bone regeneration, also permitting combinations with various thermosensitive drugs.

The synergistic interplay of hierarchy, crystal size, and Ga-promotion in the methanol-to-aromatics process over ZSM-5 zeolites.

In the context of advancing social modernization, the projected shortfall in the demand for renewable aromatic hydrocarbons is expected to widen, influenced by industries like high-end materials, pharmaceuticals, and consumer goods. Sustainable methods for aromatic production from alternative sources, particularly the methanol-to-aromatics (MTA) process using zeolite ZSM-5 and associated with the "methanol economy", have garnered widespread attention. To facilitate this transition, our project consolidates conventional strategies that impact aromatics selectivity-such as using hierarchical zeolites, metallic promoters, or altering zeolite physicochemical properties-into a unified study. Our findings demonstrate the beneficial impact of elongated crystal size and heightened zeolite hierarchy on preferential aromatics selectivity, albeit through distinct mechanisms involving the consumption of shorter olefins. While metallic promoters enhance MTA performance, crystal size, and hierarchy remain pivotal in achieving the maximized aromatics selectivity. This study contributes to a deeper understanding of achieving superior aromatics selectivity through physicochemical modifications in zeolite ZSM-5 during MTA catalysis, thereby advancing the field's comprehension of structure-reactivity relationships.

Valorization of lignin for advanced material applications: a review

A comprehensive overview of various physicochemical modification and functionalization routes of lignin to produce alternative low carbon footprint feedstock for sustainable polymers for advanced material applications is presented.

Corrective protocol to predict interference free sensor response for paper-based solution sampling coupled with heavy metal sensitive ion-selective electrodes.

Paper-based microfluidics combined with potentiometric measurement has emerged as an attractive approach for detecting various chemical ionic moieties. Detection of heavy metal ions, using paper substrates as solution sampling and delivery systems remains challenging despite efforts to introduce several physico-chemical paper substrate modifications to stop adsorption of ions onto the paper substrates. This study quantitatively investigates the adsorption of heavy metal ions on the paper substrates during paper-based potentiometric measurements and explains the super-Nernstian response of potentiometric sensors through local depletion of heavy metal ions from the solution. Consequently, based on the investigated ion adsorption, a corrective potential protocol was established for the electrodes coupled with paper-based solution sampling by predicting interference free sensor response from paper-based measurement. Furthermore, the ion adsorption was also recorded for mixed metal ion solutions to understand competitive primary/interfering ions adsorption onto the paper substrates and establish corrective measures to predict interference free sensor response. In this method, no modifications of the paper substrates are necessary before actual potentiometric measurements. The proposed corrective protocol allows prediction of sensor response based on the paper-based solution sampling potentiometric measurement, providing a simple methodological approach based on correction of potential readout of the potentiometric sensor, thus completely resigning from the need of modifying paper substrate for measurements of heavy metal ions.

Nucleic acid-based nanotherapeutics for treating sepsis and associated organ injuries.

In recent years, gene therapy has been made possible with the success of nucleic acid drugs against sepsis and its related organ dysfunction. Therapeutics based on nucleic acids such as small interfering RNAs (siRNAs), microRNAs (miRNAs), messenger RNAs (mRNAs), and plasmid DNAs (pDNAs) guarantee to treat previously undruggable diseases. The advantage of nucleic acid-based therapy against sepsis lies in the development of nanocarriers, achieving targeted and controlled gene delivery for improved efficacy with minimal adverse effects. Entrapment into nanocarriers also ameliorates the poor cellular uptake of naked nucleic acids. In this study, we discuss the current state of the art in nanoparticles for nucleic acid delivery to treat hyperinflammation and apoptosis associated with sepsis. The optimized design of the nanoparticles through physicochemical property modification and ligand conjugation can target specific organs-such as lung, heart, kidney, and liver-to mitigate multiple sepsis-associated organ injuries. This review highlights the nanomaterials designed for fabricating the anti-sepsis nanosystems, their physicochemical characterization, the mechanisms of nucleic acid-based therapy in working against sepsis, and the potential for promoting the therapeutic efficiency of the nucleic acids. The current investigations associated with nanoparticulate nucleic acid application in sepsis management are summarized in this paper. Noteworthily, the potential application of nanotherapeutic nucleic acids allows for a novel strategy to treat sepsis. Further clinical studies are required to confirm the findings in cell- and animal-based experiments. The capability of large-scale production and reproducibility of nanoparticle products are also critical for commercialization. It is expected that numerous anti-sepsis possibilities will be investigated for nucleic acid-based nanotherapeutics in the future.

Physicochemical Modifications on Fibre Reinforced Polymer Composites for Mining Applications

Polymer composites are mainly employed as an industrial material because of their chemical and corrosion resistance, especially in mining applications. As a result of the growing demand for biodegradable, ecological, and recyclable materials, organic fibres are widely used as reinforcement in polymer composites in recent years. The challenges arising from polymer composites, like environmental impact, moisture absorption, Thermomechanical property deterioration, lower durability in mining applications are discussed in this review. This work analyses the influence of certain physicochemical modifications on the reinforcement and matrix in polymer composites for mining purpose. This investigation was to understand the effectiveness of physicochemical modifications, specifically cryogenic treatment, on reinforcements and matrix to overcome the above mentioned challenges. This study also highlights the morphological and thermal changes due to the modifications. Results show the effect of these modifications on the composite and its constituents, cryogenic treatment on the organic fibre reinforcements showed increased moisture resistance, higher cellulose composition and mechanical properties, exposing the potential of using organic fibre-reinforced polymer composite in Mining applications.

Influence of a hydroelectric dam on fish mercury contamination along the Sinnamary River (French Guiana)

The Petit Saut hydroelectric dam and the upstream and downstream areas of the Sinnamary River in French Guiana (Amazon basin) have been studied from 1993 to 2020. The nearly thirty-years-long study of the monitoring of total mercury concentration in fish and the physicochemical survey of the environment made it possible to demonstrate the impact of the flooding of the forest and the role of the hydroelectric dam on the methylation of mercury. Results show that the physicochemical modifications generated by the construction of the dam led to a significant production of methylmercury (MeHg) in the anoxic part of the reservoir and downstream of the river leading to a strong spatio-temporal impact of the dam. Seven species of fishes are studied and their mercury concentrations vary according to many parameters: fish diet, position in the water column, site, lake oxycline level and time.

Physico-chemical surface modification of the natural leather using gliding arc discharge: An in-depth analysis of improving surface and mechanical properties

Leather, a widely used material in various industries, presents challenges in terms of dye uptake, hydrophilicity, and environmental concerns associated with chemical wet processing. In this context, non-thermal plasma technology offers a promising alternative for leather surface modification. In this study, the gliding arc, with air and water vapor plasmas, was used for the surface modification of natural leather for the first time. The influence of the treatment time and also the plasma gas chemistry on the surface chemical bonding, surface morphology, wettability, water absorption time and absorption capacity, color, and mechanical properties of the leather were investigated. The results showed that in the water vapor gliding arc discharge, the produced active oxygen and hydroxyl species can effectively react with the functional groups and break the relatively weak hydrocarbon CH bonds in the chemical composition of the natural leather. SEM images showed increased pore depth and diameter on the leather surface after air and water vapor plasma treatment with mean diameters of 76 μm and 92 μm, respectively. The tensile stress-strain curves illustrated that despite small cracks were created on the plasma treated samples, the elongation at break (ultimate strain) increased from 83.7 % to 88.5 % and 91.8 % for the samples treated with the air and the water vapor plasmas for 5 min, respectively. The water contact angle decreased from 96° to 55° and 48° after only 5-second treatment with the air and the water vapor plasmas, respectively. The same trend was also observed for the water absorption time and the absorption capacity of the treated samples. Also, the color analysis showed that the color change in the plasma treated samples was not detected by the unaided eye. It was also found that water vapor plasma has a better influence on the physico-chemical properties of the leather.

Effect of steam explosion and silanization of hemp fibers on polylactic acid biocomposites; analysis of mechanical-thermal properties and fungal biodegradation

Alkaline pretreated hemp fibers were modified by steam explosion and/or silanization before being compounded with polylactic acid (PLA). The fungal biodegradation of the PLA/hemp fibers composite was investigated using Aspergillus niger TISTR 3153 in an aqueous medium for 28 days, following the ISO 846: 1997 standard method. The influence of the different physicochemical modifications of hemp fibers on the fungal biodegradation of the composite was evaluated in terms of molecular weight, chemical structure, mechanical properties, thermal properties, and hygroscopic properties. The results showed that the modulus of all composites were averagely increased by 109%, compared to neat PLA. All the PLA/hemp fiber composites better retained their properties after fungal biodegradation than neat PLA. Therefore, the physicochemical treatments of fibers after alkaline pretreatment promoted the resistance of the composite to fungal biodegradation. The treatment of hemp fibers in the present work was alkalization followed by silanization, which resulted in a PLA-based composite that was suitable for outdoor applications.

Cell wall polysaccharides, phenolic extractability and mechanical properties of Aleatico winegrapes dehydrated under sun or in controlled conditions

Aleatico is an Italian red winegrape variety traditionally used partially dehydrated to produce Passito wines. The aim of this research is to assess the effect of two different off-vine withering techniques (natural sun-exposed: SUN, and controlled temperature and humidity conditions: CTR) on grapes physicochemical modifications, focusing on mechanical properties, phenolic profile, and cell-wall polysaccharide structures. The composition and extractability of polyphenols were studied before and after the two withering processes, differentiating the tissues (skin, pulp, seeds). A stronger effect on cell-wall polysaccharides composition pectin was highlighted by chemical and immunochemical approaches in SUN skins at the level of pectin chains and de-esterification, affecting grapes mechanical properties, especially for skin rigidity (<Esk). Sun-dehydrated grapes showed the highest pH (about 0.3 units more than FRESH and CTR), and the lowest acidity (−0.71 g/L vs FRESH) and anthocyanin content in wine-like solution (−41%), whereas these parameters were better preserved in controlled conditions. Instead, seeds tannins were higher in SUN than other samples, with a lower oligomers/polymers ratio. Indeed, after withering the phenolic extractability decreased in skins (total phenolics: from 60% for FRESH to 40% for SUN; anthocyanins: from 72% for FRESH to 46% for SUN) and increased in seeds (total phenolics: from 30% for FRESH to 41% for SUN) compared with fresh samples, in both cases more markedly for SUN than CTR. Skin phenolic composition after 10 days of simulated-maceration was affected by the combination of the loss/concentration balance, together with their modified release in the wine-like solution. As regards seeds, instead, the differences highlighted by the extractable profiles were due to the modified extractability as consequence of the different withering conditions and not to chemical quantitative/qualitative modifications of phenolic compounds caused by dehydration.

Photocatalytic aqueous environmental remediation via two-dimensional carbon nitride nanosheets

Graphitic carbon nitride (GCN) has garnered considerable attention across diverse fields, particularly in photocatalysis for energy and environmental applications, due to its unique physicochemical properties. Among the various structural engineering strategies applied to GCN, two-dimensional (2D) nanosheet design stands out as a fascinating direction due to the 2D geometric advantages. This review explicitly explores the various synthetic (classified as bottom-up and top-down) and physicochemical structural modification methods of GCN-NS matrix and their based composites, as well as their application in photocatalytic remediation of aqueous pollutants. The features of these synthetic strategies in the formation of 2D GCN-NS are first compared. Different modification strategies of GCN-NS, such as surface modification, crystal structure design, doping and heterojunction construction, are summarized. Furthermore, the structure-activity relationship of GCN-NS in various photocatalytic water treatments regarding light absorption, carrier transport and catalytic reaction paths is discussed. Lastly, the developed perspectives are described, including the challenge of GCN-NS-based materials. We expect this review to provide guidelines and inspirations for preparing, modifying, and utilizing two-dimensional GCN materials in the photocatalytic field.

Hydrophilic–Hydrophobic Properties of the Surface of Modified Carbonate Fillers for Asphalt

The physicochemical modification of the filler allows changing the hydrophilic–hydrophobic properties and effectively influencing the processes occurring at the filler–binder interface, on which the physicomechanical characteristics of composites largely depend. The paper presents studies related to the modification of limestone-based filler effect on the degree of its hydrophobicity and wetting with liquids of different polarity, establishing the relationship between the characteristics of hydrophobized mineral powders and the adsorption capacity in relation to water. Using mechanochemical processing with hydrophobic components GF-1 and GF-2, it was possible to obtain fillers with a sufficiently high content of hydrophobic particles (58.2% and 85.9%, respectively). It was found that the results of the contact angle (123.6° and 114.5°, respectively) and the degree of hydrophobicity do not quite correlate with each other. It was noticed that the contact angle on the powder modified with GF-1 decreases with time. Studies of the powders’ thermal effects wetting of different polarity liquids via microcalorimetry allows us to establish that with an increase in the filler hydrophobicity degree, the integral heat of immersion decreases due to a significant decrease in the probability of chemical interactions between water and powder due to the adsorption of applied surfactants molecules on the limestone active centers. The revealed endothermic effects indicate the occurrence of physical interactions due to non-polar dispersion forces. Differences in the nature of heat release and heat absorption in modified fillers indicate significant differences in the composition and mechanism of action of the used surfactants, which affected the efficiency of hydrophobization. At the same time, a linear dependence of the moisture absorption and moisture indicators, determined by independent experiments, on the degree of hydrophobicity was established.

Living Cell‐Derived Intelligent Nanobots for Precision Oncotherapy

AbstractThe progress of precision oncology medicine is always limited by the tumor off‐targeting, the drug side effects, and the treatment inefficiency due to the complex and ever‐changing tumor microenvironment. Living cells, such as blood cells and immune cells, exhibit natural tumor tropism, controllable physicochemical modification, and excellent biocompatibility, which provide an advantageous pathway for innovative and efficient tumor suppression. Armed with nanoengineering techniques, artificial living cells harness their inherent biological properties to precisely identify and eradicate tumors, demonstrating broad biological application prospects and great transformational potential in personalized cancer therapy. Here, the recent advances of living cell‐based bionanobots including platelets, red blood cells, neutrophil, macrophage, and CAR‐T cells for cancer precision therapy and immune regulation are summarized, and the efficient anti‐tumor strategies for engineering living cell nanorobots to overcome complex biological barriers and immune suppression are also outlined (e.g., immunotherapy, sonodynamic therapy, chemo/radiotherapy, and phototherapy). In addition, the study discusses the advantages, limitations, and current challenges of artificial living cell‐based drug delivery systems, and provide perspectives on the future development of living cell‐mediated precision tumor nanomedicine.

Application of chitosan-based materials in wastewater treatment

Chitosan, as a natural polysaccharide material, plays a great role in the field of wastewater treatment due to its good biodegradability, antimicrobial activity, and other properties. However, it may have some differences in the processes of adsorption, flocculation, and membrane separation. We comprehensively describe the application effect and mechanism of action of chitosan-based materials on the above three major water treatment processes. In the adsorption process, chitosan-based adsorbents such as hydrogels and chitosan beads are prepared by cross-linking, impregnation, and the introduction of functional groups. These chitosan-based materials exerted efficient removal performance in the adsorption of heavy metals, organic dyes, anionic pollutants, etc., which was attributed to their large specific surface area and abundant functional groups. In the flocculation process, the chitosan-based materials were modified by grafting and modifying their shape, while heavy metal ions, organic dyes, and algae were removed using processes such as chelation and charge neutralization. In the membrane separation process, a number of nanofiltration and microfiltration membranes were created by coating chitosan ions, and physicochemical modification was done for the separation of heavy metal ions and emulsified oil droplets in water to improve the fouling resistance and retention rate of the membrane materials. This paper reviews the application of chitosan-based materials in wastewater treatment and proposes that in-depth studies on their toxicity and reusability should be conducted in the future, with a view to playing a role in areas such as the removal of malodorous water odors.