Effect of Antisolvent Used to Regenerate Cellulose Treated with Ionic Liquid on Its Properties.

The solvolysis reaction with ionic liquids is one of the most frequently used methods for producing nanometer-sized cellulose. In this study, the nanocellulose was obtained by reacting microcrystalline cellulose with 1-ethyl-3-methylimidazolium acetate (EmimOAc). The aim of this research was to determine the influence of various antisolvents used in the regeneration of cellulose after treatment with ionic liquid on its properties. The following antisolvents were used in this research: acetone, acetonitrile, water, ethanol and a mixture of acetone and water in a 1:1 v/v ratio. The nanocellulose was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), dynamic light scattering (DLS), scanning electron microscopy (SEM) and elemental analysis (EA). The results show that the antisolvent used to regenerate cellulose after the solvolysis reaction with EmimOAc affects its properties. Water, ethanol and a mixture of acetone and water successfully removed the used ionic liquid from the cellulose structure, while acetone and acetonitrile were unable to completely remove EmimOAc from the cellulosic material. The results of the XRD analysis indicate that there is a correlation between the ionic liquid content in the regenerated cellulose and its degree of crystallinity. Among the tested solvents, water leads to the effective removal of EmimOAc from the cellulose structure, which is additionally characterized by the smallest particle size and non-formation of agglomerates.

The effect of polylactic acid ordering on the long-term corrosion protection capacity of biodegradable magnesium alloys.

The polylactic acid (PLA) coatings of different crystallinity were prepared on biodegradable Mg-2.2Zn-0.3Ca alloy wires to improve the long-term anti-corrosion properties. The composition characteristics and microstructure of the samples were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscope (FTIR), wide angle X-ray diffraction (WAXD) and scanning electron microscope (SEM). The corrosion resistance of all samples was investigated by immersion tests and electrochemical techniques in vitro simulated body fluid (SBF). The results indicated heat treatment improved the crystallinity of PLA coating and heated-coating performed protective behaviors in the short and long-term immersion. The corrosion rate of heated samples was lower than that of unheated samples and exhibited superior long term protective effect for Mg alloy wires. The lifetime of heated sample (H2) increased significantly from 33 to 55 days. The initial electrochemical performance of unheated coating was better than heated coating, but it declined more rapidly during the long-term immersion. These results indicated that PLA coating could not ignore the effect of its crystallinity to anti-corrosion ability, and only the suit heat treatment makes PLA coating more ordering and achieves higher corrosion resistance in vitro immersion. Therefore, it has promising potential by controlling effectively the PLA ordering for surgical implant applications.

Effect of non-thermal acidic and alkaline modifications on the structural, pasting, rheological, and functional properties of cassava (Manihot esculenta) starch.

This study aimed to investigate the effects of acid or alkali modification of isolated cassava starch (ICS) on its physicochemical properties. Acetic acid concentrations of 5%, 10%, and 20% v/v (0.87, 1.73, and 3.46 M, respectively) and calcium hydroxide concentrations of 0.15%, 0.20%, and 0.30% w/w (0.02, 0.025, and 0.04 M, respectively) were tested independently and compared with untreated isolated starch. The scanning electron microscope (SEM) shows starches with polyhedral and semispherical shapes; these modifications do not change the surface of the starch granules. Nanocrystals with orthorhombic crystal structure were extracted from ICS. Transmission electron microscopy (TEM) shows crystallites with a size (two-dimensional) of 20 ± 5 nm in length and 10 ± 2 nm in width and reveals that this starch contains nanocrystals with orthorhombic crystal structure. The X-ray patterns show that these nanocrystals are unaffected by acidic or alkaline treatments. The Ca+2 and CH3COO- ions do not interact with these nanocrystals. The alkaline treatment only affects the gelatinization temperature at a Ca(OH)2 concentration of 0.30%. Low concentrations of acidic and alkaline treatments affect the ability of cassava starch to absorb water and reduce the peak and final viscosity. The infrared spectra show that the modifications lead to C-H and C═C bond formations. ICS-B 0.30 can modify the amorphous regions of the starch, and the acid treatment leads to acetylation, which was confirmed by the presence of an IR band at 1740 cm-1.

Optimization of Heat-Moisture Treatment Conditions for High-Amylose Starch and Its Application in High-Resistant Starch Triticale Noodles.

Heat-moisture treatment (HMT) is a widely used method for modifying starch properties with the potential to reduce the digestibility of high-amylose starch (HAS). This study aimed to optimize the HMT conditions for HAS and apply the resulting HMT-HAS to triticale noodles to develop low-glycemic-index products. HMT significantly increased the resistant starch (RS) content and decreased the rapidly digestible starch (RDS) content of HAS. The treatment conditions-temperature, heating time, and moisture content-were found to significantly influence the starch composition. Optimal HMT conditions were determined using response surface methodology: a temperature of 108 °C, a heating time of 5.8 h, and a moisture content of 25.50%. Under these conditions, the RS content of HMT-HAS was 60.23%, nearly double that of the untreated sample. Increasing the level of HMT-HAS in triticale noodles led to significant decreases in short-range order, relative crystallinity, and viscosities, while the RS content increased from 12.08% to 34.41%. These findings suggest that incorporating HMT-HAS into triticale noodles effectively enhances starch digestive resistance, supporting the development of functional, low-glycemic-index triticale-based foods.

Assessment of Changes in Selected Features of Pine and Birch Wood after Impregnation with Graphene Oxide.

In this work, pine and birch wood were modified by graphene oxide using a single vacuum impregnation method. The research results indicate that the impregnation of wood with graphene oxide increases the crystallinity of cellulose in both pine and birch wood, and the increase in crystallinity observed in the case of birch was more significant than in the case of pine. FT-IR analyses of pine samples impregnated with graphene oxide showed changes in intensity in the absorption bands of 400-600, 700-1500 cm-1, and 3200-3500 cm-1 and a peak separation of 1102 cm-1, which may indicate new C-O-C connections. In the case of birch, only some differences were noticed related to the vibrations of the OH group. The proposed modification also affects changes in the color of the wood surface, with earlywood containing more graphene oxide than latewood. Analysis of scanning electron microscope images revealed that graphene oxide adheres flat to the cell wall. Considering the differences in the anatomical structure of both wood species, the research showed a statistically significant difference in water absorption and retention of graphene oxide in wood cells. Graphene oxide does not block the flow of water in the wood, as evidenced by the absorbability of the working liquid at the level of 580-602 kg/m3, which corresponds to the value of pure water absorption by wood in the impregnation method using a single negative pressure. In this case, higher graphene oxide retention values were obtained for pine wood.

Modification of the Surface Crystallinity of Polyphenylene Sulfide and Polyphthalamide Treated by a Pulsed-Arc Atmospheric Pressure Plasma Jet.

Atmospheric plasma jets generated from air or nitrogen using commercial sources with relatively high energy densities are commonly used for industrial applications related to surface treatments, especially to increase the wettability of polymers or to deposit thin films. The heat fluxes to which the substrates are subjected are typically in the order of 100-300 W/cm2, depending on the treatment conditions. The temperature rise in the treated polymer substrates can have critical consequences, such as a change in the surface crystallinity or even the surface degradation of the materials. In this work, we report the phase transitions of two semicrystalline industrial-grade polymer resins reinforced with glass fibers, namely polyphenylene sulfide (PPS) and polyphthalamide (PPA), subjected to plasma treatments, as well as the modeling of the associated heat transfer phenomena using COMSOL Multiphysics. Depending on the treatment time, the surface of PPS becomes more amorphous, while PPA becomes more crystalline. These results show that the thermal history of the materials must be considered when implementing surface engineering by this type of plasma discharge.

Patterning of Organic Semiconductors Leads to Functional Integration: From Unit Device to Integrated Electronics.

The use of organic semiconductors in electronic devices, including transistors, sensors, and memories, unlocks innovative possibilities such as streamlined fabrication processes, enhanced mechanical flexibility, and potential new applications. Nevertheless, the increasing technical demand for patterning organic semiconductors requires greater integration and functional implementation. This paper overviews recent efforts to pattern organic semiconductors compatible with electronic devices. The review categorizes the contributions of organic semiconductor patterning approaches, such as surface-grafting polymers, capillary force lithography, wettability, evaporation, and diffusion in organic semiconductor-based transistors and sensors, offering a timely perspective on unconventional approaches to enable the patterning of organic semiconductors with a strong focus on the advantages of organic semiconductor utilization. In addition, this review explores the opportunities and challenges of organic semiconductor-based integration, emphasizing the issues related to patterning and interconnection.

Influence of crystalline properties on starch functionalization from the perspective of various physical modifications: A review.

The relationship between structural properties and functional characteristics of starch remains a hot subject among researchers. The crystalline property is a substantial characteristic of starch granules, undergoing different changes during modification techniques. These changes are closely related to the functional properties of modified starches. Physical modifications are eco-friendly techniques and are widely adopted for starch modifications. Therefore, understanding the impact of changes in crystalline properties during different physical modifications on starch functionality is the ultimate way to improve their industrial utilization. However, the existing literature still lacks the elucidation of changes in functional properties of starch in accordance with its crystalline properties during different physical treatments. Hence, this review summarizes the effects of the most important and widely used physical modifications on starch crystalline properties, highlighting the alterations in various functional properties such as hydration, pasting, gelatinization, and in vitro digestibility resulting from changes in crystalline characteristics in a single comprehensive discussion. Furthermore, the current review gives direction for envisaging the functionalization of starches based on deviations in the crystalline properties during several physical treatments.

Chemical characterization of hibiscus rosa-sinensis plant fibers facilitated through design of experiments and artificial neural network hybrid approach.

The integration of natural fibers into Fiber Reinforced Polymers (FRPs) has emerged as a promising avenue for sustainable and high-performance composite materials. Natural fibers, derived from plants, offer notable advantages such as renewability, low cost, and environmental friendliness. Among these natural fibers, Hibiscus Rosa-Sinensis (HRS) plant fibers have gained significant attention owing to their widespread availability and unique mechanical properties. In this study, HRS fibers were chemically treated using Sodium Hydroxide (NaOH), Potassium Permanganate (KMnO4), and Acetic Acid (CH3COOH) at different weight percentages (3, 4, 5 Wt.%) and solutionizing times (1, 2, 3 h) based on Taguchi's L27 orthogonal array. The fibers, extracted from epidermis of the stems, underwent cleaning and chemical treatment after water retting. The crystallinity index, determined via X-ray Diffraction (XRD), indicated a maximum value of 65.77%. Thermo-gravimetric analysis (TGA) exhibited a degradation temperature of 365.24 °C and a material loss of 63.11%. Potassium Permanganate treatment at 4 Wt.% and 3 h of solutionizing time has yielded the best results. Multi-Layer Perceptron Artificial Neural Network (MLP-ANN) has been successfully applied to accurately predict the output physical characteristics of chemically treated HRS fibers using experimental data. The results are in close alignment with the literature. Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS) analyses have provided valuable insights into the microstructure and constituents of the chemically treated HRS fibers. This research emphasises on the effectiveness of the chemical treatment process in enhancing the properties of HRS plant fibers for potential composite applications.

Synergistically Improved Crystallinity and Molecular Doping Ability of Polythiophene-Diketopyrropyrrole Derivatives by m-Trifluoromethylbenzene Containing Side Chains for Improved Thermoelectric Materials.

m-Trifluoromethylbenzene (FB) groups have been widely employed in various fields; however, no studies have reported the use of FB in side chains to enhance the carrier mobility and molecular doping of conjugated polymers. In this study, based on density functional theory (DFT) calculations, we discovered that FB groups can effectively bind to [FeCl4]-, the counterion of the p-type dopant FeCl3, thereby increasing doping ability. Consequently, FB groups were incorporated into the side chains of thiophene-diketopyrrolopyrrole-based donor-acceptor (D-A)-conjugated polymers, and a series of random conjugated polymers were synthesized (denoted as PDPPFB-x, where x represents the molar ratio of the FB side chain). The findings revealed that an appropriate number of FB groups can decrease the π-π stacking distances, enhance the films' crystallinity, and consequently improve the charge transfer ability. Furthermore, after doping with FeCl3, the UV-vis-NIR spectra indicated that the doping efficiency was augmented by increasing the molar fraction of the FB side chain. Among these polymers, PDPPFB-10 exhibited the highest conductivity and power factor, which were 2.0 and 1.5 times higher than those of PDPPFB-0, respectively. These results illustrated a straightforward molecular design strategy for enhancing the crystallinity and conductivity of conjugated polymers, thereby expanding the way to optimize their thermoelectric performance.

Influence of Glycerol on the Surface Morphology and Crystallinity of Polyvinyl Alcohol Films.

The structure and physicochemical properties of polyvinyl alcohol (PVA) and PVA/glycerol films have been investigated by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetry/differential thermal analysis (TG/DTA), and advanced scanning probe microscopy (SPM). In the pure PVA films, SPM allowed us to observe ribbon-shaped domains with a different frictional and elastic contrast, which apparently originated from a correlated growth or assembly of PVA crystalline nuclei located within individual PVA clusters. The incorporation of 22% w/w glycerol led to modification in shape of those domains from ribbon-like in pure PVA to rounded in PVA/glycerol 22% w/w films; changes in the relative intensities of the XRD peaks and a decrease in the amorphous halo in the XRD pattern were also detected, while the DTA peak corresponding to the melting point remained at almost the same temperature. For higher glycerol content, FT-IR revealed additional glycerol-characteristic peaks presumably related to the formation of glycerol aggregates, and XRD, FT-IR, and DTA all indicated a reduction in crystallinity. For more than 36% w/w glycerol, the plasticization of the films complicated the acquisition of SPM images without tip-induced surface modification. Our study contributes to the understanding of crystallinity in PVA and how it is altered by a plasticizer such as glycerol.

Mechanical Properties and Crystallinity of Specific PLA/Cellulose Composites by Surface Modification of Nanofibrillated Cellulose.

Polylactic acid (PLA) has inherent drawbacks, such as its amorphous structure, which affect its mechanical and barrier properties. The use of nanofibrillated cellulose (NFC) mixed with PLA for the production of composites has been chosen as a solution to the above problems. A PLA/NFC composite was produced by solution casting. Before use, the cellulose was modified using a silane coupling agent. The composite films were investigated via X-ray diffraction, as well as by mechanical, physical, thermal analyses and by differential scanning calorimeter. The crystallinity was four times that of pure PLA and the water vapor transmission rate decreased by 76.9% with the incorporation of 10 wt% of NFC. The tensile strength of PLA/NFC blend films increased by 98.8% with the incorporation of 5 wt% of NFC. The study demonstrates that the addition of NFC improved the properties of PLA. This provides a solid foundation for the enhancement of the performance of PLA products.

Piezoelectric Properties of As-Spun Poly(vinylidene Fluoride)/Multi-Walled Carbon Nanotube/Zinc Oxide Nanoparticle (PVDF/MWCNT/ZnO) Nanofibrous Films.

Conductive multi-walled carbon nanotubes (MWCNTs) as well as piezoelectric zinc oxide (ZnO) nanoparticles are frequently used as a single additive and dispersed in polyvinylidene fluoride (PVDF) solutions for the fabrication of piezoelectric composite films. In this study, MWCNT/ZnO binary dispersions are used as spinning liquids to fabricate composite nanofibrous films by electrospinning. Binary additives are conducive to increasing the crystallinity, piezoelectric voltage coefficient, and consequent piezoelectricity of as-spun films owing to the stretch-enhanced polarization of the electrospinning process under an applied electric field. PCZ-1.5 film (10 wt. % PVDF/0.1 wt. % MWCNTs/1.5 wt. % ZnO nanoparticles) contains the maximum ß-phase content of 79.0% and the highest crystallinity of 87.9% in nanofibers. A sensor using a PCZ-1.5 film as a functional layer generates an open-circuit voltage of 10 V as it is subjected to impact loads with an amplitude of 6 mm at 10 Hz. The piezoelectric sensor reaches a power density of 0.33 µW/cm2 and a force sensitivity of 582 mV/N. In addition, the sensor is successfully applied to test irregular motions of a bending finger and stepping foot. The result indicates that electrospun PVDF/MWCNT/ZnO nanofibrous films are suitable for wearable devices.

Research on the Thermal Aging Mechanism of Polyvinyl Alcohol Hydrogel.

Polyvinyl alcohol (PVA) hydrogels find applications in various fields, including machinery and tissue engineering, owing to their exceptional mechanical properties. However, the mechanical properties of PVA hydrogels are subject to alteration due to environmental factors such as temperature, affecting their prolonged utilization. To enhance their lifespan, it is crucial to investigate their aging mechanisms. Using physically cross-linked PVA hydrogels, this study involved high-temperature accelerated aging tests at 60 °C for 80 d and their performance was analyzed through macroscopic mechanics, microscopic morphology, and microanalysis tests. The findings revealed three aging stages, namely, a reduction in free water, a reduction in bound water, and the depletion of bound water, corresponding to volume shrinkage, decreased elongation, and a "tough-brittle" transition. The microscopic aging mechanism was influenced by intermolecular chain spacing, intermolecular hydrogen bonds, and the plasticizing effect of water. In particular, the loss of bound water predominantly affected the lifespan of PVA hydrogel structural components. These findings provide a reference for assessing and improving the lifespan of PVA hydrogels.

High aspect ratio cellulose nanofibrils with low crystallinity for strong and tough films.

Cellulose nanofibril (CNF) films with both high strength and high toughness are attractive for applications in energy, packaging, and flexible electronics. However, simultaneously achieving these mechanical properties remains a significant challenge. Herein, a multiscale structural optimization strategy is proposed to prepare high aspect ratio CNFs with reduced crystallinity for strong and tough films. Carboxymethylation coupled with mild mechanical disintegration is employed to modulate the multiscale structure of CNFs. The as-prepared CNFs feature an aspect ratio of >800 and a crystallinity of <60 %. The film prepared using CNFs with a high aspect ratio (~1100) and reduced crystallinity (~54 %) exhibits a tensile strength of 229.9 ± 9.9 MPa and toughness of 22.2 ± 1.4 MJ/m3. The underlying mechanism for balancing these mechanical properties is unveiled. The high aspect ratio of the CNFs facilitates the transfer and distribution of local stress, thus endowing the corresponding film with high strength and toughness. Moreover, the low crystallinity of the CNFs permits the movement of the cellulose chains in the amorphous regions, thereby dissipating energy and finally increasing the film toughness. This work introduces an innovative and straightforward method for producing strong and tough CNF films, paving the way for their broader applications.

Prospects of crude enzymes in replacing pure enzymes for dissolving pulp production.

High-purity cellulose from paper pulp can be obtained after appropriate treatments involving pure xylanases and cellulases/endoglucanases. This study investigated the efficacy of using crude xylanase and cellulase instead of commercial ones to improve process economics. Kraft paper grade pulp produced from veneer waste, hardwood, and non-wood sources was utilized as a more sustainable option. Crude xylanase and cellulase from isolated soil bacteria Bacillus pumilus 3GAH and Bacillus subtilis PJK6 were used for process optimization. The correlation between Fock reactivity, chain scission, and crystallinity after crude-cellulase treatment was established through chemical, FTIR, and XRD analyses. Pentosans in kraft pulp were reduced from an initial 18.7% to 4.9% through sequential treatments with crude xylanase and alkali. Subsequent crude-cellulase treatment, even at 8 U/g o.d. pulp, improved Fock reactivity from 28.2% to 61.2%, fulfilling a major criterion for viscose. Thus, crude enzymes can be effectively used for the efficient and economical upgrading of paper pulp to dissolving pulp.

Enhanced Fenton-like reactions via interface electron reconstruction in low-crystallinity FeCo bimetallic metal-organic frameworks: Bidirectional control of Fe (III) and Co (II) sites.

In this study, the activity and stability of Fenton-like reactions are enhanced by constructing a low-crystallinity FeCo bimetallic metal-organic framework (FeCox-BDC (BDC denotes as terephthalic acid)) through interface electron reconstruction. However, the specific origins and mechanisms of their enhanced activity, particularly in Fenton-like reactions, remains unclear. Systematic analysis revealed that the isomorphic substitution of Co (II) reduces the coordination number and d-electron count at local Fe (III) sites, shifting the d-band centers (-1.59 eV) closer to the Fermi level. Additionally, Co 3d-orbitals can accept electrons, improving the occupation of antibonding orbitals. Notably, Fe (III) and Co (II) sites exhibit a synergistic effect: Fe (III) sites strongly adsorbed the Oα point of the peroxy bond (lOαOß), while Co (II) sites efficiently activated Oß. Within 5 min, FeCo1/3-BDC achieved a 98 % reduction in Rhodamine-B (RhB), surpassing Fe-BDC by a factor of 76 and homogeneous Fenton catalytic systems (Co (II)/peroxymonosulfate (PMS) and Fe (III)/Co (II)/PMS). This work provides a profound understanding of interface electron reconstruction, offering valuable insights into guiding Fenton-like mechanisms.

Lignocellulose sustainable composites from agro-waste Asparagus bean stem fiber for polymer casting applications: Effect of fiber treatment.

In the past decades, lignocellulose fibers have attracted significant attention due to their low density, environmental friendliness, and biodegradability. Consequently, researchers are intensifying their efforts to explore the potential of lignocellulosic fibers as sustainable alternatives to synthetic fibers in polymer composites. Among various natural fibers identified as potential reinforcements, agro-waste from the Asparagus Bean stem (ABS) which has been discarded as landfill after harvest has emerged as a promising source of lignocellulose fibers for promoting sustainability. This study investigates the reinforcement suitability of ABSF in polymer matrices. A water-retting process was used for extraction, followed by treatment with a 5 % alkali solution. Cellulose content was enhanced to 65 wt%, and fiber density increased to 1.13 g/cm3 after chemical treatment. Thermogravimetric analysis indicated improved thermal stability of the treated fibers up to 247 °C. Morphological analysis showed increased surface roughness and impurity removal. To evaluate the reinforcing effect of the chemical treatment, epoxy composites with 10 wt% reinforcement were developed. The mechanical properties of these composites improved significantly, with more than 1.1 times when used alkali-treated ABSF as reinforcement. Flexural properties were substantially enhanced, with flexural strength increasing from 90.53 MPa to 122.71 MPa and flexural modulus from 2.41 GPa to 2.95 GPa due to better fiber-matrix interaction and removal of weak, amorphous constituents. The primary objective of this study is to demonstrate that ABSF is a viable alternative raw material for composite reinforcement, suitable for developing lightweight structural applications.

Anti-solvent materials enhanced structural and optical properties on ambiently fabricated perovskite thin films.

Perovskite solar cells (PSCs) hold potential for low-cost, high-efficiency solar energy, but their sensitivity to moisture limits practical application. Current fabrication requires controlled environments, limiting mass production. Researchers aim to develop stable PSCs with longer lifetimes under ambient conditions. In this research work, we investigated the stability of perovskite films and solar cells fabricated and annealed in natural air using four different anti-solvents: toluene, ethyl acetate, diethyl ether, and chlorobenzene. Films (about 300 nm thick) were deposited via single-step spin-coating and subjected to ambient air-atmosphere for up to 30 days. We monitored changes in crystallinity, electrical properties, and optics over time. Results showed a gradual degradation in the films' crystallinity, morphology, and electro-optical properties. Notably, films made with ethyl acetate exhibited superior stability compared to other solvents. These findings contribute to advancing stable and high-performance PSCs manufactured under normal ambient conditions. In addition, we also discuss the possible machine learning (ML) approach to our future work direction to optimize the materials structures, and synthesis process parameters for future high-efficient perovskite solar cells fabrication.

Investigation of the link between first-order kinetic models of the in vitro digestion of native starches and the accompanying changes in their crystallinity and structure.

Starch is the main source of dietary energy for humans. In order to understand the mechanisms governing native starch in vitro digestion, digestion data for six starches [wheat, maize, (waxy) maize, rice, potato and pea] of different botanical sources were fitted with the most common first-order kinetic models, i.e. the single, sequential, parallel and combined models. Parallel and combined models provided the most accurate fits and showed that all starches studied except potato starch followed a biphasic in vitro digestion pattern. The biological relevance of the kinetic parameters was explored by determining changes in crystallinity and molecular structure of the undigested starch residues during in vitro digestion. While the crystallinity of the undigested potato starch residues did not change substantially, a respectively small and large decrease in their amylose content and chain length during in vitro digestion was observed, indicating that amylose was digested slightly preferentially over amylopectin in native starch. However, the molecular structure of the starch residues changed too slowly and/or only to an insufficient extent to relate it to the kinetic parameters of the digested fractions predicted by the models. Such parameters thus need to be interpreted with caution, as their biological relevance still needs to be proven.