Probing the influence of composition and cross-linking degree on single-chain nanoparticles from poly(tetrahydrofuran-ran-epichlorohydrin) copolymers: Insights from neutron scattering, calorimetry, and dielectric spectroscopy.

The industrial sector has made significant strides in the development of multicomponent and multiphasic polymer materials, including polymer blends, composites (such as nanocomposites), and various copolymers. Random copolymers, characterized by their statistical arrangement of repeating units, are particularly noteworthy due to their tunability from amorphous to semicrystalline states. In this study, we focus on poly(tetrahydrofuran-ran-epichlorohydrin) (P(THF-ran-ECH)) copolymers, which serve as precursors for single-chain nanoparticles (SCNPs). These SCNP-based materials are of particular interest as they bridge the gap between traditional polymers and colloids. This research comprehensively investigates how the type and degree of internal cross-linking influence the structure and dynamics of P(THF-ran-ECH) copolymers and their SCNPs. Techniques such as quasielastic neutron scattering (QENS), differential scanning calorimetry (DSC), and broadband dielectric spectroscopy (BDS) were employed to study copolymers with varying compositions and levels of cross-linking. By analyzing two samples with different epichlorohydrin (ECH) contents (13 mol% and 27 mol%), we aim to control crystallization and explore its effects on dynamic behavior. Our results show that both the composition and the degree of cross-linking significantly impact the dynamics of the SCNPs, with SCNPs exhibiting slower dynamics compared to their precursor copolymers. Furthermore, semicrystalline samples display faster dynamics in SCNPs than amorphous samples. These findings provide valuable insights for the design and optimization of advanced multicomponent polymer systems.

Complexity of confined water vitrification and its glass transition temperature.

The ability of vitrification when crossing the glass transition temperature (Tg) of confined and bulk water is crucial for myriad phenomena in diverse fields, ranging from the cryopreservation of organs and food to the development of cryoenzymatic reactions, frost damage to buildings, and atmospheric water. However, determining water's Tg remains a major challenge. Here, we elucidate the glass transition of water by analyzing the calorimetric behavior of nano-confined water across various pore topologies (diameters: 0.3 to 2.5 nm). Our approach involves subjecting confined water to annealing protocols to identify the temperature and time evolution of nonequilibrium glass kinetics. Furthermore, we complement this calorimetric approach with the dynamics of confined water, as seen by broadband dielectric spectroscopy and linear calorimetric measurements, including the fast scanning technique. This study demonstrated that confined water undergoes a glass transition in the temperature range of 170 to 200 K, depending on the confinement size and the interaction with the confinement walls. Moreover, we also show that the thermal event observed at ~136 K must be interpreted as an annealing prepeak, also referred to as the "shadow glass transition." Calorimetric measurements also allow the detection of a specific heat step above 200 K, which is insensitive to annealing and, thereby, interpreted as a true thermodynamic transition. Finally, by connecting our results to bulk water behavior, we offer a comprehensive understanding of confined water vitrification with potential implications for numerous applications.

P(MMA-co-MAA)/cellulose nanofibers composites: Effect of hydrogen bonds on molecular mobility.

Cellulose nanofibers (CNFs) nanocomposites were prepared using poly(methylmethacrylate-co-methacrylic acid) (PMMA-co-MAA) to investigate the macromolecular mobility within the composite, with particular focus on the effect of H-bonding. Dynamic mechanical analysis (DMA) and broadband dielectric spectroscopy (BDS) were used to fully characterize the molecular mobility for which the effect of the introduction of H-bond forming moieties and the addition of CNFs (5 and 15 wt%) were assessed. Despite similar Tg values (determined by Differential Scanning Calorimetry), a deeper analysis of the relaxation times associated with the α-relaxation evidenced a significant effect induced by CNFs, which is in fact slowing down the macromolecular relaxation processes. The activation energy of the ß-relaxation remained unchanged despite the introduction of MAA units in the main chain and the successive addition of CNFs. However, the latter led to the appearance at low frequencies of a new ß'-relaxation correlated with the interactions between the CNF surface -OH groups and the -COOH groups of the matrix. The γ-relaxation showed a 45 % increase in activation energy from PMMA to PMMA-co-MAA + CNF nanocomposites regardless of the CNF content, due to the possibility of CNFs to interact and hinder the motion of the main chain methyl groups in α position.

An experimental toolbox for the physical characterization of thermal insulating polymeric foams.

Recent advancements in polymer science and manufacturing technologies triggered new developments of porous materials used for mitigating heat losses, such as thermal insulating polymeric foams. The major bottleneck in the optimization of these products, however, remains the absence of analytical methods able to scrutinize their large design space reasonably quickly and cost-effectively. This manuscript targets the paucity of data for polymeric foams by illustrating, at a proof-of-principle level, that several well-established analytical methods including optical microscopy, pycnometry, dielectric spectroscopy, thermogravimetric analysis, and nuclear magnetic resonance can be exploited for an extensive, yet logistically efficient, characterization of these materials. The purpose of this study is thus introducing an experimental platform for the characterization of market foam products and for the development of new polymeric foams with pore sizes that are particularly relevant for industrial and residential thermal insulation. Since this work introduces several new methodologies, it may be used as a guide for both laboratory users and specialists in the field, who may further improve the herein proposed experimental concepts.

Image of the solid-state rotary motion encoded in the dielectric response.

The future development of advanced molecular systems with controlled rotation requires the development of an effective methodology for assessing the rotational performance of artificial machine components. We identified two patterns of the dielectric behavior for polar rotators in a static non-polar framework of sizable crystal showing relations between the spectral and molecular-level features of solid-state rotary motion. Various functionalization of phenylene rotors with a fluorine atom(s) changed rotational performance from high to low with rotational barriers ranging from 6.06 to 11.84 kcal mol-1. The meta-F-substitution favored rotator-rotator contacts allowing for the implementation of fast rotary motion. Contrary, the presence of rotator-stator contacts inhibited independent rotator dynamics leading to opposite spectral behavior in terms of temperature evolution of loss peak amplitude. Our observations, supported by an analysis based on an asymmetric double well-potential model, show that easily noticeable spectral differences encoded some molecular-level information important for the implementation of rotary motion.

Critical Model Insight into Broadband Dielectric Properties of Neopentyl Glycol (NPG).

This report presents the low-frequency (LF), static, and dynamic dielectric properties of neopentyl glycol (NPG), an orientationally disordered crystal (ODIC)-forming material important for the barocaloric effect applications. High-resolution tests were carried out for 173K

Microwave dielectric properties of normal, fibroelastotic, and malignant human lung tissue.

Technological development of microwave treatment and detection techniques for lung cancer requires accurate and comprehensive knowledge of the microwave dielectric properties of human lung tissue. We characterize the dielectric properties of room temperature human lung tissue from 0.5 to 10 GHz for three lung tissue groups: normal, fibroelastotic, and malignant. We fit a two-pole Debye model to the measured frequency-dependent complex permittivity and calculate the median Debye parameters for the three groups. We find that malignant lung tissue is approximately 10% higher in relative permittivity and conductivity compared to normal lung tissue; this trend matches previously reported normal versus malignant data for other biological tissues. There is little contrast between benign lung tissue with fibroelastosis and malignant lung tissue. We extrapolate our data from room temperature to 37 °C using a temperature-dependence model for animal lung tissue and use the Maxwell-Garnett dielectric mixing model to predict the dielectric properties of inflation-dynamic human lung tissue; both approximations correspond with previously reported dielectric data of bovine and porcine lung tissue.

Water rotational relaxation time measurement by shortwave infrared micro spectroscopy(SWIR) at sub-zero temperatures.

The shortwave infrared spectroscopy (SWIR) is the noble method which allows to evaluate the rotational relaxation time of water (RRTW) in a sample. Because SWIR requires the reference sample of pure water, the measurement temperature is limited only at above 0 °C. In this study, we expanded this temperature limitation of SWIR by using alternative reference solutions with freezing points below 0 °C, including sugar and glycerol solutions. The results showed that some reference sample solutions are useable for evaluating RRTW in samples below 0 °C. It was found that RRTW in solution measured by newly proposed SWIR agrees with RRTW measured by dielectric spectroscopy in 10% accuracy when it is shorter than 100psec.

Plasmid DNA Complexes in Powder Form Studied by Spectroscopic and Diffraction Methods.

Currently, new functional materials are being created with a strong emphasis on their ecological aspect. Materials and devices based on DNA biopolymers, being environmentally friendly, are therefore very interesting from the point of view of applications. In this paper, we present the results of research on complexes in the powder form based on plasmid DNA (pDNA) and three surfactants with aliphatic chains containing 16 carbon atoms (cetyltrimethylammonium chloride, benzyldimethylhexadecylammonium chloride and hexadecylpyridinium chloride). The X-ray diffraction results indicate a local hexagonal packing of DNA helices in plasmid DNA complexes, resembling the packing for corresponding complexes based on linear DNA. Based on the Fourier-transform infrared spectroscopy results, the DNA conformation in all three complexes was determined as predominantly of A-type. The two relaxation processes revealed by dielectric spectroscopy for all the studied complexes are connected with two different contributions to total conductivity (crystallite part and grain boundaries). The crystallite part (grain interior) was interpreted as an oscillation of the polar surfactant head groups and is dependent on the conformation of the surfactant chain. The influence of the DNA type on the properties of the complexes is discussed, taking into account our previous results for complexes based on linear DNA. We showed that the type of DNA has an impact on the properties of the complexes, which has not been demonstrated so far. It was also found that the layer of pDNA-surfactant complexes can be used as a layer with variable specific electric conductivity by selecting the frequency, which is interesting from an application point of view.

Novel nano composites from Citrus limon and Citrullus colocynthis agricultural wastes for biomedical applications.

In recent years, academic and industrial research has focused on using agro-waste for energy and new material production to promote sustainable development and lessen environmental issues. In this study, new nanocomposites based on polyvinyl alcohol (PVA)-Starch using two affordable agricultural wastes, Citrus limon peels (LP) and Citrullus colocynthis (Cc) shells and seeds powders with different concentrations (2, 5, 10, and 15 wt%) as bio-fillers were prepared. The nanocomposites were characterized by Dielectric Spectroscopy, Fourier-Transform Infrared (FTIR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and water swelling ratio. The antimicrobial properties of the nanocomposites against Escherichia coli, Staphylococcus aureus, and Candida albicans were examined to investigate the possibility of using such composites in biomedical applications. Additionally, the biocompatibility of the composites on human normal fibroblast cell lines (HFB4) was tested using MTT (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) assay. The results demonstrate that the filler type and concentration strongly affect the film's properties. The permittivity ε', dielectric loss ε″ and conductivity σdc increased by increasing filler content but still in the insulators range that recommend such composites to be used in the insulation purposes. Both bio fillers control the water uptake, and the samples filled with LP were more water resistant. The polyvinyl alcohol/starch incorporated with 5 wt% LP and Cc have antimicrobial effects against all the tested microorganisms. Increasing the filler content has a negative impact on cell viability.

Dielectric Modes in Antiferroelectric and Ferroelectric Liquid Crystals in a Pure Enantiomeric Version and a Racemic Mixture.

The dielectric properties of synclinic (ferroelectric SmC*) and anticlinic (antiferroelectric SmCA*) smectic liquid crystals composed of molecules of one chiral version (S) are presented and compared with properties of racemic mixture (R, S), showing SmC and SmCA phases. The racemic mixture completely loses its ferroelectric and antiferroelectric properties. Surprisingly, only one dielectric mode observed in the antiferroelectric SmCA* phase disappeared in the dielectric response of the racemic SmCA phase. Additionally, we observed that in the SmC phase, seen in the racemic mixture, the weak dielectric mode (named the X mode) is detected, which seems to be the continuation of the PL mode existing in the racemic SmCA. Moreover, this mode in the racemic SmC has nothing to do with the Goldstone mode, typical for the SmC* phase. This paper describes in detail the real and imaginary parts of dielectric permittivity in smectic phases for the enantiomer and racemate with and without a DC field, compares the properties of the X and PL modes, and discusses the full scheme of dielectric modes in enantiomer and racemate.

Microwave Dielectric Response of Bovine Milk as Pregnancy Detection Tool in Dairy Cows.

The most reliable methods for pregnancy diagnosis in dairy herds include rectal palpation, ultrasound examination, and evaluation of plasma progesterone concentrations. However, these methods are expensive, labor-intensive, and invasive. Thus, there is a need to develop a practical, non-invasive, cost-effective method that can be implemented on the farm to detect pregnancy. This study suggests employing microwave dielectric spectroscopy (MDS, 0.5-40 GHz) as a method to evaluate reproduction events in dairy cows. The approach involves the integration of MDS data with information on milk solids to detect pregnancy and identify early embryonic loss in dairy cows. To test the ability to predict pregnancy according to these measurements, milk samples were collected from (i) pregnant and non-pregnant randomly selected cows, (ii) weekly from selected cows (n = 12) before insemination until a positive pregnancy test, and (iii) daily from selected cows (n = 10) prior to insemination until a positive pregnancy test. The results indicated that the dielectric strength of Δε and the relaxation time, τ, exhibited reduced variability in the case of a positive pregnancy diagnosis. Using principal component analysis (PCA), a clear distinction between pregnancy and nonpregnancy status was observed, with improved differentiation upon a higher sampling frequency. Additionally, a neural network machine learning technique was employed to develop a prediction algorithm with an accuracy of 73%. These findings demonstrate that MDS can be used to detect changes in milk upon pregnancy. The developed machine learning provides a broad classification that could be further enhanced with additional data.

Modification of the Dielectric and Thermal Properties of Organic Frameworks Based on Nonterminal Epoxy Liquid Crystal with Silicon Dioxide and Titanium Dioxide.

A nonterminal liquid crystal epoxy monomer is used to create an epoxy-amine network with a typical diamine 4,4'diaminodiphenylmethane. The plain matrix is compared to matrices modified with inorganic fillers: TiO2 or SiO2. Conditions of the curing reaction and glass transition temperatures in the cured products are determined through differential scanning calorimetry and broadband dielectric spectroscopy. The curing process is also followed through optical and electrical observations. The dielectric response of all investigated networks reveals a segmental α-process related to structural reorientation (connected to the glass transition). In all products, a similar process associated with molecular motions of polar groups also appears. The matrix modified with TiO2 exhibits two secondary relaxation processes (ß and γ). Similar processes were observed in the pure monomer. An advantage of the network with the TiO2 filler is a shorter time or lower temperature required for optimal curing conditions. The physical properties of cured matrices depend on the presence of a nematic phase in the monomer and nonterminal functional groups in the aliphatic chains. In effect, such cured matrices can have more flexibility and internal order than classical resins. Additional modifiers used in this work shift the glass transition above room temperature and influence the fragility index in both cases.

The Influence of the Molecular Structure of Compounds on Their Properties and the Occurrence of Chiral Smectic Phases.

We have designed new chiral smectic mesogens with the -CH2O group near the chiral center. We synthesized two unique rod-like compounds. We determined the mesomorphic properties of these mesogens and confirmed the phase identification using dielectric spectroscopy. Depending on the length of the oligomethylene spacer (i.e., the number of methylene groups) in the achiral part of the molecules, the studied materials show different phase sequences. Moreover, the temperature ranges of the observed smectic phases are different. It can be seen that as the length of the alkyl chain increases, the liquid crystalline material shows more mesophases. Additionally, its clearing (isotropization) temperature increases. The studied compounds are compared with the structurally similar smectogens previously synthesized. The helical pitch measurements were performed using the selective reflection method. These materials can be useful and effective as chiral components and dopants in smectic mixtures targeted for optoelectronics and photonics.

The Dominance of Pretransitional Effects in Liquid Crystal-Based Nanocolloids: Nematogenic 4-methoxybenzylidene-4'-butylaniline with Transverse Permanent Dipole Moment and BaTiO3 Nanoparticles.

The report presents static, low-frequency, and dynamic dielectric properties in the isotropic liquid, nematic, and solid phases of MBBA and related nanocolloids with paraelectric BaTiO3 nanoparticles (spherical, d = 50 nm). MBBA (4-methoxybenzylidene-4'-butylaniline) is a liquid crystalline compound with a permanent dipole moment transverse to the long molecular axis. The distortions-sensitive analysis of the dielectric constant revealed its hidden pretransitional anomaly, strongly influenced by the addition of nanoparticles. The evolution of the dielectric constant in the nematic phase shows the split into two regions, with the crossover coinciding with the standard melting temperature. The 'universal' exponential-type behavior of the low-frequency contribution to the real part of the dielectric permittivity is found. The critical-like pretransitional behavior in the solid phase is also evidenced. This is explained by linking the Lipovsky model to the Mossotti catastrophe concept under quasi-negative pressure conditions. The explicit preference for the 'critical-like' evolution of the apparent activation enthalpy is worth stressing for dynamics. Finally, the long-range, 'critical-like' behavior of the dissipation factor (D = tgδ), covering the isotropic liquid and nematic phases, is shown.

The effect of ionic redistributions on the microwave dielectric response of cytosol water upon glucose uptake.

The sensitivity of cytosol water's microwave dielectric (MD) response to D-glucose uptake in Red Blood Cells (RBCs) allows the detailed study of cellular mechanisms as a function of controlled exposures to glucose and other related analytes like electrolytes. However, the underlying mechanism behind the sensitivity to glucose exposure remains a topic of debate. In this research, we utilize MDS within the frequency range of 0.5-40 GHz to explore how ionic redistributions within the cell impact the microwave dielectric characteristics associated with D-glucose uptake in RBC suspensions. Specifically, we compare glucose uptake in RBCs exposed to the physiological concentration of Ca2+ vs. Ca-free conditions. We also investigate the potential involvement of Na+/K+ redistribution in glucose-mediated dielectric response by studying RBCs treated with a specific Na+/K+ pump inhibitor, ouabain. We present some insights into the MD response of cytosol water when exposed to Ca2+ in the absence of D-glucose. The findings from this study confirm that ion-induced alterations in bound/bulk water balance do not affect the MD response of cytosol water during glucose uptake.

Investigation of the Effectiveness of Silicon Nitride as a Reinforcement Agent for Polyethylene Terephthalate Glycol in Material Extrusion 3D Printing.

Polyethylene terephthalate glycol (PETG) and silicon nitride (Si3N4) were combined to create five composite materials with Si3N4 loadings ranging from 2.0 wt.% to 10.0 wt.%. The goal was to improve the mechanical properties of PETG in material extrusion (MEX) additive manufacturing (AM) and assess the effectiveness of Si3N4 as a reinforcing agent for this particular polymer. The process began with the production of filaments, which were subsequently fed into a 3D printer to create various specimens. The specimens were manufactured according to international standards to ensure their suitability for various tests. The thermal, rheological, mechanical, electrical, and morphological properties of the prepared samples were evaluated. The mechanical performance investigations performed included tensile, flexural, Charpy impact, and microhardness tests. Scanning electron microscopy and energy-dispersive X-ray spectroscopy mapping were performed to investigate the structures and morphologies of the samples, respectively. Among all the composites tested, the PETG/6.0 wt.% Si3N4 showed the greatest improvement in mechanical properties (with a 24.5% increase in tensile strength compared to unfilled PETG polymer), indicating its potential for use in MEX 3D printing when enhanced mechanical performance is required from the PETG polymer.

Rheological and dielectric behavior of sodium carboxymethyl cellulose (NaCMC)/Ca2+ and esterified NaCMC/Ca2+ hydrogels: Correlating microstructure and dynamics with properties.

Polyelectrolyte-based conductive hydrogels are being extensively explored for applications in energy storage and as electrode materials for batteries. We synthesized ionically crosslinked sodium carboxymethyl cellulose (NaCMC), esterified NaCMC, and Ca2+ doped esterified NaCMC hydrogels. This work aims to understand the effect of Ca2+ ions on the NaCMC and esterified NaCMC. FTIR, SEM, Rheology and EIS studies were performed to understand the structure and dynamics of hydrogels. Results confirmed that Ca2+ ions have an important role in determining the rheological and dielectric response of hydrogels. Power law behavior was observed in their rheological response with exponent (n) of 0.81 for G' and 0.76 for G″ of ionically crosslinked NaCMC, 5.38 for G' and 4.70 for G″ of esterified NaCMC, whereas, negative exponents -1.44 for G' and -1.10 for G″ of Ca2+ ion doped esterified NaCMC. Ionically crosslinked NaCMC hydrogels have relaxation times (τ) in the range of 8.9 × 10-5 s-2.8 × 10-5 s may be due to the formation of temporary dipoles by electrostatic bridge formations with dc conductivity of (0.1 S/cm-5 S/cm), whereas, esterified NaCMC showed relaxation times (10-3 s-8.9 × 10-5 s) with increasing ester crosslinks and dc conductivity of (0.05 S/cm-0.8 S/cm). Interestingly, Ca2+ ion doped esterified hydrogels showed multiple dielectric relaxations on Ca2+ ion addition with different relaxation times may be due to change in ionic environment. The understanding obtained from this work may be useful for designing tuneable hydrogels with optimum electrical and mechanical properties.

In situ process analytical technology for real time viable cell density and cell viability during live-virus vaccine production.

Viable cell density (VCD) and cell viability (CV) are key performance indicators of cell culture processes in biopharmaceutical production of biologics and vaccines. Traditional methods for monitoring VCD and CV involve offline cell counting assays that are both labor intensive and prone to high variability, resulting in sparse sampling and uncertainty in the obtained data. Process analytical technology (PAT) approaches offer a means to address these challenges. Specifically, in situ probe-based measurements of dielectric spectroscopy (also commonly known as capacitance) can characterize VCD and CV continuously in real time throughout an entire process, enabling robust process characterization. In this work, we propose in situ dielectric spectroscopy as a PAT tool for real time analysis of live-virus vaccine (LVV) production. Dielectric spectroscopy was collected across 25 discreet frequencies, offering a thorough evaluation of the proposed technology. Correlation of this PAT methodology to traditional offline cell counting assays was performed, in which VCD and CV were both successfully predicted using dielectric spectroscopy. Both univariate and multivariate data analysis approaches were evaluated for their potential to establish correlation between the in situ dielectric spectroscopy and offline measurements. Univariate analysis strategies are presented for optimal single frequency selection. Multivariate analysis, in the form of partial least squares (PLS) regression, produced significantly higher correlations between dielectric spectroscopy and offline VCD and CV data, as compared to univariate analysis. Specifically, by leveraging multivariate analysis of dielectric information from all 25 spectroscopic frequencies measured, PLS models performed significantly better than univariate models. This is particularly evident during cell death, where tracking VCD and CV have historically presented the greatest challenge. The results of this work demonstrate the potential of both single and multiple frequency dielectric spectroscopy measurements for enabling robust LVV process characterization, suggesting that broader application of in situ dielectric spectroscopy as a PAT tool in LVV processes can provide significantly improved process understanding. To the best of our knowledge, this is the first report of in situ dielectric spectroscopy with multivariate analysis to successfully predict VCD and CV in real time during live virus-based vaccine production.

Segmental relaxation of sequence defined polymers.

The dynamical behavior of sequence defined polymers, P(CnEG4), was studied using dielectric spectroscopy showing one segmental relaxation in addition to a secondary relaxation. In case of segmental relaxation, the relaxation times strongly depend on the molecular weight at low temperatures, while at higher temperatures, unlike to linear homo polymers, this effect levels out. With increasing length of C-units, the segmental relaxation accelerates. This is also reflected in the glass transition temperature, extracted from dielectric spectroscopy. With increasing length of C-units the glass transition temperature decreases, compatible with the accelerated segmental relaxation.