In-situ investigation of supercooling behaviour during high-pressure shift freezing of pure water and sucrose solution.

Supercooling is a main controllable factor for the fundamental understanding the high-pressure shift freezing (HPSF). In the study, a self-developed device based on the diamond anvil cell (DAC) and confocal Raman microscopy was utilized to realize an in-situ investigation of supercooling behaviour during HPSF of the pure water and sucrose solution. The spectra were used to determine the freezing point which is shown as a spectral phase marker (SD). The hydrogen bond strengths of water and sucrose solution under supercooling states were estimated by peak position and peak area ratio of sub-peaks. The results showed that the OH stretching bands had redshift under supercooling states. Moreover, the addition of sucrose molecules could strengthen the hydrogen bonding strength of water molecules under supercooling states. Thus, the DAC combined with Raman spectroscopy could be considered a novel strategy for a deep understanding of the supercooling behaviour during HPSF.

Exploring the effect of protein secondary structure on the solid state and physical stability of protein-based amorphous solid dispersions.

Amorphous solid dispersions (ASDs) using proteins as carriers have emerged as a promising strategy for stabilizing amorphous drug molecules. Proteins possess diverse three-dimensional structures that significantly influence their own properties and may also impact the properties of ASDs. We prepared ß-lactoglobulin (BLG) with different contents of ß-sheet and α-helical secondary structures by initially dissolving BLG in different mixed solvents, containing different ratios of water, methanol/ethanol, and acetic acid, followed by spray drying of the solutions. Our findings revealed that an increase in α-helical content resulted in a decrease in the glass transition temperature (Tg) of the protein. Subsequently, we utilized the corresponding mixed solvents to dissolve both BLG and the model drug celecoxib (CEL), allowing the preparation of ASDs containing either ß-sheet-rich or α-helix/random coil-rich BLG. Using spray drying, we successfully developed BLG-based ASDs with drug loadings ranging from 10 wt% to 90 wt%. At drug loadings below 40 wt%, samples prepared using both methods exhibited single-phase ASDs. However, heterogeneous systems formed when the drug loading exceeded 40 wt%. At higher drug loadings, physical stability assessments demonstrated that the α-helix/random coil-rich BLG structure exerted a more pronounced stabilizing effect on the drug-rich phase compared to the ß-sheet-rich BLG. Overall, our results highlight the importance of considering protein secondary structure in the design of ASDs.

Star-PCL shape memory polymer (SMP) scaffolds with tunable transition temperatures for enhanced utility.

Thermoresponsive shape memory polymers (SMPs) prepared from UV-curable poly(ε-caprolactone) (PCL) macromers have the potential to create self-fitting bone scaffolds, self-expanding vaginal stents, and other shape-shifting devices. To ensure tissue safety during deployment, the shape actuation temperature (i.e., the melt transition temperature or Tm of PCL) must be reduced from ∼55 °C that is observed for scaffolds prepared from linear-PCL-DA (Mn ∼ 10 kg mol-1). Moreover, increasing the rate of biodegradation would be advantageous, facilitating bone tissue healing and potentially eliminating the need for stent retrieval. Herein, a series of six UV-curable PCL macromers were prepared with linear or 4-arm star architectures and with Mns of 10, 7.5, and 5 kg mol-1, and subsequently fabricated into six porous scaffold compositions (10k, 7.5k, 5k, 10k★, 7.5k★, and 5k★) via solvent casting particulate leaching (SCPL). Scaffolds produced from star-PCL-tetraacrylate (star-PCL-TA) macromers produced pronounced reductions in Tm with decreased Mnversus those formed with the corresponding linear-PCL-diacrylate (linear-PCL-DA) macromers. Scaffolds were produced with the desired reduced Tm profiles: 37 °C < Tm < 55 °C (self-fitting bone scaffold), and Tm ≤ 37 °C (self-expanding stent). As macromer Mn decreased, crosslink density increased while % crystallinity decreased, particularly for scaffolds prepared from star-PCL-TA macromers. While shape memory behavior was retained and radial expansion pressure increased, this imparted a reduction in modulus but with an increase in the rate of degradation.

In vitro evaluation of shape-memory hydrogels for removable dental prostheses and optimization of phase-transition temperature for intraoral use.

STATEMENT OF PROBLEM: Removable dental prostheses require periodic relining with the loss of intaglio surface fit because of mucosal shape changes over time. Therefore, a new material with high adaptability to tissue changes over time would be beneficial. PURPOSE: This study focused on a shape-memory gel (SMG) that softens when heated, retains its shape when cooled, and returns to its original shape when reheated. The purpose was to optimize SMG for intraoral use by controlling the ratio of 2 acrylate monomers and to evaluate the changes in the shape memory and physical properties of SMG with temperature and to evaluate biocompatibility. MATERIAL AND METHODS: SMG specimens were synthesized using the following mixing ratios of 2 monomers, docosyl acrylate (DA) and stearyl acrylate (SA): 0:100, 25:75, 50:50, 75:25, and 100:0. SMG specimens were photopolymerized using a fluorescent light-polymerizing unit. To evaluate shape memory as a function of temperature, permanent deformation was measured based on the standardized compression set test for thermoplastic rubber. For evaluation of the physical properties and cytotoxicity, a 3-dimensionally printed denture base material was used as the control material. All assessments were compared between the groups by using 1-way analysis of variance followed by the Tukey-Kramer multiple comparison test (α=.05). RESULTS: SMGs with a higher amount of DA maintained their compressed shape at room and intraoral temperatures. However, the SMG matrices softened and recovered their original shapes above 60 °C. SMGs showed Shore A hardness equivalent to that of the denture-base polymer material at intraoral temperatures because of the high phase-transition temperature. The low water solubility of SMGs supported the biocompatibility test results. CONCLUSIONS: SMG, in which the phase-transition temperature was controlled by mixing acrylate monomers with different melting points, exhibited shape memory in the intraoral environment. The results indicate the feasibility of applying SMG for the fabrication of removable dental prostheses because of its high adaptability to tissue changes over time and biocompatibility.

Development and characterization of colloidal pNIPAM-methylcellulose microgels with potential application for drug delivery in dentoalveolar tissue engineering strategies.

Incorporation of growth factors, signaling molecules and drugs can be vital for the success of tissue engineering in complex structures such as the dentoalveolar region. This has led to the development of a variety of drug release systems. This study aimed to develop pNIPAM-methylcellulose microgels with different synthesis parameters based on a 23 full factorial design of experiments for this application. Microgel properties, including volume phase transition temperature (VPTT), hydrodynamic size, drug loading and release, and cytocompatibility were systematically evaluated. The results demonstrated successful copolymerization and development of the microgels, a hydrodynamic size ranging from ∼200 to ∼500 nm, and VPTT in the range of 34-39 °C. Furthermore, loading of genipin, capable of inducing odontoblastic differentiation, and its sustained release over a week was shown in all formulations. Together, this can serve as a solid basis for the development of tunable drug-delivering pNIPAM-methylcellulose microgels for specific tissue engineering applications.

Low transition temperature mixture-based extraction of 14 pesticides from tomato samples and their high-performance liquid chromatography-tandem mass spectrometry analysis.

The extensive use of pesticides to control pest infestations has led to the development of analytical methods to determine pesticide residues in food matrices to prevent food exposure. However, most developed analytical methods do not consider impact on the environment in terms of the toxicity of the chemicals used and the amount of waste produced. An environmentally-friendly method, based on a miniaturized matrix solid-phase dispersion followed by high-performance liquid chromatography-tandem mass spectrometry, for the analysis of fourteen pesticides in tomatoes, was exploited. For the recovery of pesticides from tomato samples, a low transition temperature mixture (LTTM), containing choline chloride and sesamol 1:3 molar ratio, was employed. Extraction parameters like sample-to-dispersant ratio, extraction solvent volume and LTTM volume were optimized through a Box-Behnken design. The 1:4 sample-to-dispersant ratio, 900 µL of ethanol as extraction solvent and 50 µL of LTTM ensured the best result considering the pesticides' peak areas. The optimized analytical method was validated obtaining the following results: linearity range was between LOQ and 5 mg kg-1 with a minimum R2 of 0.9944 for tebufenozide, values in the range of 0.001-0.023 and 0.004-0.076 mg kg-1 were obtained for LOD and LOQ respectively, while peak areas intra-day and inter-day repeatability were maximum of 10.19 and 9.15 %, respectively. The analytical method was then applied to real samples studying whole, pulp and peel tomato pool. The analysis of whole and tomato pulp revealed the presence of seven and eight of the fourteen investigated pesticides, respectively. However, their concentration was lower than the limit of quantification. In tomato peel, five pesticides, namely dimethomorph, methoxyfenozide, pyraclostrobin, pyriproxyfen, and spiromesifen were quantified and their concentrations were below maximum residue levels.

Impact of the polymer dispersity on the properties of curcumin/polyvinylpyrrolidone amorphous solid dispersions.

Amorphous solid dispersions (ASD) are known to enhance the absorption of poorly water-soluble drugs. In this work we synthesise well-defined Polyvinylpyrrolidone (PVP) to establish the impact of dispersity and chain-end functionality on the physical properties of Curcumin (CUR)/PVP ASD. Thermodynamic characterisation of synthesised PVP emphasises a strong effect of the dispersity on the glass transition temperature (Tg), 50 °C higher for synthesised PVP than for commercial PVP K12 of same molar mass. This increase of Tg affects the thermodynamic properties of CUR/PVP ASD successfully formulated up to 70 wt% of CUR by milling or solvent evaporation. The evolution of both the Tg and CUR solubility values versus CUR content points out the development of fairly strong CUR-PVP interactions that strengthen the antiplasticising effect of PVP on the Tg of ASD. However, for ASD formulated with commercial PVP this effect is counterbalanced at low CUR content by a plasticising effect due to the shortest PVP chains. Moreover, the overlay of the phase and state diagrams highlights the strong impact of the polymer dispersity on the stability of CUR/PVP ASD. ASD formulated with low dispersity PVP are stable on larger temperature and concentration ranges than those formulated with PVP K12.

Effect of Moisture Content on Ion Diffusion and Glass Transition Temperature in Wood Cell Walls.

Understanding and controlling the diffusion of ions and chemicals within the secondary plant cell walls are pivotal in various applications of biomasses. Recent studies have shown that inorganic ion diffusion through secondary cell walls is controlled by a moisture-induced glass transition in amorphous polysaccharides, including amorphous cellulose and hemicelluloses. Understanding the diffusion of ions in these structures has been the subject of numerous recent experiments; however, a deep understanding of the underlying mechanisms of interactions between ion atoms and water/hemicellulose molecules is still lacking. This study uses molecular dynamics simulations to elucidate the diffusion mechanisms of potassium and chloride ions in the cell walls under varying moisture content. The results reveal that a higher moisture content leads to the formation of solvent layers around the ions and reduces the charge interaction between the functional groups of wood polymers and ions. Hence, a higher moisture content results in an improved diffusion rate of ions within the domain. The simulation results also show that higher moisture content lowers the glass transition temperature, promoting diffusion of ions in the system. In contrast, increases in the ion concentration increase the glass transition temperature of the system and degrade the diffusion of ions in the system.

Molecular interactions of hydrated co-amorphous systems of prilocaine and lidocaine.

It is generally accepted that water as a plasticizer can decrease the glass transition temperatures (Tgs) of amorphous drugs and drug excipient systems. However, previous studies suggest that water, as an anti-plasticizer, can increase the Tgs of co-amorphous systems of prilocaine (PRL) and lidocaine (LID). In order to investigate the intermolecular interactions between water and co-amorphous PRL-LID systems, Fourier transform infrared spectroscopy (FTIR) and principal component analysis (PCA) were conducted. Water was found to bind with the carbonyl groups of PRL and LID molecularly evenly in the hydrated co-amorphous PRL-LID systems. Quantum chemical simulations visually confirmed the interactions between water and co-amorphous PRL-LID systems. Furthermore, the physical stability of hydrated co-amorphous PRL-LID systems was improved due to the anti-plasticizing effect of water, compared with the anhydrous samples. The preference of water to interact with the carbonyl groups of PRL and LID as binding sites could be associated with the anti-plasticizing effect of water on the co-amorphous PRL-LID systems.

Strong and ultrafast stimulus-healable lignin-based composite elastomers with excellent adhesion properties.

With the increased environmental issues, advanced high-performance and multifunctional polymeric materials derived from biomass have tremendous attention due to the great potential to replace their traditional petroleum-based counterparts. In this work, a series of lignin graft copolymers, lignin-graft-poly(n-butyl acrylate-co-acrylic acid) (Lig-g-P(BA-co-AA)), were rationally prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. These lignin-based copolymers demonstrate good thermal stability and tunable glass transition temperature (Tg) values. The mechanical performance, including tensile strength, extensibility, Young's modulus, and toughness can be facilely adjusted by the BA/AA feed ratio and lignin content during polymerization. Owing to the extraordinary photothermal conversion ability of lignin, the Lig-B550 copolymer, containing 11.8 wt% lignin content, shows excellent stimulus-healing behavior within 1 min with a 97.1 % healing efficiency under near-infrared (NIR) laser irradiation. Moreover, the Lig-g-P(BA-co-AA) copolymers exhibit remarkable adhesion property, broadening their potential applications in the adhesive area. This grafting strategy is versatile and efficient, conferring the resultant lignin-based composite elastomers with dramatically enhanced mechanical properties and unprecedented photothermal behavior, which can inspire the further development of strong lignin-based sustainable elastomers.

Influence of water and trehalose on α- and ß-relaxation of freeze-dried lysozyme formulations.

Molecular mobility in form of alpha and beta relaxations is considered crucial for characterization of amorphous lyophilizates and reflected in the transition temperatures Tgα and Tgß. Based on an overview of applied methods to study beta relaxations, Dynamic Mechanical analysis was used to measure Tgα and Tgß in amorphous freeze-dried samples. Lysozyme and trehalose as well as their mixtures in varying ratios were investigated. Three different residual moisture levels, ranging from roughly 0.5-7 % (w/w), were prepared via equilibration of the freeze-dried samples. Known plasticising effects of water on Tgα were confirmed, also via differential scanning calorimetry. In addition and contrary to expectations, an influence of water on the Tgß also was observed. On the other hand, an increasing amount of trehalose lowered Tgα but increased Tgß showing that Tgα and Tgß are not paired. The findings were interpreted with regard to their underlying molecular mechanisms and a correlation with the known influences of water and trehalose on stability. The results provide encouraging hints for future stability studies of freeze-dried protein formulations, which are urgently needed, not least for reasons of sustainability.

Ionic liquids: environmentally sustainable materials for energy conversion and storage applications.

Ionic liquids (ILs), often known as green designer solvents, have demonstrated immense application potential in numerous scientific and technological domains. ILs possess high boiling point and low volatility that make them suitable environmentally benign candidates for many potential applications. The more important aspect associated with ILs is that their physicochemical properties can be effectively changed for desired applications just by tuning the structure of the cationic and/or anionic part of ILs. Furthermore, these eco-friendly designer materials can function as electrolytes or solvents depending on the application. Owing to the distinctive properties such as low volatility, high thermal and electrochemical stability, and better ionic conductivity, ILs are nowadays immensely used in a variety of energy applications, particularly in the development of green and sustainable energy storage and conversion devices. Suitable ILs are designed for specific purposes to be used as electrolytes and/or solvents for fuel cells, lithium-ion batteries, supercapacitors (SCs), and solar cells. Herein, we have highlighted the utilization of ILs as unique green designer materials in Li-batteries, fuel cells, SCs, and solar cells. This review will enlighten the promising prospects of these unique, environmentally sustainable materials for next-generation green energy conversion and storage devices. Ionic liquids have much to offer in the field of energy sciences regarding fixing some of the world's most serious issues. However, most of the discoveries discussed in this review article are still at the laboratory research scale for further development. This review article will inspire researchers and readers about how ILs can be effectively applied in energy sectors for various applications as mentioned above.

Physiochemical and mechanical characterisation of orthodontic 3D printed aligner material made of shape memory polymers (4D aligner material).

OBJECTIVES: To conduct a physiochemical and mechanical material analysis on 3D printed shape-memory aligners in comparison to thermoformed aligners. MATERIALS AND METHODS: Four materials were examined, including three thermoformed materials: CA Pro (CP), Zendura A (ZA), Zendura FLX (ZF), and one 3D printed material: Tera Harz (TC-85). Rectangular strips measuring 50 × 10 × 0.5 mm were produced from each material. Five tests were conducted, including differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), shape recovery tests, three-points bending (3 PB), and Vickers surface microhardness (VH). RESULTS: DSC recorded glass transition temperatures (Tg) at 79.9 °C for CP, 92.2 °C for ZA, 107.1 °C for ZF, and 42.3 °C for TC-85. In DMA analysis at 20-45 °C, a prominent decrease in storage modulus was observed, exclusively for TC-85, as the temperature increased. Notably, within the temperature range of 30-45 °C, TC-85 exhibited substantial shape recovery after 10 min, reaching up to 86.1 %, while thermoformed materials showed minimal recovery (1.5-2.9 %). In 3 PB test (at 30, 37, 45 °C), ZA demonstrated the highest force at 2 mm bending, while TC-85 exhibited the lowest. Regarding VH at room temperature, there was a significant decrease for both ZA and ZF after thermoforming. ZA had the highest hardness, followed by ZF and TC-85, with CP showing the lowest values. CONCLUSIONS: TC-85 demonstrates exceptional shape memory at oral temperature, improving adaptation, reducing force decay, and enabling, together with its higher flexibility, extensive tooth movement per step. Additionally, it maintains microhardness similar to thermoformed sheets, ensuring the durability and effectiveness of dental aligners. CLINICAL RELEVANCE: The 3D printed aligner material with shape memory characteristics (4D aligner) has revolutionized the orthodontic aligner field. It showed mechanical properties more suitable for orthodontic treatment than thermoforming materials. Additionally, it offers enhanced control over aligner design and thickness, while optimizing the overall workflow. It also minimizes material wastage, and reduces production expenses.

Atomistic Simulations of Polydisperse Lignin Melts Using Simple Polydisperse Residue Input Generator.

Understanding the physics of lignin will help rationalize its function in plant cell walls as well as aiding practical applications such as deriving biofuels and bioproducts. Here, we present SPRIG (Simple Polydisperse Residue Input Generator), a program for generating atomic-detail models of random polydisperse lignin copolymer melts i.e., the state most commonly found in nature. Using these models, we use all-atom molecular dynamics (MD) simulations to investigate the conformational and dynamic properties of polydisperse melts representative of switchgrass (Panicum virgatum L.) lignin. Polydispersity, branching and monolignol sequence are found to not affect the calculated glass transition temperature, Tg. The Flory-Huggins scaling parameter for the segmental radius of gyration is 0.42 ± 0.02, indicating that the chains exhibit statistics that lie between a globular chain and an ideal Gaussian chain. Below Tg the atomic mean squared displacements are independent of molecular weight. In contrast, above Tg, they decrease with increasing molecular weight. Therefore, a monodisperse lignin melt is a good approximation to this polydisperse lignin when only static properties are probed, whereas the molecular weight distribution needs to be considered while analyzing lignin dynamics.

Transformer-Based Representation of Organic Molecules for Potential Modeling of Physicochemical Properties.

In this work, we study the use of three configurations of an autoencoder neural network to process organic substances with the aim of generating meaningful molecular descriptors that can be employed to develop property prediction models. A total of 18,322,500 compounds represented as SMILES strings were used to train the model, demonstrating that a latent space of 24 units is able to adequately reconstruct the data. After AE training, an analysis of the latent space properties in terms of compound similarity was carried out, indicating that this space possesses desired properties for the potential development of models for forecasting physical properties of organic compounds. As a final step, a QSPR model was developed to predict the boiling point of chemical substances based on the AE descriptors. 5276 substances were used for the regression task, and the predictive ability was compared with models available in the literature evaluated on the same database. The final AE model has an overall error of 1.40% (1.39% with augmented SMILES) in the prediction of the boiling temperature, while other models have errors between 2.0 and 3.2%. This shows that the SMILES representation is comparable and even outperforms the state-of-the-art representations widely used in the literature.

Molecular Dynamics and Near-Tg Phenomena of Cyclic Thioethers.

This article presents the synthesis and molecular dynamics investigation of three novel cyclic thioethers: 2,3-(4'-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2-ene (compound 1), 2,3,14,15-bis(4',4″(5″)-methylbenzo)-1,4,7,10,13,16,19,22,25-octathiacyclotetracosa-2,14-diene (compound 2), and 2,3,8,9-bis(4',4″(5″)-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2,8-diene (compound 3). The compounds exhibit relatively high glass transition temperatures (Tg), which range between 254 and 283 K. This characteristic positions them within the so-far limited category of crown-like glass-formers. We demonstrate that cyclic thioethers may span both the realms of ordinary and sizeable molecular glass-formers, each featuring distinct physical properties. Furthermore, we show that the Tg follows a sublinear power law as a function of the molar mass within this class of compounds. We also reveal multiple dielectric relaxation processes of the novel cyclic thioethers. Above the Tg, their dielectric loss spectra are dominated by a structural relaxation, which originates from the cooperative reorientation of entire molecules and exhibits an excess wing on its high-frequency slope. This feature has been attributed to the Johari-Goldstein (JG) process. Each investigated compound exhibits also at least one intramolecular secondary non-JG relaxation stemming from conformational changes. Their activation energies range from approximately 19 kJ/mol to roughly 40 kJ/mol. Finally, we analyze the high-pressure molecular dynamics of compound 1, revealing a pressure-induced increase in its Tg with a dTg/dp coefficient equal to 197 ± 8 K/GPa.

Ice modulatory effect of the polysaccharide FucoPol in directional freezing.

Directional freezing harnesses crystal growth development to create aligned solid structures or etchable patterns, useful for directed ice growth in cryobiology and cryoprinting for tissue engineering. We have delved into the ice-modulating properties of FucoPol, a fucose-rich, bio-based polysaccharide. Previous research on FucoPol revealed its non-colligative hysteresis in kinetic freezing point, reduced crystal dimensions and cryoprotective effect. Here, FucoPol reshaped developing sharp, anisotropic obloid ice dendrites into linearly-aligned, thin, isotropic spicules or tubules (cooling rate-dependent morphology). The effect was enhanced by increased concentration and decreased cooling rate, but major reshaping was observed with 5 µM and below. These structures boasted remarkable enhancements: uniform alignment (3-fold), tip symmetry (5.9-fold) and reduced thickness (5.3-fold). The ice-modulating capability of FucoPol resembles the Gibbs-Thomson effect of antifreeze proteins, in particular the ice reshaping profiles of type I antifreeze proteins and rattlesnake venom lectins, evidenced by a 52.6 ± 2.2° contact angle (θ) and spicular structure generation. The high viscosity of FucoPol solutions, notably higher than that of sucrose, plays a crucial role. This viscosity dynamically intensifies during directional freezing, leading to a diffusion-limited impediment that influences dendritic formation. Essentially, the ice-modulating prowess of FucoPol not only reinforces its established cryoprotective qualities but also hints at its potential utility in applications that harness advantageous ice growth for intentional structuring. For instance, its potential in cryobioprinting is noteworthy, offering an economical, biodegradable resource, of easy removal, sidestepping the need for toxic reagents. Moreover, FucoPol fine-tunes resulting ice structures, enabling the ice-etching of biologically relevant patterns within biocompatible matrices for advanced tissue engineering endeavors.

Amorphization of different furosemide polymorphic forms during ball milling: Tracking solid-to-solid phase transformations.

Ball milling is used, not only to reduce the particle size of pharmaceutical powders, but also to induce changes in the physical properties of drugs. In this work we prepared three crystal forms of furosemide (forms Ⅰ, Ⅱ, and Ⅲ) and studied their solid phase transformations during ball milling. Powder X-ray diffraction and modulated differential scanning calorimetry were used to characterize the samples after each milling time on their path to amorphization. Our results show that forms Ⅰ and III directly converted into an amorphous phase, while form Ⅱ first undergoes a polymorphic transition to form Ⅰ, and then gradually loses its crystallinity, finally reaching full amorphousness. During ball milling of forms Ⅰ and Ⅱ, the glass transition temperature (Tg) of the amorphous fraction of the milled material remains almost unchanged at 75 °C and 74 °C, respectively (whilst the amorphous content increases). In contrast, the Tg values of the amorphous fraction of milled form III increase with increasing milling times, from 63 °C to 71 °C, indicating an unexpected phenomenon of amorphous-to-amorphous transformation. The amorphous fraction of milled forms I and II samples presented a longer structural relaxation (i.e., lower molecular mobility) than the amorphous fraction of milled form III samples. Moreover, the structural relaxation time remained the same for the increasing amorphous fraction during milling of forms I and II. In contrast, the structural relaxation times were always shorter for the amorphous fraction of form III, but increased with increasing amorphous content during milling, confirming amorphous-to-amorphous transformation.

Harnessing Variabilities in Digital Melt Curves for Accurate Identification of Bacteria.

Digital PCR combined with high resolution melt (HRM) is an emerging method for identifying pathogenic bacteria with single cell resolution via species-specific digital melt curves. Currently, the development of such digital PCR-HRM assays entails first identifying PCR primers to target hypervariable gene regions within the target bacteria panel, next performing bulk-based PCR-HRM to examine whether the resulting species-specific melt curves possess sufficient interspecies variability (i.e., variability between bacterial species), and then digitizing the bulk-based PCR-HRM assays with melt curves that have high interspecies variability via microfluidics. In this work, we first report our discovery that the current development workflow can be inadequate because a bulk-based PCR-HRM assay that produces melt curves with high interspecies variability can, in fact, lead to a digital PCR-HRM assay that produces digital melt curves with unwanted intraspecies variability (i.e., variability within the same bacterial species), consequently hampering bacteria identification accuracy. Our subsequent investigation reveals that such intraspecies variability in digital melt curves can arise from PCR primers that target nonidentical gene copies or amplify nonspecifically. We then show that computational in silico HRM opens a window to inspect both interspecies and intraspecies variabilities and thus provides the missing link between bulk-based PCR-HRM and digital PCR-HRM. Through this new development workflow, we report a new digital PCR-HRM assay with improved bacteria identification accuracy. More broadly, this work can serve as the foundation for enhancing the development of future digital PCR-HRM assays toward identifying causative pathogens and combating infectious diseases.

Tricyclic Diester and 2,5-Furandicarboxylic Acid for the Synthesis of Biobased Hydrolysis Copolyesters with High Glass Transition Temperatures.

The reluctance of a polyester with high glass transition temperature (Tg) and mechanical properties to hydrolyze is a well-known fact, for instance, the high hydrolysis resistance of aromatic polyesters based on terephthalic acid and 2,5-furandicarboxylic acid (FDCA). The synthesis of polyesters that have a high Tg (>100 °C) and a fast hydrolytic degradation quality at the same time is a valuable topic. Herein, a renewable rigid diester, N,N'-trans-1,4-cyclohexane-bis(pyrrolidone-4-methyl carboxylate) (CBPC), was obtained via Michael addition. CBPC was copolymerized with FDCA and ethylene glycol to prepare a series of copolyesters PECxEFy with a high Mn over 30 kDa. PECxEFy showed a Tg range of 75.2-109.2 °C which outdistanced the most biobased polyesters. The thermal stability of all PECxEFy remained unchanged with the introduction of CBPC. Moreover, PECxEFy presented superior mechanical performances which were matching or exceeding those of commercial polyethylene terephthalate (PET) and polylactic acid (PLA). PECxEFy was stable in air but was able to undergo noticeable hydrolytic degradation, proving their enhanced degradability. And the regulation between CBPC and FDCA composition can be leveraged to adjust the degradation and environmental durability of PECxEFy, up to practical applications. Computational studies systematically revealed the relationship between CBPC with a tricyclic structure and the improved Tg and hydrolyzation properties. The outstanding thermal and mechanical performances and hydrolysis of these copolyesters appear to be promising candidates for renewable alternatives to industrial petrochemical polyesters.