Bulk Properties Research Articles

Surface Characterization of Bone-Level and Tissue-Level PEEK and Titanium Dental Implant Scan Bodies After Repeated Autoclave Sterilization Cycles

Background: Sterilization is required for any biomedical device intended to be used in contact with the human body. Several studies have reported alterations in the bulk and surface properties of such devices after repeated sterilization cycles. These surface modifications may influence other clinical parameters. Therefore, the aim of this study was to investigate the surface and chemical properties of implant scan bodies (SBs) after consecutive autoclave sterilization procedures. Methods: The objective was to analyze the scan bodies using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) for chemical analysis and an optical profilometer to analyze the surface roughness. Results: FTIR spectra depicted the appearance of peak at 1741 and 1100 cm−1 due to the diphenyl ether band disappearance. The XPS spectra showed alterations in the elemental composition after autoclaving and roughness were significantly reduced in PEEK BL and TL SBs. Conclusions: These results indicated that some surface modifications were induced by repeated sterilization cycles.

Unveiling the Influence of Natural Weathering on the Nanomechanical Properties of Magnetorheological Elastomers

Examining the physical aging of materials is essential for assessing their long-term performance and determining their suitability for specific applications. Material aging involves changes from their initial state, including deterioration or degradation. A key example of such a progressive, continuous process is the aging of materials in response to natural weathering conditions. While extensive research has focused on macro- and micro-scale aging, further investigation at the nanoscale could provide a more detailed understanding of material deterioration. This study explores the nanomechanical properties of magnetorheological elastomers (MREs) after nine months of natural weathering, focusing on stiffness, elasticity, surface roughness, and adhesion at the nanometer scale. Atomic Force Microscopy (AFM) with a sharp tip affixed to a cantilever was employed to characterize these properties. After nine months of exposure to natural weathering, MREs exhibited unique nanomechanical changes compared to their bulk properties, highlighting the significance of nanoscale analysis. At the nanoscale, the nanomechanical properties of MREs, including stiffness and elasticity, exhibited noticeable alterations within the first month of exposure, followed by a gradual reduction, and slight increments observed up to the nine-month mark. Surface roughness steadily increased over the nine months, while adhesion energy initially rose during the first month before gradually decreasing by the end of the study. These findings provide valuable insights into the material's mechanical behavior and offer a deeper understanding of its structural and functional properties at the nanoscale.

Molecular composition difference of electron donating moieties between natural organic matter and effluent organic matter probed by chlorine dioxide

Lignin- and tannin-like phenolic compounds are shown to be the major compositions of electron donating moieties (EDM) of aquatic natural organic matter (NOM). However, little is known about the compositions of EDMs within effluent organic matter (EfOM). In the present study, chlorine dioxide (ClO2) was used as a selectively oxidative probe to investigate the difference in the molecular composition of EDM between NOM and EfOM due to its high selectivity towards electron-rich compounds. The results showed that there was a large difference in the bulk and molecular properties of ClO2-reactive moieties between EfOM and NOM. Specifically, ClO2-reactive moieties of EfOM are distributed in a narrower molecular weight range (i.e., 0.9 kDa to 3.0 kDa) compared to NOM (i.e.,1.0 kDa to 20 kDa). The molecular-level analysis demonstrated that highly aromatic, reduced formulas (O/C = 0.33 ± 0.16; H/C = 1.10 ± 0.34) referring the lignin- and tannin-like compounds within both NOM and EfOM were susceptible to oxidation by ClO2, while more saturated formulas including the peptide-like formulas (H/C = 1.59 ± 0.36) within EfOM were reactive towards ClO2. Furthermore, the nitrogen (N)-containing formulas in EfOM are suggested to be the major EDMs compared to the CHO-only formulas dominating the EDM in NOM. This study has important implications for understanding of the origin and chemical nature of EDM in DOM from various sources and provide molecular-level evidence for the selectivity of ClO2 as an oxidant towards DOM.

A Call for a Different Plant Modelling Paradigm and a New Generation of Software

This paper is an invitation to change the plant modeling paradigm to achieve much easier convergence and ensure model consistency between different incarnations of the plant model, while retaining accuracy on par with the rigorous models. Rigorous physical properties [property/mole] are replaced by [property/mass] approximation at local conditions, making bulk properties much less sensitive to changes in stream composition. This eliminates the need for stream mole fractions and stream compositions can be described by linear component mass flows. Detailed process flow diagram is a common topology for all models. Different incarnations of node models are employed at different levels of abstraction (planning, scheduling, optimization, control, design), ensuring inheritance, consistency and increasing accuracy of solutions as plant model instances move from mass to mass-energy, to mass-energy-and-approximate-stream-properties. After the plant model with approximate properties is solved, they are updated via rigorous thermodynamic methods and the plant model is resolved until convergence.

Predicting the diffusion coefficients of rejuvenators into bitumens using molecular dynamics, machine learning, and force field atom types

This study explores the use of chemical descriptors derived from force field atom types to predict Fickian diffusion coefficients of rejuvenators in bitumen, utilizing machine learning models trained on data from 240 non-equilibrium molecular dynamics simulations. The simulations cover three bitumen types (NO, TO, FO), five aging degrees, and four temperatures (60 °C, 120 °C, 160 °C, 200 °C), capturing diffusion coefficients ranging from 0.0068e-10 m2/s in highly aged bitumens at 60 °C to 4.35e-10 m2/s in fresher samples at 200 °C. The MLM, built with 18 chemical descriptors for bitumen and rejuvenator sides, achieves an R2 of 0.97, accurately predicting diffusion across varied conditions. This approach abstracts away from the need for repeated MD simulations, enabling diffusion predictions even for systems outside the original dataset. The manuscript presents three case studies to illustrate how the model can be used for the iterative design of rejuvenators by optimizing molecular structures based on critical chemical features, such as rejuvenator oxygen content, bitumen sulfur content, and molecular weights. It also demonstrates how the model offers a practical framework for understanding the diffusion and performance of rejuvenators by linking time-dependent factors—such as concentration, depth, and rejuvenation time—with the bulk properties of bitumen-rejuvenator systems, facilitating industrial applications

Hydrocarbon potential, source correlation, and paleoenvironmental reconstruction of the Jurassic interval in the Zey Gawra Oilfield, Kurdistan Region, Iraq

A comprehensive geochemical analysis for the Sargelu, Naokelekan, and Najmah formations cutting rock and crude oil samples from Z1, Z3, and Z5 wells of Hawler Block, Kurdistan Region, Iraq have been studied for source rock evaluation. Depending on the total organic carbon (TOC) content from pyrolysis analyses, the Sargelu and Naokelekan formations are regarded as very good source rocks, and fair source rock for the Najmah Formation. The organic matter in the Sargelu Formation is characterized by types II and mixed II and III kerogens. However, the Naokelekan and Najmah formations are characterized by type II kerogen. The Sargelu and Naokelekan formations’ organic matters are at mature stages; hence, in the oil window, whereas Najmah Formation’s organic matter is at immature stage. Pyrolysis study shows that the Sargelu Formation is oil and gas prone, while the Najmah and Naokelekan formations are oil prone. The biomarkers and bulk properties of the selected oils from Gas Chromatography (GC) and Gas Chromatography-Mass Spectroscopy (GC/MS) analysis show that they originated by the same source rocks. The geochemical characteristics indicate a carbonate source in a reducing environment for the studied formations and oils. Based on the oleanane index, tricyclic terpane indices, C28S/C29S ratios, and gammacerane index, the relative age of the oils and cuttings of Sargelu, Naokelekan, and Najmah formations is Middle to Late Jurassic and deposited under moderate saline condition. The biomarkers parameters show evidence that molecules from the cutting rocks of the Sargelu and Naokelekan formations are related to the oils in Z1, Z3, and Z5 wells. However, they are not related to the Najmah Formation.

Effect of carbon ion implantation on the superconducting properties of MgB2 bulks prepared by powder-in-sealed-tube method

We studied the effect of carbon (C) ion implantation on the microstructure and superconducting properties of bulk MgB2 prepared by the powder-in-sealed-tube (PIST) method. FESEM and TEM analysis indicate microstructural changes due to carbon ion implantation. DC magnetization measurements reveal a slight improvement of TC and small ΔTC values due to ion implantation. The JC(B) characteristics of implanted samples show a significant enhancement of JC compared with pristine MgB2 at 10 and 20 K. MgB2 samples implanted with 80 keV carbon ions with a dose of 2 × 1016 ions cm−2 show maximum enhancement in JC i.e., 2.07 × 105 A/cm2 at 5 T and 10 K. The flux pinning force density curves are theoretically analyzed using the Dew-Hughes model. The results reveal that significant enhancements in the flux pinning properties are contributed by the normal point defects caused by carbon ion implantation, which acts as a strong pinning center.

Au@TiO2 Core-Shell Nanoparticles with Nanometer-Controlled Shell Thickness for Balancing Stability and Field Enhancement in Plasmon-Enhanced Photocatalysis.

Plasmonic core-shell nanostructures can make photocatalysis more efficient for several reasons. The shell imparts stability to the nanoparticles, light absorption is expanded, and electron-hole pairs can be separated more effectively, thus reducing recombination losses. The synthesis of metal@TiO2 core-shell nanoparticles with nanometer control over the shell thickness and understanding its effect on the resulting photocatalytic efficiency still remains challenging. In the present study, a synthesis method is presented for preparing Au@TiO2 core-shell nanoparticles with ultrathin shells that can be accurately tuned in the range of 2-12 nm, based on the controlled slow hydrolysis of a titanium precursor. Electromagnetic simulations combined with comprehensive characterization of the opto-physical bulk properties, as well as energy electron loss spectroscopy and electron tomography reconstructions at the nanoscale, aid in understanding the crucial role of the shell in improving both the activity as well as the stability in a photocatalytic reaction. Ultrathin shells in the order of 2 nm do not suffice to prevent sintering of the nanoparticles upon annealing, with a consequent loss of plasmonic properties. After reaching an optimum for a shell of 4 nm, further increasing the shell thickness again reduces the plasmonic properties by a weakened plasmonic coupling. This trend is confirmed by photocatalytic hydrogen evolution experiments, as well as stearic acid degradation tests. With this study, we prove and emphasize the crucial importance of carefully controlling the shell thickness in plasmonic core-shell structures, so their maximum application potential may be unlocked.

Interfacial and Bulk Properties of Potato and Faba Protein in Connection with Physical Emulsion Stability at Various pH Values and High Salt Concentrations

The protein transition motivates the use of plant proteins, but their application in food emulsions is challenging, especially when high concentrations of oil and salt are needed for formulation and sensory properties. In the present work, we connect the iso-electric point of two potato protein isolates (patatin-rich, POPI-200; protease inhibitor-rich, POPI-300) and a faba protein isolate (FPI) to the behavior in the bulk phase and at the interface, and relate this to the physical stability of 45 wt% oil-in-water (O/W) emulsions in the presence of NaCl at pH 4.0–7.0. In the absence of NaCl, a higher bulk viscosity was found at the iso-electric point (IEP), especially for the FPI. In the presence of NaCl, the viscosity of the POPI-200 solutions was highest, followed by POPI-300, and that of the FPI was lowest, irrespective of the pH. Both POPIs showed faster initial adsorption at the O/W interface in the absence of NaCl, and formed a more elastic layer compared to the FPI. For all proteins, salt addition leads to less elastic films. Interestingly, the interfaces were more elastic at a pH close to the IEP of the protein in the presence of NaCl. Both POPI-stabilized emulsions showed higher stability (smaller size and less oiling off) than the FPI-stabilized emulsions, which makes potato proteins relevant for food emulsion product formulation, even under high salt conditions.

Thermodynamic properties of pinned nanobubbles.

We present molecular dynamics simulations to study the thermodynamics of nanobubbles trapped at the mouth of narrow slit pores. Except when the slit dimensions are comparable to typical molecular sizes, the predictions of macroscopic thermodynamic theory are recovered by our simulations. Our simulations confirm that in this case, the internal pressure of stable nanobubbles is independent of the bubble radius and the surface tension and only depends on the bulk properties of the solute-containing solution, i.e., the chemical potential balance. However, in the case of extreme confinement, the pressure is not a suitable quantity to describe the thermodynamics of the bubbles, while the balance of the chemical potentials is.

Equality of Magnetization and Edge Current for Interacting Lattice Fermions at Positive Temperature

We prove that the magnetization is equal to the edge current in the thermodynamic limit for a large class of models of lattice fermions with finite-range interactions satisfying local indistinguishability of the Gibbs state, a condition known to hold for sufficiently high temperatures. Our result implies that edge currents in such systems are determined by bulk properties and are therefore stable against large perturbations near the boundaries. Moreover, the equality persists also after taking the derivative with respect to the chemical potential. We show that this form of bulk-edge correspondence is essentially a consequence of homogeneity in the bulk and locality of the Gibbs state. An important intermediate result is a new version of Bloch’s theorem for two-dimensional systems, stating that persistent currents vanish in the bulk.

Hybrid Mass Spectrometry Applied across the Production of Antibody Biotherapeutics.

Post expression from the host cells, biotherapeutics undergo downstream processing steps before final formulation. Mass spectrometry and biophysical characterization methods are valuable for examining conformational and stoichiometric changes at these stages, although typically not used in biomanufacturing, where stability is assessed via bulk property studies. Here we apply hybrid MS methods to understand how solution condition changes impact the structural integrity of a biopharmaceutical across the processing pipeline. As an exemplar product, we use the model IgG1 antibody, mAb4. Flexibility, stability, aggregation propensity, and bulk properties are evaluated in relation to perfusion media, purification stages, and formulation solutions. Comparisons with Herceptin, an extensively studied IgG1 antibody, were conducted in a mass spectrometry-compatible solution. Despite presenting similar charge state distributions (CSD) in native MS, mAb4, and Herceptin show distinct unfolding patterns in activated ion mobility mass spectrometry (aIM-MS) and differential scanning fluorimetry (DSF). Herceptin's greater structural stability and aggregation onset temperature (Tagg) are attributed to heavier glycosylation and kappa-class light chains, unlike the lambda-class light chains in mAb4. Hydrogen-deuterium exchange mass spectrometry (HDX-MS) revealed that mAb4 undergoes substantial structural changes during purification, marked by high flexibility, low melting temperature (Tm), and prevalent repulsive protein-protein interactions but transitions to a compact and stable structure in high-salt and formulated environments. Notably, in formulation, the third constant domain (CH3) of the heavy chain retains flexibility and is a region of interest for aggregation. Future work could translate features of interest from comprehensive studies like this to targeted approaches that could be utilized early in the development stage to aid in decision-making regarding targeted mutations or to guide the design space of bioprocesses and formulation choices.

First-principles calculations to investigate the bulk, electronic, optical and thermoelectric properties of BaGe[formula omitted]As[formula omitted] and BaGe[formula omitted]P[formula omitted] alloys

The structural, elastic, electronic, and optical properties of BaGe2As2 and BaGe2P2 have been theoretically investigated, but their thermoelectric properties have not been reported. The current work aimed at conducting an exhaustive study on the bulk, electronic, and optical properties as well as the thermoelectric property of BaGe2As2 and BaGe2P2 zintl phase compounds. Density functional theory implemented in Quantum ESPRESSO code combined with other processing codes such as Thermo−pw and BoltzTrap were employed in this study. The lattice constants computed were found to agree well with the other theoretical and experimental results, demonstrating validity of the study. Both compounds are brittle, elastically anisotropic and mechanically as well thermodynamically stable. The materials in this investigation were discovered to be semiconductors with indirect band gaps of 0.73 eV and 1.14 eV for BaGe2As2 and BaGe2P2 respectively. Therefore, both materials are appropriate for use in the electronics sector, notably in temperature control applications. The PDOS analysis suggests that P and As in BaGe2P2 and BaGe2As2, respectively, dominate the conduction band, whereas Ge dominates the valence band in both cases. The results also show that BaGe2P2 out-performs BaGe2As2 in terms of optical absorption coefficient. Both BaGe2As2 and BaGe2P2 are excellent p-type thermoelectric materials but BaGe2P2 has a greater figure of merit than BaGe2As2, making it a potential thermoelectric material. Lastly, the figure of merit values determined in this study are considered approximations since the lattice thermal conductivities of complex BaGe2As2 and BaGe2P2 compounds were not computed due to limited computational resources.

Characterisation of TOI-406 as a showcase of the THIRSTEE program. A two-planet system straddling the M-dwarf density gap

The exoplanet sub-Neptune population currently poses a conundrum, as to whether small-size planets are volatile-rich cores without an atmosphere, or rocky cores surrounded by a H-He envelope. To test the different hypotheses from an observational point of view, a large sample of small-size planets with precise mass and radius measurements is the first necessary step. On top of that, much more information will likely be needed, including atmospheric characterisation and a demographic perspective on their bulk properties. We present here the concept and strategy of the project, which aims to shed light on the composition of the sub-Neptune population across stellar types by increasing their number and improving the accuracy of bulk density measurements, as well as investigating their atmospheres and performing statistical, demographic analysis. We report the first results of the program, characterising a new two-planet system around the M-dwarf TOI-406. We analysed and ground-based photometry together with high-precision ESPRESSO and NIRPS/HARPS radial velocities to derive the orbital parameters and investigate the internal composition of the two planets orbiting TOI-406. TOI-406 hosts two planets with radii and masses of $R_ c c and b b orbiting with periods of $3.3$ and $13.2$ days, respectively. The inner planet is consistent with an Earth-like composition, while the external one is compatible with multiple internal composition models, including volatile-rich planets without H/He atmospheres. The two planets are located in two distinct regions in the mass-density diagram, supporting the existence of a density gap among small exoplanets around M dwarfs. With an equilibrium temperature of only $=368$ K, TOI-406 b stands up as a particularly interesting target for atmospheric characterisation with JWST in the low-temperature regime.

“Clicking” Amphiphilic Block Copolymers onto POSS Core: A General Approach for “Star-like” Polymers with Different Symmetry

“Star-like” macromolecules have been widely studied because of their unique physical and chemical properties, which play a great role in many important application fields. In this study, a library of star-like amphiphilic block copolymers consisting of a polyhedral oligomeric silsesquioxane (POSS) core and polyethylene glycol-bolck-polystyrene (PEGm-b-PSn) diblock copolymer arms with an exact arm number were prepared through a robust copper-catalysed azide-alkyne cycloadditions (CuAAC) and strain-promoted azide-alkyne cycloaddition (SPAAC) click reactions. Moreover, homo- and mikto-arms star polymers with different compositions were obtained by precisely regulating the central symmetry of the POSS core. The target polymers and intermediate products were characterized by nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), Fourier transform infrared (FT-IR) spectroscopy, and matrix-assisted laser desorption ionization time-of-flight (MALDI-ToF) mass spectrometry. This study demonstrates the chemical robustness of the novel POSS-based building block and establishes a general and efficient approach to prepare star-like macromolecules, especially for asymmetric heteroarm star-like macromolecules, which serve as important model compounds in the study of their bulk properties as well as self-assembling behaviors.

Exploring Structural Anisotropy in Amorphous Tb-Co via Changes in Medium-Range Ordering.

Amorphous thin films grown by magnetron co-sputtering exhibit changes in atomic structure with varying growth and annealing temperatures. Structural variations influence the bulk properties of the films. Scanning nanodiffraction performed in a transmission electron microscope (TEM) is applied to amorphous Tb17Co83 (a-Tb-Co) films deposited over a range of temperatures to measure relative changes in medium-range ordering (MRO). These measurements reveal an increase in MRO with higher growth temperatures and a decrease in MRO with higher annealing temperatures. The trend in MRO indicates a relationship between the growth conditions and local atomic ordering. By tilting select films, the TEM measures variations in the local atomic structure as a function of orientation within the films. The findings support claims that preferential ordering along the growth direction results from temperature-mediated adatom configurations during deposition, and that oriented MRO correlates with increased structural anisotropy, explaining the strong growth-induced perpendicular magnetic anisotropy found in rare earth-transition metal films. Beyond magnetic films, we propose the tilted FEM workflow as a method of extracting anisotropic structural information in a variety of amorphous materials with directionally dependent bulk properties, such as films with inherent bonding asymmetry grown by physical vapor deposition.

Polar Order in a Fluid Like Ferroelectric with a Tilted Lamellar Structure – Observation of a Polar Smectic C (SmCP) Phase

AbstractThe spontaneous polarisation of the SmCP phase is over two orders of magnitude larger than that found in conventional ferroelectric SmC phase of chiral materials used in some LCD devices. Fully atomistic molecular dynamics simulations faithfully and spontaneously reproduce the proposed structure and associated bulk properties; comparison of experimental and simulated X‐ray scattering patterns shows excellent agreement. The materials disclosed here have significantly smaller dipole moments than typical polar liquid crystals such as RM734 which suggests the role of molecular electrical polarity in generating polar order is perhaps overstated, a view supported by consideration of other molecular systems.

Revised 4-Point Water Model for the Classical Drude Oscillator Polarizable Force Field: SWM4-HLJ.

In this work the 4-point polarizable SWM4 Drude water model is reparametrized. Multiple models were developed using different strategies toward reproduction of specific target data. Results indicate that no individual model can reproduce all the selected target data in the context of the present form of the potential energy function. The changes considered in the new models include, 1) variations in the gas phase dipole moment, 2) variations in the molecular polarizability, 3) variations of the distance between the oxygen and the M site, 4) variation of the oxygen Lennard-Jones (LJ) parameters, 5) introduction of a LJ potential to the hydrogen atoms, and 6) variations of the H-O-H angle. Detailed analysis is presented for 3 new water models from which a final model, SWM4-HLJ, is selected as the future default model for the Drude polarizable force field. The model maintains the gas phase dipole moment as the experimental value while the remaining listed terms were adjusted including a larger H-O-H angle (108.12). Compared to its predecessor, SWM4-NDP, the self-diffusion coefficient, water dimer properties, and water cluster energies are greatly improved. The temperature dependence of the density of the new model also performs better. Overall, the new SWM4-HLJ water model is a general improvement and a good balance between microscopic and bulk properties is achieved.

Achieving antibiofouling on microporous membranes prepared with a green solvent via spraying an aqueous antifouling copolymer solution

This study highlights a comprehensive investigation into the fabrication and characterization of sustainable membranes for antifouling applications. It utilizes γ-valerolactone as a green solvent to obtain microfiltration polyvinylidene difluoride (PVDF) membranes, and leverages spray-coating technique to modify these membranes. This research aims to enhance the surface and bulk properties of PVDF membranes while promoting sustainable practices. Chemical analyses of the membranes reveal that the surface and bulk of the membranes were successfully modified. Dynamic water contact angle measurements indicated that a 10 mg/mL coating solution (PVDF_10) resulted in the highest hydrophilicity. Different biofouling tests were conducted using proteins and bacteria. In adhesion tests with BSA, and E. coli, the PVDF_10 membrane demonstrated the highest resistance, reducing adhesion by approximately 83 % and 94 %, respectively. Additionally, cyclical water/bacterial filtration tests demonstrated that PVDF_10 membrane achieved a higher flux recovery ratio compared to commercial hydrophilic PVDF membranes. The modification remained stable even after 6 weeks of immersion in water. This study highlights the potential of γ-GVL and the spray-coating technique as environmentally friendly solvents and modification techniques for producing green antifouling PVDF membranes, aligning with sustainable practices and significantly enhancing membrane performance.

First principles investigations on structural, electronic, optical, and thermodynamical properties of bulk and surfaces of In2CO

This study reports first-principles investigations of the structural, electronic, thermal, and optical properties of a novel material In2CO in bulk phase and slab models in (001), (100), (101), and (011) orientations to develop a fundamental understanding of its characteristics. The material appeared structurally as well as dynamically stable in the orthorhombic phase. The thermal properties demonstrated that the material's heat capacity is more temperature-sensitive than entropy and enthalpy. The electronic band structure analysis revealed that the orthorhombic phase material is a semiconductor with a narrow indirect band gap. The electronic structures modeled using the spin-orbit coupling yielded the metallic phase of the slabs except for (001) orientation. The electromagnetic absorption characteristics of the compound are also investigated to explore the material's potential in optoelectronic applications. The direction-dependent study of optical characteristics revealed that the (001) slab of the material can be an efficient infrared detector. The survey findings provide instrumental outcomes in utilizing In2CO in electronic and optoelectronic applications.