Dissipation Shifts Research Articles

Development and Characterization of Silibinin-Loaded Nanoemulsions: A Promising Mucoadhesive Platform for Enhanced Mucosal Drug Delivery

Background: Silibinin (SLB), a flavonoid derived from milk thistle, exhibits promising therapeutic properties but faces significant clinical limitations due to poor solubility and bioavailability. Objectives: This study focuses on the development and characterization of SLB-loaded nanoemulsions designed for mucosal delivery. Methods: Nanoemulsions were prepared using the spontaneous emulsification method, guided by pseudoternary phase diagrams to determine selected component ratios. Comprehensive characterization included particle size, polydispersity index (PDI), zeta potential, encapsulation efficiency, rheological properties, and surface tension. Mucoadhesive properties were evaluated using quartz crystal microbalance with dissipation (QCM-D) to quantify interactions with mucin layers. Results: The combination of Capryol 90, Tween 80, and Transcutol in selected proportions yielded nanoemulsions with excellent stability and solubilization capacity, enhancing the solubility of silibinin by 625 times compared to its intrinsic solubility in water. The ternary phase diagram indicated that achieving nanoemulsions with particle sizes between 100 and 300 nm required higher concentrations of surfactants (60%), relative to oil (20%) and water (20%), with formulations predominantly composed of Smix (surfactant and cosurfactant mixture in a 1:1 ratio). Rheological analysis revealed Newtonian behavior, characterized by constant viscosity across varying shear rates and a linear torque response, ensuring ease of application and mechanical stability. QCM-D analysis confirmed strong mucoadhesive interactions, with significant frequency and dissipation shifts, indicative of prolonged retention and enhanced mucosal drug delivery. Furthermore, contact angle measurements showed a marked reduction in surface tension upon interaction with mucin, with the SLB-loaded nanoemulsion demonstrating superior wettability and strong mucoadhesive potential. Conclusions: These findings underscore the suitability of SLB-loaded nanoemulsions as a robust platform for effective mucosal drug delivery, addressing solubility and bioavailability challenges while enabling prolonged retention and controlled therapeutic release.

An investigation of the effect of the protein corona on the cellular uptake of nanoliposomes under flow conditions using quartz crystal microgravimetry with dissipation.

When nanoparticle delivery systems are immersed in biological fluids, a complex assembly of proteins forms on their surface, creating a protein corona. The protein corona alters the physicochemical properties, toxicity, biodistribution, cellular uptake, and immune response of the nanoparticles, and consequently, their therapeutic efficacy. Currently, there is a lack of in vitro methods to assess the effects of the protein corona on nanoparticle uptake under dynamic flow and assess their binding kinetics in real-time. Here, we introduce quartz crystal microbalance with dissipation (QCM-D) as an in vitro technique, capable of incorporating dynamic flow, to study the effect of the protein corona on the binding of nanoliposome (NLP) formulations to cell surfaces as a first step in their cellular uptake. The interactions of four NLP formulations (low PEGylated, high PEGylated, negatively charged and positively charged NLPs) with A375 melanoma and THP1 cell lines were assessed by QCM-D, before and after the formation of a protein corona. Through real-time recording of the frequency and dissipation shifts (Δf and ΔD, respectively), the QCM-D results provided strong evidence of the role of the protein corona in the cellular interaction of these NLP formulations, with a variation in their adsorption kinetics depending on their initial composition. NLP's attachment to the cell surface was the lowest for PEGylated NLPs (<5%), while the positively charged NLPs showed the highest cellular attachment (≈100%), regardless of the presence of the protein corona or cell type. The effect of the protein corona was more pronounced for the negatively charged NLPs, where a significant reduction in the NLP attachment was observed. To complement the QCM-D data on the NLP attachment and to determine whether the NLP attachment leads to cellular uptake, confocal microscopy and flow cytometry were used to confirm NLP uptake by A375 and THP1 cells. Proteomic analysis revealed a differential composition of the protein corona on the various NLPs with possible implications for their sequestration and cellular uptake. Collectively, the findings suggest that QCM-D can be an important tool to study the binding of NLP formulations or other nanoparticles with cell membranes under dynamic flow, which very often differs from nanoparticle uptake under static conditions.

Size-dependent thermoelastic dissipation and frequency shift in micro/nano cylindrical shell based on surface effect and dual-phase lag heat conduction model

Size-dependent thermoelastic dissipation and frequency shift in micro/nano cylindrical shell based on surface effect and dual-phase lag heat conduction model

Insight into the mechanism of synergy of ultrasound and high pressure homogenization on the emulsion stability and interfacial behaviors of α-lactalbumin with mogroside V

Due to uneven distribution amino acid residues of α-lactalbumin (αLA) at oil-water interface, some measurement should be adopted to improve its interfacial behavior and emulsion stability. Therefore, this study focused on the mechanism of synergy of ultrasound and high pressure homogenization on the emulsion stability and interfacial behaviors of α-lactalbumin with mogroside V (MGV). Four treatments were adopted: ultrasound (US), high pressure homogenization (HPH) and combined treatment (US-HPH and HPH-US). Primarily, emulsion stability of αLA/MGV was analyzed. US-HPH or HPH-US exhibited better emulsion stability than US or HPH. Especially, HPH-US-αLA/MGV emulsion was not stratified at the given time (45 d), which was the most stable emulsion. Moreover, the micromorphology of emulsion showed that MGV and UH/HPH treatment suppressed the aggregation of αLA emulsion droplet. In addition, interfacial adsorption mass and viscoelasticity of physical treated αLA was improved with MGV in the order of HPH-US > US-HPH > US > HPH, specifically, frequency shift (ΔF) and dissipation shift (ΔD) of HPH-US-αLA/MGV was 42.2% and 32.5% higher than that without MGV. This finding may provide a potential approach for obtaining natural and high-efficient protein-based emulsifier in food industry.

Anisotropic Particle Deposition Kinetics from Quartz Crystal Microbalance Measurements: Beyond the Sphere Paradigm.

Deposition kinetics of polymer particles characterized by a prolate spheroid shape on gold sensors modified by the adsorption of poly(allylamine) was investigated using a quartz crystal microbalance and atomic force microscopy. Reference measurements were also performed for polymer particles of a spherical shape and the same diameter as the spheroid shorter axis. Primarily, the frequency and dissipation shifts for various overtones were measured as a function of time. These kinetic data were transformed into the dependence of the complex impedance, scaled up by the inertia impedance, upon the particle size to the hydrodynamic boundary layer ratio. The results obtained for low particle coverage were interpolated, which enabled the derivation of Sauerbrey-like equations, yielding the real particle coverage using the experimental frequency or dissipation (bandwidth) shifts. Experiments carried out for a long deposition time confirmed that, for spheroids, the imaginary and real impedance components were equal to each other for all overtones and for a large range of particle coverage. This result was explained in terms of a hydrodynamic, lubrication-like contact of particles with the sensor, enabling their sliding motion. In contrast, the experimental data obtained for spheres, where the impedance ratio was a complicated function of overtones and particle coverage, showed that the contact was rather stiff, preventing their motion over the sensor. It was concluded that results obtained in this work can be exploited as useful reference systems for a quantitative interpretation of bioparticle, especially bacteria, deposition kinetics on macroion-modified surfaces.

Artifact Correction of Light Induced Detuning in QCM-D Experiments.

The quartz crystal microbalance with dissipation (QCM-D) has become an efficient and versatile measurement technique for investigating in situ the external stimuli responsiveness such as pH, temperature, or chemical gradients of surface-active substances at solid-liquid interfaces. However, light responsive adsorption investigation is more challenging presumably since the quartz crystal itself reacts to optical stimulation, showing frequency and dissipation shifts known as light induced detuning (LID). This yields an effective measurement artifact and makes data interpretation with respect to dynamic interactions of light responsive materials rather challenging. Here we introduce a simple guideline for correcting the artifacts of the QCM sensor response on irradiation to ensure quantitative analysis for light responsive materials via OCM-D. We also show that the LID depends on the adsorption properties of the sensor and the solvent properties (ionic concentration or viscosity), providing a guideline to minimize impact of the LID.

Mechanical responses and acoustic emission behaviors of coal under compressive differential cyclic loading (DCL): a numerical study via 3D heterogeneous particle model

The stability of coal walls (pillars) can be seriously undermined by diverse in-situ dynamic disturbances. Based on a 3D particle model, this work strives to numerically replicate the major mechanical responses and acoustic emission (AE) behaviors of coal samples under multi-stage compressive cyclic loading with different loading and unloading rates, which is termed differential cyclic loading (DCL). A Weibull-distribution-based model with heterogeneous bond strengths is constructed by both considering the stress–strain relations and AE parameters. Six previously loaded samples were respectively grouped to indicate two DCL regimes, the damage mechanisms for the two groups are explicitly characterized via the time-stress-dependent variation of bond size multiplier, and it is found the two regimes correlate with distinct damage patterns, which involves the competition between stiffness hardening and softening. The numerical b-value is calculated based on the magnitudes of AE energy, the results show that both stress level and bond radius multiplier can impact the numerical b-value. The proposed numerical model succeeds in replicating the stress–strain relations of lab data as well as the elastic-after effect in DCL tests. The effect of damping on energy dissipation and phase shift in numerical model is summarized.

Tensile energy dissipation and mechanical properties of the knee meniscus: relationship with fiber orientation, tissue layer, and water content.

Introduction: The knee meniscus distributes and dampens mechanical loads. It is composed of water (∼70%) and a porous fibrous matrix (∼30%) with a central core that is reinforced by circumferential collagen fibers enclosed by mesh-like superficial tibial and femoral layers. Daily loading activities produce mechanical tensile loads which are transferred through and dissipated by the meniscus. Therefore, the objective of this study was to measure how tensile mechanical properties and extent of energy dissipation vary by tension direction, meniscal layer, and water content. Methods: The central regions of porcine meniscal pairs (n = 8) were cut into tensile samples (4.7mm length, 2.1mm width, and 0.356mm thickness) from core, femoral and tibial components. Core samples were prepared parallel (circumferential) and perpendicular (radial) to the fibers. Tensile testing consisted of frequency sweeps (0.01-1Hz) followed by quasi-static loading to failure. Dynamic testing yielded energy dissipation (ED), complex modulus (E*), and phase shift (δ) while quasi-static tests yielded Young's Modulus (E), ultimate tensile strength (UTS), and strain at UTS (εUTS). To investigate how ED is influenced by the specific mechanical parameters, linear regressions were performed. Correlations between sample water content (φw) and mechanical properties were investigated. A total of 64 samples were evaluated. Results: Dynamic tests showed that increasing loading frequency significantly reduced ED (p < 0.05). Circumferential samples had higher ED, E*, E, and UTS than radial ones (p < 0.001). Stiffness was highly correlated with ED (R2 > 0.75, p < 0.01). No differences were found between superficial and circumferential core layers. ED, E*, E, and UTS trended negatively with φw (p < 0.05). Discussion: Energy dissipation, stiffness, and strength are highly dependent on loading direction. A significant amount of energy dissipation may be associated with time-dependent reorganization of matrix fibers. This is the first study to analyze the tensile dynamic properties and energy dissipation of the meniscus surface layers. Results provide new insights on the mechanics and function of meniscal tissue.

Physical treatment synergized with natural surfactant for improving gas–water interfacial behavior and foam characteristics of α-lactalbumin

The purpose of this study was to investigate effect of physical treatment (ultrasound, U/high pressure homogenization, H/combined treatment, UH or HU) and surfactant (Mogroside V, Mog) on air/water interface adsorption and foaming properties of α-lactalbumin (ALa). Firstly, the binding of Mog and all physical-treated ALa was a static quenching process. Mog had the greatest binding affinity for HU-ALa among all treated samples. U or H treatment could change surface hydrophobicity of ALa/Mog complex. Secondly, at the molar ratio (ALa:Mog) of 1:50, foaming ability (FA) of all ALa samples got the maximum. The sequence of FA in ALa and ALa/Mog complex was listed as follow: HU > U > H > UH. Moreover, foaming stability (FS) of HU-ALa was the highest, followed by H-ALa, U-ALa and UH-ALa. Meanwhile, low concentration Mog increased FS of ALa or UH-ALa, but it reduced FS of H-ALa, U-ALa and HU-ALa. Quartz crystal microbalance with dissipation monitoring (QCM-D) experiment indicated that ALa/Mog complex after U or H treatment was quickly absorbed at air/water interface, compared with the treated ALa, and HU-ALa/Mog had the largest frequency shift. In addition, HU-ALa had the thickest bubble membrane and the highest dissipation shift in all samples, indicating that the absorbed membrane thickness and viscoelasticity of samples was correlated with foam stability. Therefore, U and H treatment synergism with Mog was an effective approach to enhance foam properties of ALa, which indicated that HU-treated ALa/Mog complex could be viewed as the safe and efficient foaming agent applied in food processing.

Self-organized limit cycles in red-detuned atom-cavity systems

Recent experimental advances in the field of cold-atom cavity QED provide a powerful tool for exploring nonequilibrium correlated quantum phenomena beyond conventional condensed-matter scenarios. We present the dynamical phase diagram of a driven Bose-Einstein condensate coupled with the light field of a cavity, with a transverse driving field red-detuned from atomic resonance. We identify regions in parameter space showing dynamical instabilities in the form of limit cycles, which evolve into chaotic behavior in the strong driving limit. Such limit cycles originate from the interplay between cavity dissipation and atom-induced resonance frequency shift, which modifies the phase of cavity mode and gives excessive negative feedback on the atomic density modulation, leading to instabilities of the superradiant scattering. We find interesting merging of the limit cycles related by a ${Z}_{2}$ symmetry, and identify a limit cycle formed by purely atomic excitations. The effects of quantum fluctuations and atomic interactions are also investigated.

A Two-Phase Model for Adsorption from Solution Using Quartz Crystal Microbalance with Dissipation.

Quartz crystal microbalance with dissipation (QCM-D) conveniently monitors mass and mechanical property changes of thin films on solid substrates with exquisite resolution. QCM-D is frequently used to measure dissolved solute/sol adsorption isotherms and kinetics. Unfortunately, currently available methodologies to interpret QCM-D data treat the adlayer as a homogeneous medium, which does not adequately describe solution-adsorption physics. Tethering of the adsorbate to the solid surface is not explicitly recognized, and the liquid solvent is included in the adsorbate mass, which is especially in error for low coverages. Consequently, the areal mass of adsorbate (i.e., solute adsorption) is overestimated. Further, friction is not considered between the bound adsorbate and the free solvent flowing in the adlayer. To overcome these deficiencies, we develop a two-phase (2P) continuum model that self-consistently determines adsorbate and liquid-solvent contributions and includes friction between the attached adsorbate and flowing liquid solvent. We then compare the proposed 2P model to those of Sauerbrey for a rigid adlayer and Voinova et al. for a viscoelastic-liquid adlayer. Effects of 2P-adlayer properties are examined on QCM-D-measured frequency and dissipation shifts, including adsorbate volume fraction and elasticity, adlayer thickness, and overtone number, thereby guiding data interpretation. We demonstrate that distinguishing between adsorbate adsorption and homogeneous-film adsorption is critical; failing to do so leads to incorrect adlayer mass and physical properties.

Single-junction quantum-circuit refrigerator

We propose a quantum-circuit refrigerator (QCR) based on photon-assisted quasiparticle tunneling through a single normal-metal–insulator–superconductor (NIS) junction. In contrast to previous studies with multiple junctions and an additional charge island for the QCR, we directly connect the NIS junction to an inductively shunted electrode of a superconducting microwave resonator making the device immune to low-frequency charge noise. At low characteristic impedance of the resonator and parameters relevant to a recent experiment, we observe that a semiclassical impedance model of the NIS junction reproduces the bias voltage dependence of the QCR-induced damping rate and frequency shift. For high characteristic impedances, we derive a Born–Markov master equation and use it to observe significant non-linearities in the QCR-induced dissipation and frequency shift. We further demonstrate that, in this regime, the QCR can be used to initialize the linear resonator into a non-thermal state even in the absence of any microwave drive.

A quartz crystal microbalance method to quantify the size of hyaluronan and other glycosaminoglycans on surfaces

Hyaluronan (HA) is a major component of peri- and extra-cellular matrices and plays important roles in many biological processes such as cell adhesion, proliferation and migration. The abundance, size distribution and presentation of HA dictate its biological effects and are also useful indicators of pathologies and disease progression. Methods to assess the molecular mass of free-floating HA and other glycosaminoglycans (GAGs) are well established. In many biological and technological settings, however, GAGs are displayed on surfaces, and methods to obtain the size of surface-attached GAGs are lacking. Here, we present a method to size HA that is end-attached to surfaces. The method is based on the quartz crystal microbalance with dissipation monitoring (QCM-D) and exploits that the softness and thickness of films of grafted HA increase with HA size. These two quantities are sensitively reflected by the ratio of the dissipation shift (ΔD) and the negative frequency shift (− Δf) measured by QCM-D upon the formation of HA films. Using a series of size-defined HA preparations, ranging in size from ~ 2 kDa tetrasaccharides to ~ 1 MDa polysaccharides, we establish a monotonic yet non-linear standard curve of the ΔD/ − Δf ratio as a function of HA size, which reflects the distinct conformations adopted by grafted HA chains depending on their size and surface coverage. We demonstrate that the standard curve can be used to determine the mean size of HA, as well as other GAGs, such as chondroitin sulfate and heparan sulfate, of preparations of previously unknown size in the range from 1 to 500 kDa, with a resolution of better than 10%. For polydisperse samples, our analysis shows that the process of surface-grafting preferentially selects smaller GAG chains, and thus reduces the average size of GAGs that are immobilised on surfaces comparative to the original solution sample. Our results establish a quantitative method to size HA and other GAGs grafted on surfaces, and also highlight the importance of sizing GAGs directly on surfaces. The method should be useful for the development and quality control of GAG-based surface coatings in a wide range of research areas, from molecular interaction analysis to biomaterials coatings.

Uniformly accelerated Brownian oscillator in (2+1)D: Temperature-dependent dissipation and frequency shift

We consider an Unruh-DeWitt detector modeled as a harmonic oscillator that is coupled to a massless quantum scalar field in the (2+1)-dimensional Minkowski spacetime. We treat the detector as an open quantum system and employ a quantum Langevin equation to describe its time evolution, with the field, which is characterized by a frequency-independent spectral density, acting as a stochastic force. We investigate a point-like detector moving with constant acceleration through the Minkowski vacuum and an inertial one immersed in a thermal reservoir at the Unruh temperature, exploring the implications of the well-known non-equivalence between the two cases on their dynamics. We find that both the accelerated detector's dissipation rate and the shift of its frequency caused by the coupling to the field bath depend on the acceleration temperature. Interestingly enough this is not only in contrast to the case of inertial motion in a heat bath but also to any analogous quantum Brownian motion model in open systems, where dissipation and frequency shifts are not known to exhibit temperature dependencies. Nonetheless, we show that the fluctuating-dissipation theorem still holds for the detector-field system and in the weak-coupling limit an accelerated detector is driven at late times to a thermal equilibrium state at the Unruh temperature.

Inkjet-Printed Phospholipid Bilayers on Titanium Oxide Surfaces: Towards Functional Membrane Biointerfaces.

Functional biointerfaces hold broad significance for designing cell-responsive medical implants and sensor devices. Solid-supported phospholipid bilayers are a promising class of biological materials to build bioinspired thin-film coatings, as they can facilitate interactions with cell membranes. However, it remains challenging to fabricate lipid bilayers on medically relevant materials such as titanium oxide surfaces. There are also limitations in existing bilayer printing capabilities since most approaches are restricted to either deposition alone or to fixed microarray patterning. By combining advances in lipid surface chemistry and on-demand inkjet printing, we demonstrate the direct deposition and patterning of covalently tethered lipid bilayer membranes on titanium oxide surfaces, in ambient conditions and without any surface pretreatment process. The deposition conditions were evaluated by quartz crystal microbalance-dissipation (QCM-D) measurements, with corresponding resonance frequency (Δf) and energy dissipation (ΔD) shifts of around −25 Hz and <1 × 10−6, respectively, that indicated successful bilayer printing. The resulting printed phospholipid bilayers are stable in air and do not collapse following dehydration; through rehydration, the bilayers regain their functional properties, such as lateral mobility (>1 µm2/s diffusion coefficient), according to fluorescence recovery after photobleaching (FRAP) measurements. By taking advantage of the lipid bilayer patterned architectures and the unique features of titanium oxide’s photoactivity, we further show how patterned cell culture arrays can be fabricated. Looking forward, this work presents new capabilities to achieve stable lipid bilayer patterns that can potentially be translated into implantable biomedical devices.

Mechanistic understanding of the discrete morphology formed by multi-cycle assembly of tannic acid with Poloxamer 188 on silicon using QMC-D

Formation of discrete microdome-shaped features on planar silicon surfaces through multi-cycles of alternate adsorption of tannic acid (TA) and Poloxamer 188 of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (P188) has been reported recently. To further our understanding of the underlying fundamentals, we turned to quartz crystal microbalance with dissipation (QCM-D) for non-invasive monitoring of the process using SiO 2 -coated quartz crystals. Different concentrations of TA and P188 solutions were used for the step-by-step assembly, and the corresponding QCM-D responses were investigated. Additional TA-P188 assemblies were prepared on silicon substrates using the same concentration settings and subjected to surface morphology characterizations before and after drying. The results showed that increasing the concentration of P188 causes increased restructuring of the constructs during the assembling process, and leads to the formation of well-hydrated but less spherically shaped morphology with more continuity in coverage. In contrast, increasing TA concentration helps the assembled discrete features grow in size without inducing drastic change in morphology, and the large dissipation shift recorded is most likely related to water trapped in between the features. Furthermore, the study revealed that, besides the amphiphilic nature of P188 and the right solution concentration of TA, the surface of the underlying silicon substrate being hydrophilic is also instrumental in achieving discrete features of TA-P188 assembly. Collectively, findings reported herein allow for further tailored design of functional surfaces using TA and P188 as building blocks.

Effect of ionic strength on the sequential adsorption of whey proteins and low methoxy pectin on a hydrophobic surface: A QCM-D study

The effect of ionic strength on the sequential adsorption of whey protein isolate (WPI) and low methoxy pectin (LMP) onto a hydrophobic surface was investigated through a real-time QCM-D technique. A gold sensor was hydrophobically modified to simulate the oil-water interface. At neutral pH, whey proteins readily adsorbed onto the hydrophobic surface and formed a viscoelastic, heterogeneous layer. With increasing ionic strength of the continuous phase, the protein layer became more compact and less hydrated. A similar but stronger effect was observed upon switching the pH from 7.0 to 4.5 (i.e. close to the iso-electric point of WPI). The sequential adsorption of LMP onto the pre-formed protein layer was studied at pH 4.5 over a wide range of ionic strengths (from 7 to 500 mM). The enhanced frequency and dissipation shifts indicated the adsorption of LMP, as well as changes in interfacial viscoelasticity. Especially, a non-monotonic ionic strength dependency (i.e. maxima at 20 mM after rinsing) was observed for both frequency and dissipation shifts, which suggested that the added salt facilitated the electrostatic deposition of LMP. However, the much smaller shifts at higher ionic strength (e.g. up to 500 mM) were mainly due to less hydration of the adsorbed LMP layer rather than an appreciably reduced LMP adsorption. Similarly, upon exposure of the pre-formed mixed layer (at pH 4.5 with an ionic strength of 20 mM) to higher ionic strengths (up to 500 mM), most of the LMP remained adsorbed, even at the highest ionic strength considered. The obtained results provide interesting insights in the characteristics of protein-polysaccharide bilayers which are known to be promising emulsion stabilizers.

Analysis of the chemical network in a volume-production high-current negative hydrogen ion source

Complex simulations (e.g. multi-dimensional fluid models) usually prevent the use of very large chemistry models. In this work, the important physicochemical processes in a volume-production high-current negative hydrogen ion source (HCNHIS) are identified for a pressure range of 1–100 Torr using a global model. The particle species include H2(υ = 0–14), H(n = 1–3), , , H+, H−, and electrons. The simulation results indicate that for the production of negative hydrogen ions through dissociative attachments, the high vibrational levels of hydrogen molecules are important at low pressures, and the ground state and low vibrational levels of hydrogen molecules play an increasingly important role with increasing pressure. The reactions involving the ground state, low vibrational levels, and neighboring levels of each level tend to dominate the production of vibrational levels and transitions between them in the volume-production HCNHIS. With increasing pressure, the electron energy dissipation shifts from dissociation of H2(υ = 0) and electron excitation of H2(υ = 0) through an indirect mechanism followed by radiative decay (the EV process) to electron excitation of H2(υ = 0) through a resonant mechanism (the eV process). A valuable subset of reactions provided by the simplified model is proposed in the investigated pressure range, which could be incorporated in more complex simulations. The results obtained with the simplified model under different simulation conditions are within an acceptable error margin of the results for the full model, which indicates that the robustness of the simplified model of chemical reactions is guaranteed to some extent.

In situ investigation of lysozyme adsorption into polyelectrolyte brushes by quartz crystal microbalance with dissipation

A well understanding about protein adsorption into charged polymer brushes is of importance in the elucidation of mechanism and important phenomena (such as “chain delivery” effect) in protein adsorption on polymer-grafted ion exchange adsorbents. In this work, quartz crystal microbalance with dissipation (QCM-D) was introduced to in situ investigate lysozyme adsorption on QCM sensors grafted with poly(3-sulfopropyl methacrylate) ( p SPM) via atom transfer radical polymerization. It was achieved by analyzing frequency ( f ) and energy dissipation ( D ) shift simultaneously on p SPM-grafted sensors. The result showed that an initial decrease in Δ D was typical of lysozyme adsorption on p SPM-grafted sensor and more significant with an increase of chain length and grafting density. It was attributed to significant water release in the hydration layer of protein and polymer chains in lysozyme adsorption into p SPM brushes. On p SPM-grafted sensors with long and dense chains, furthermore, lysozyme transitioned from monolayer to multilayer adsorption and the maximum adsorbed amount was obtained to be 374.0 ng·cm −2 among all p SPM-grafted sensors in this work. The results in D - f plot further revealed that lysozyme adsorption into p SPM brushes increased the rigidity of adsorbed layer and little structure adjustment of adsorbed lysozyme. It was unfavorable for “chain delivery” effect for facilitated transport of adsorbed protein. This work provided valuable insight into protein adsorption in p SPM brushes and outlined a feasible approach to increasing mass transport in polymer-grafted ion exchange adsorbents.

Impact of dimensionless length scale parameter on material dependent thermoelastic attenuation and study of frequency shifts of rectangular microplate resonators

Quality factor is one of the decisive performance parameters of micro/nano plate resonators based sensors and filters .Various energy dissipation mechanisms limit the maximum attainable quality factor, and in micro/nano scales thermoelastic damping is a critical energy loss mechanism. When the devices are scaled down, in order to accurately model micro/nano scale resonators, non-classical elasticity theories like Modified Couple Stress Theory (MCST) are valid. In this paper, by including a length scale parameter (l) the size effects were incorporated in the analysis and thermoelastic energy dissipation and related attenuation were found to be diminished by selecting a dimensionless length scale parameter i.e. l/h. Thermoelastic attenuation and frequency shifts related to thermoelastic damping in microplate rectangular resonators with five structural materials (SiC, polySi, diamond, Si and GaAs) were investigated with l/h =0.The attenuation related to thermoelastic energy dissipation and frequency shifts were found to be minimum for polySi material. With the inclusion of size effect, the impact of dimensionless length scale parameter on thermoelastic attenuation of polySi based microplate resonators was also explored. The conventional thermoelastic damping analysis in rectangular plate was modified by applying Modified Couple Stress Theory and the impact of dimensionless length scale (l/h) on thermoelastic energy attenuation was simulated numerically using MATLAB 2015.