TDG prediction model improvement by analysis and validation of experiments on a dam model.

The combination of aerated flows and a high-pressure environment in a stilling basin can result in the supersaturation of total dissolved gas (TDG) downstream of hydraulic projects, posing an ecological risk to aquatic populations by inducing gas bubble disease (GBD) or other negative effects. There is limited literature reporting TDG mass transfer experiments on a complete physical dam model; most existing research is based on measurements in prototype tailwaters. In this study, TDG mass transfer experiments were conducted on a physical model of an under-constructed dam, with TDG-supersaturated water as the inflow, and TDG concentrations were meticulously monitored within the stilling basin. The measurements indicate that the TDG saturation at the outlet of the stilling basin decreased by 13.7% and 10.6% compared to the inlet for the two cases, respectively. Subsequently, an improved TDG prediction model was developed by incorporating a sub-grid air entrainment model and a phase-constrained scalar model. The numerical simulation results were compared with experimental data, indicating a maximum error in TDG saturation at all measured points of less than ± 3%. Moreover, the TDG saturation showed an error of only ± 0.3% at the outlet of the stilling basin. This model has broad applicability to various flow types for obtaining TDG mass transfer results and evaluating mitigation measures of TDG supersaturation to reduce the harmful effects on aquatic ecosystems.

Basics of Sterile Compounding: Sterilization Methods in Sterile Product Manufacturing.

Sterilization methods to produce sterile preparations include heat, gas, radiation, and filtration. This article focuses on heat, gas, and radiation sterilization, plus a brief introduction to bright-light sterilization. Microbiology basics and microbial death kinetics, key to understanding why these sterilization methods work, will also be briefly discussed. Filtration sterilization will be covered in a separate article.

The effects of synthesis gas feedstocks and oxygen perturbation on hydrogen production by Parageobacillus thermoglucosidasius.

BACKGROUND: The facultatively anaerobic thermophile Parageobacillus thermoglucosidasius is able to produce hydrogen gas (H2) through the water-gas shift (WGS) reaction. To date this process has been evaluated under controlled conditions, with gas feedstocks comprising carbon monoxide and variable proportions of air, nitrogen and hydrogen. Ultimately, an economically viable hydrogenogenic system would make use of industrial waste/synthesis gases that contain high levels of carbon monoxide, but which may also contain contaminants such as H2, oxygen (O2) and other impurities, which may be toxic to P. thermoglucosidasius. RESULTS: We evaluated the effects of synthesis gas (syngas) mimetic feedstocks on WGS reaction-driven H2 gas production by P. thermoglucosidasius DSM 6285 in small-scale fermentations. Improved H2 gas production yields and faster onset towards hydrogen production were observed when anaerobic synthetic syngas feedstocks were used, at the expense of biomass accumulation. Furthermore, as the WGS reaction is an anoxygenic process, we evaluated the influence of O2 perturbation on P. thermoglucosidasius hydrogenogenesis. O2 supplementation improved biomass accumulation, but reduced hydrogen yields in accordance with the level of oxygen supplied. However, H2 gas production was observed at low O2 levels. Supplementation also induced rapid acetate consumption, likely to sustain growth. CONCLUSION: The utilisation of anaerobic syngas mimetic gas feedstocks to produce H2 and the relative flexibility of the P. thermoglucosidasius WGS reaction system following O2 perturbation further supports its applicability towards more robust and continuous hydrogenogenic operation.

Prediction of Individual Gas Yields of Supercritical Water Gasification of Lignocellulosic Biomass by Machine Learning Models.

Supercritical water gasification (SCWG) of lignocellulosic biomass is a promising pathway for the production of hydrogen. However, SCWG is a complex thermochemical process, the modeling of which is challenging via conventional methodologies. Therefore, eight machine learning models (linear regression (LR), Gaussian process regression (GPR), artificial neural network (ANN), support vector machine (SVM), decision tree (DT), random forest (RF), extreme gradient boosting (XGB), and categorical boosting regressor (CatBoost)) with particle swarm optimization (PSO) and a genetic algorithm (GA) optimizer were developed and evaluated for prediction of H2, CO, CO2, and CH4 gas yields from SCWG of lignocellulosic biomass. A total of 12 input features of SCWG process conditions (temperature, time, concentration, pressure) and biomass properties (C, H, N, S, VM, moisture, ash, real feed) were utilized for the prediction of gas yields using 166 data points. Among machine learning models, boosting ensemble tree models such as XGB and CatBoost demonstrated the highest power for the prediction of gas yields. PSO-optimized XGB was the best performing model for H2 yield with a test R2 of 0.84 and PSO-optimized CatBoost was best for prediction of yields of CH4, CO, and CO2, with test R2 values of 0.83, 0.94, and 0.92, respectively. The effectiveness of the PSO optimizer in improving the prediction ability of the unoptimized machine learning model was higher compared to the GA optimizer for all gas yields. Feature analysis using Shapley additive explanation (SHAP) based on best performing models showed that (21.93%) temperature, (24.85%) C, (16.93%) ash, and (29.73%) C were the most dominant features for the prediction of H2, CH4, CO, and CO2 gas yields, respectively. Even though temperature was the most dominant feature, the cumulative feature importance of biomass characteristics variables (C, H, N, S, VM, moisture, ash, real feed) as a group was higher than that of the SCWG process condition variables (temperature, time, concentration, pressure) for the prediction of all gas yields. SHAP two-way analysis confirmed the strong interactive behavior of input features on the prediction of gas yields.

Structural Elucidation of Ubiquitin via Gas-Phase Ion/Ion Cross-Linking Reactions Using Sodium-Cationized Reagents Coupled with Infrared Multiphoton Dissociation.

Accurate structural determination of proteins is critical to understanding their biological functions and the impact of structural disruption on disease progression. Gas-phase cross-linking mass spectrometry (XL-MS) via ion/ion reactions between multiply charged protein cations and singly charged cross-linker anions has previously been developed to obtain low-resolution structural information on proteins. This method significantly shortens experimental time relative to conventional solution-phase XL-MS but has several technical limitations: (1) the singly deprotonated N-hydroxysulfosuccinimide (sulfo-NHS)-based cross-linker anions are restricted to attachment at neutral amine groups of basic amino acid residues and (2) analyzing terminal cross-linked fragment ions is insufficient to unambiguously localize sites of linker attachment. Herein, we demonstrate enhanced structural information for alcohol-denatured A-state ubiquitin obtained from an alternative gas-phase XL-MS approach. Briefly, singly sodiated ethylene glycol bis(sulfosuccinimidyl succinate) (sulfo-EGS) cross-linker anions enable covalent cross-linking at both ammonium and amine groups. Additionally, covalently modified internal fragment ions, along with terminal b-/y-type counterparts, improve the determination of linker attachment sites. Molecular dynamics simulations validate experimentally obtained gas-phase conformations of denatured ubiquitin. This method has identified four cross-linking sites across 8+ ubiquitin, including two new sites in the N-terminal region of the protein that were originally inaccessible in prior gas-phase XL approaches. The two N-terminal cross-linking sites suggest that the N-terminal half of ubiquitin is more compact in gas-phase conformations. By comparison, the two C-terminal linker sites indicate the signature transformation of this region of the protein from a native to a denatured conformation. Overall, the results suggest that the solution-phase secondary structures of the A-state ubiquitin are conserved in the gas phase. This method also provides sufficient sensitivity to differentiate between two gas-phase conformers of the same charge state with subtle structural variations.

Occurrence and Fate of Per- and Polyfluoroalkyl Substances (PFAS) in Atmosphere: Size-Dependent Gas-Particle Partitioning, Precipitation Scavenging, and Amplification.

The concerns about the fate of per- and polyfluoroalkyl substances (PFAS) in the atmosphere are continuously growing. In this study, size-fractionated particles, gas, and rainwater samples were simultaneously collected in Shijiazhuang, China, to investigate the multiphase distribution of PFAS in the atmosphere. Perfluoroalkyl carboxylic acids (PFCAs) dominated the total concentration of PFAS in atmospheric media. A strong positive relationship (0.79 < R2 < 0.99) was observed between the concentration of PFCAs and organic matter fraction (fOM) in different particle size fractions, while no such relationship for perfluoroalkyl sulfonic acids (PFSAs) and fOM, suggesting fOM may be an important factor influencing the size-dependent distribution of PFCAs. Temperature played a key role in the gas-particle partitioning of PFAS, while it did not significantly affect their particle-size-dependent distribution. The associative concentration fluctuation of particle and particle-bound PFAS during precipitation suggested that precipitation scavenging was an important mechanism for the removal of PFAS from the atmosphere. Furthermore, temporary increases in atmospheric PFAS concentrations were observed during the precipitation. Fugacity ratios of PFAS in rainwater and gas phase (log fR/fG ranged between 2.0 and 6.6) indicated a strong trend for PFAS to diffuse from the rainwater to the gas phase during the precipitation, which may explain that the concentration of PFAS in the gas phase continued to increase even at the end of the precipitation.

Comparison of carrier gases for the separation and quantification of mineral oil hydrocarbon (MOH) fractions using online coupled high performance liquid chromatography-gas chromatography-flame ionisation detection.

On-line coupled high performance liquid chromatography-gas chromatography-flame ionisation detection (HPLC-GC-FID) was used to compare the effect of hydrogen, helium and nitrogen as carrier gases on the chromatographic characteristics for the quantification of mineral oil hydrocarbon (MOH) traces in food related matrices. After optimisation of chromatographic parameters nitrogen carrier gas exhibited characteristics equivalent to hydrogen and helium regarding requirements set by current guidelines and standardisation such as linear range, quantification limit and carry over. Though nitrogen expectedly led to greater peak widths, all required separations of standard compounds were sufficient and humps of saturated mineral oil hydrocarbons (MOSH) and aromatic mineral oil hydrocarbons (MOAH) were appropriate to enable quantitation similar to situations where hydrogen or helium had been used. Slightly increased peak widths of individual hump components did not affect shapes and widths of the MOSH and MOAH humps were not significantly affected by the use of nitrogen as carrier gas. Notably, nitrogen carrier gas led to less solvent peak tailing and smaller baseline offset. Overall, nitrogen may be regarded as viable alternative to hydrogen or helium and may even extend the range of quantifiable compounds to highly volatile hydrocarbon eluting directly after the solvent peak.

Quantum-level investigation of air decomposed pollutants gas sensor (Pd-modified g-C3N4) influenced by micro-water content.

In the electrical industry, there are many hazardous gases that pollute the environment and even jeopardize human health, so timely detection and effective control of these hazardous gases is of great significance. In this work, the gas-sensitive properties of Pd-modified g-C3N4 interface for each hazardous gas molecule were investigated from a microscopic viewpoint, taking the hazardous gases (CO, NOx) that may be generated in the power industry as the detection target. Then, the performance of Pd-modifiedg-C3N4 was evaluated for practical applications as a gas sensor material. Novelly, an unconventional means was designed to briefly predict the effect of humidity on the adsorption properties of this sensor material. The final results found that Pd-modified g-C3N4 is most suitable as a potential gas-sensitizing material for NO2 gas sensors, followed by CO. Interestingly, Pd-modified g-C3N4 is less suitable as a potential gas-sensitizing material for NO gas sensors, but has the potential to be used as a NO cleaner (adsorbent). Unconventional simulation explorations of humidity effects show that in practical applications Pd-modified g-C3N4 remains a promising material for gas sensing in specific humidity environments. This work reveals the origin of the excellent properties of Pd-modified g-C3N4 as a gas sensor material and provides new ideas for the detection and treatment of these three hazardous gases.

Solution of time-fractional gas dynamics equation using Elzaki decomposition method with Caputo-Fabrizio fractional derivative.

In this article, Elzaki decomposition method (EDM) has been applied to approximate the analytical solution of the time-fractional gas-dynamics equation. The time-fractional derivative is used in the Caputo-Fabrizio sense. The proposed method is implemented on homogenous and non-homogenous cases of the time-fractional gas-dynamics equation. A comparison between the exact and approximate solutions is also provided to show the validity and accuracy of the technique. A graphical representation of all the retrieved solutions is shown for different values of the fractional parameter. The time development of all solutions is also represented in 2D graphs. The obtained results may help understand the physical systems governed by the gas-dynamics equation.

Plastic waste gasification using oxygen-enriched air and steam: Experimental and model results from a large pilot-scale reactor.

Advanced thermochemical technologies for plastic waste valorization represent an interesting alternative to waste-to-energy options. They are particularly appealing for waste-to-hydrogen and waste-to-chemicals applications, with autothermal steam-oxygen gasification in fluidized bed reactors showing the greatest market potential. The study describes a series of experimental tests carried out on a large pilot-scale fluidized bed gasifier, using steam and O2-enriched air, with increasing fractions of oxygen. Different values of the main operating parameters are varied: equivalence ratio (0.22-0.25), steam-to-carbon ratio (0.7-1.13), and steam-to-oxygen ratio (up to 3.2). The fuel consists of real mixed plastic waste coming from separate collection of municipal solid wastes. The data obtained are used to investigate in depth the role of the main operating parameters and to improve and validate a recently developed one-dimensional kinetic model for waste gasification. The validation shows a good agreement between experimental data and model results, suggesting the reliability of the model to predict the reactor behavior under conditions of pure steam-oxygen gasification, relevant to many industrial applications. It has been found that the equivalence ratio is the parameter that most affects the syngas composition. At a constant equivalent ratio, the molar fraction of oxygen in the enriched air shows a limited influence on syngas composition while the steam is crucial in controlling the temperature along the reactor. Provided that the steam-to-carbon molar ratio is larger than 1.5, steam affects mainly the reactor temperature rather than the syngas composition, qualifying the steam-to-oxygen molar ratio as an instrumental parameter for smooth plant operation.

Janus Membrane-Based Wearable pH Sensor with Sweat Absorption, Gas Permeability, and Self-Adhesiveness.

Wearable biomedical sensors have enabled noninvasive and continuous physiological monitoring for daily health management and early detection of chronic diseases. Among biomedical sensors, wearable pH sensors attracted significant interest, as pH influences most biological reactions. However, conformable pH sensors that have sweat absorption ability, are self-adhesive to the skin, and are gas permeable remain largely unexplored. In this study, we present a pioneering approach to this problem by developing a Janus membrane-based pH sensor with self-adhesiveness on the skin. The sensor is composed of a hydrophobic polyurethane-polydimethylsiloxane porous hundreds nanometer-thick substrate and a hydrophilic poly(vinyl alcohol)-poly(acrylic acid) porous nanofiber layer. This Janus membrane exhibits a thickness of around 10 µm, providing a conformable adhesion to the skin. The simultaneous realization of solution absorption, gas permeability, and self-adhesiveness makes it suitable for long-term continuous monitoring without compromising the comfort of the wearer. The pH sensor was tested successfully for continuous monitoring for 7.5 h, demonstrating its potential for stable analysis of skin health conditions. The Janus membrane-based pH sensor holds significant promise for comprehensive skin health monitoring and wearable biomedical applications.

Research on high performance combustible gas concentration sensor based on pyramid beam splitter matrix.

Combustible gas concentration detection faces challenges of increasing accuracy, and sensitivity, as well as high reliability in harsh using environments. The special design of the optical path structure of the sensitive element provides an opportunity to improve combustible gas concentration detection. In this study, the optical path structure of the sensitive element was newly designed based on the Pyramidal beam splitter matrix. The infrared light source was modulated by multi-frequency point signal superimposed modulation technology. At the same time, concentration detection results and confidence levels were calculated using the 4-channel combustible gas concentration detection algorithm based on spectral refinement. Through experiment, it is found that the sensor enables full-range measurement of CH4, at the lower explosive limit (LEL, CH4 LEL of 5%), the reliability level is 0.01 parts-per-million (PPM), and the sensor sensitivity is up to 0.5PPM. The sensor is still capable of achieving PPM-level detections, under extreme conditions in which the sensor's optical window is covered by 2/3, and humidity is 85% or dust concentration is 100mg/m3. Those improve the sensitivity, robustness, reliability, and accuracy of the sensor.

Measuring volume fractions of a three-phase flow without separation utilizing an approach based on artificial intelligence and capacitive sensors.

Many different kind of fluids in a wide variety of industries exist, such as two-phase and three-phase. Various combinations of them can be expected and gas-oil-water is one of the most common flows. Measuring the volume fraction of phases without separation is vital in many aspects, one of which is financial issues. Many methods are utilized to ascertain the volumetric proportion of each phase. Sensors based on measuring capacity are so popular because this kind of sensor operates seamlessly and autonomously without necessitating any form of segregation or disruption for measuring in the process. Besides, at the present moment, Artificial intelligence (AI) can be nominated as the most useful tool in several fields, and metering is no exception. Also, three main type of regimes can be found which are annular, stratified, and homogeneous. In this paper, volume fractions in a gas-oil-water three-phase homogeneous regime are measured. To accomplish this objective, an Artificial Neural Network (ANN) and a capacitance-based sensor are utilized. To train the presented network, an optimized sensor was implemented in the COMSOL Multiphysics software and after doing a lot of simulations, 231 different data are produced. Among all obtained results, 70 percent of them (161 data) are awarded to the train data, and the rest of them (70 data) are considered for the test data. This investigation proposes a new intelligent metering system based on the Multilayer Perceptron network (MLP) that can estimate a three-phase water-oil-gas fluid's water volume fraction precisely with a very low error. The obtained Mean Absolute Error (MAE) is equal to 1.66. This dedicates the presented predicting method's considerable accuracy. Moreover, this study was confined to homogeneous regime and cannot measure void fractions of other fluid types and this can be considered for future works. Besides, temperature and pressure changes which highly temper relative permittivity and density of the liquid inside the pipe can be considered for another future idea.

Characterization and health risks of short- and medium-chain chlorinated paraffins in the gas and size-fractionated particulate phases in ambient air.

Short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) have garnered significant attention because they have persistence and potential toxicity, and can undergo long-distance transport. Chlorinated paraffins (CPs) inhaled in the size-fractionated particulate phase and gas phase can carry different risks to human health due to their ability to accumulate in different regions of the respiratory tract and exhibit varying deposition efficiencies. In our study, large-volume ambient air samples in both the size-fractionated particulate phase (Dp < 1.0 µm, 1.0-2.5 µm, 2.5-10 µm, and Dp ≥ 10 µm) and gas phase were collected simultaneously in Beijing using an active sampler. The overall levels of SCCPs and MCCPs were relatively high, the ranges being 57-881 and 30-385 ng/m3, respectively. SCCPs tended to be partitioned in the gas phase (on average 75% of the ΣSCCP concentration), while MCCPs tended to be partitioned in the particulate phase (on average 62% of the ΣMCCP concentration). Significant correlations were discovered between the logarithm-transformed gas-particle partition coefficients (KP) and predicted subcooled vapor pressures (PL0) (p < 0.01 for SCCPs and MCCPs) and between the logarithm-transformed KP values and octanol-air partition coefficients (KOA) (p < 0.01 for SCCPs and MCCPs). Thus, the slopes indicated that organic matter absorption was the dominant process involved in gas-particle partitioning. We used the ICRP model to calculate deposition concentrations for particulate-associated CPs in head airways region (15.6-71.4 ng/m³), tracheobronchial region (0.8-4.8 ng/m³), and alveolar region (5.1-21.9 ng/m³), then combined these concentrations with the CP concentrations in the gas phase to calculate estimated daily intakes (EDIs) for inhalation. The EDIs for SCCPs and MCCPs through inhalation of ambient air for the all-ages group were 67.5-184.2 ng/kg/day and 19.7-53.7 ng/kg/day, respectively. The results indicated that SCCPs and MCCPs in ambient air do not currently pose strong risks to human health in the study area.

Ultrathin Boundary-Less SnO2 Films with Surface-Activated Two-Dimensional Nanograins Enable Fast and Sensitive Hydrogen Gas Sensing.

Fast and reliable semiconductor hydrogen sensors are crucially important for the large-scale utilization of hydrogen energy. One major challenge that hinders their practical application is the elevated temperature required, arising from undesirable surface passivation and grain-boundary-dominated electron transportation in the conventional nanocrystalline sensing layers. To address this long-standing issue, in the present work, we report a class of highly reactive and boundary-less ultrathin SnO2 films, which are fabricated by the topochemical transformation of 2D SnO transferred from liquid Sn-Bi droplets. The ultrathin SnO2 films are purposely made to consist of well-crystallized quasi-2D nanograins with in-plane grain sizes going beyond 30 nm, whereby the hydroxyl adsorption and grain boundary side-effects are effectively suppressed, giving rise to an activated (101)-dominating dangling-bond surface and a surface-controlled electrical transportation with an exceptional electron mobility of 209 cm2 V-1 s-1. Our work provides a new cost-effective strategy to disruptively improve the gas reception and transduction of SnO2. The proposed chemiresistive sensors exhibit fast, sensitive, and selective hydrogen sensing performance at a much-reduced working temperature of 60 °C. The remarkable sensing performance as well as the simple and scalable fabrication process of the ultrathin SnO2 films render the thus-developed sensors attractive for long awaited practical applications in hydrogen-related industries.

Unrecognized extensive charge of microbial gas in the Junggar basin.

Different from the Qaidam basin with about 320 billion m3 microbial gas, only limited microbial gases were found from the Junggar basin with similarly abundant type III kerogen. To determine whether microbial gases have not yet identified, natural gas samples from the Carboniferous to Cretaceous in the Junggar basin have been analyzed for chemical and stable isotope compositions. The results reveal some of the gases from the Mahu sag, Zhongguai, Luliang and Wu-Xia areas in the basin may have mixed with microbial gas leading to straight ethane to butane trends with a "dogleg" light methane in the Chung's plot. Primary microbial gas from degradation of immature sedimentary organic matter is found to occur in the Mahu sag and secondary microbial gas from biodegradation of oils and propane occurred in the Zhongguai, Luliang and Beisantai areas where the associated oils were biodegraded to produce calcites with δ13C values from + 22.10‰ to + 22.16‰ or propane was biodegraded leading to its 13C enrichment. Microbial CH4 in the Mahu sag is most likely to have migrated up from the Lower Wuerhe Formation coal-bearing strata by the end of the Triassic, and secondary microbial gas in Zhongguai and Beisantan uplifts may have generated after the reservoirs were uplifted during the period of the Middle and Late Jurassic. This study suggests widespread distribution of microbial gas and shows the potential to find large microbial gas accumulation in the basin.

Diverse type I and type II methanotrophs cultivated from an Indian freshwater wetland habitat

Wetlands are the main natural sources of methane emissions, which make up a significant portion of greenhouse gas emissions. Such wetland patches serve as rich habitats for aerobic methanotrophs. Limited knowledge of methanotrophs from tropical wetlands widens the scope of study from these habitats. In the present study, a freshwater wetland in a tropical region in India was sampled and serially diluted to obtain methanotrophs in culture. This was followed by the isolation of methanotrophs on agarose-containing plates, incubated under methane: air atmosphere. Methanotrophs are difficult to cultivate, and very few cultures of methanotrophs are available from tropical wetlands. Our current study reports the cultivation of a diverse community of methanotrophs from six genera, namely, Methylomonas, Methylococcus, Methylomagnum, Methylocucumis (type I methanotrophs) along with Methylocystis, Methylosinus (type II methanotrophs). A high abundance of methanotrophs (106–1010 methanotrophs/g fresh weight) was observed in the samples. A Methylococcus strain could represent a putative novel species that was also isolated. Cultures of Methylomagnum and Methylocucumis, two newly described type I methanotrophs exclusively found in rice fields, were obtained. A large number of Methylomonas koyamae strains were cultured. Our study is pioneering in the documentation of culturable methanotrophs from a typical tropical wetland patch. The isolated methanotrophs can act as models for studying methanotroph-based methane mitigation from wetland habitats and can be used for various mitigation and valorization applications. (AU)

Dimethyl sulfoxide as a gas phase charge-reducing agent for the determination of PEGylated proteins' intact mass.

Determination of PEGylated proteins' intact mass by mass spectrometry is challenging due to the molecules' large size, excessive charges, and instrument limitations. Previous efforts have been reported. However, signal variability, ion coalescence, and a generally low degree of robustness have been observed. In this work, we have explored the capabilities of post-column infusion of dimethyl sulfoxide (DMSO) following reversed-phase liquid chromatography-mass spectrometry (RP-LCMS) to determine PEG-filgrastim' intact mass, and to characterize its PEG moiety. The method was optimized around reproducibility (six preparations, and three injection replicates) with an in-house prepared PEG-filgrastim standard. The method showed a mass accuracy of ≤1.2 Da. The average molecular weight (MWEO=483) was 40 147.9 Da. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were observed to be 40 101.1 and 40 113.9 Da, respectively, both with an RSD of 0.03%. The molecular weight distribution of ethylene oxide (EO), the polydispersity index (PDI), was 1.0003 for all preparations with a minimum and maximum number of EO units of 448 ± 2 and 516 ± 2, respectively. The method was finally applied to commercially available Neulasta® lots where the Mn and Mw were 39 995.8 and 40 008.8 Da, respectively, both with an RSD of 0.1%. The minimum and maximum EO units across the lots were observed to be 444.5 ± 1.5 and 514 ± 3, respectively. The PDI for all Neulasta® lots was 1.0003. This study provides an insightful characterization of Neulasta® and describes a robust LC-MS methodology for the characterization of the PEGylated proteins.

Modeling Nonlinear Dynamics of Functionalization Layers: Enhancing Gas Sensor Sensitivity for Piezoelectrically Driven Microcantilever.

This article presents a parametrized response model that enhances the limit of detection (LOD) of piezoelectrically driven microcantilever (PD-MC) based gas sensors by accounting for the adsorption-induced variations in elastic properties of the functionalization layer (binder) and the nonlinear motional dynamics of the PD-MC. The developed model is demonstrated for quantifying cadaverine, a volatile biogenic diamine whose concentration is used to assess the freshness of meat. At low concentrations of cadaverine, an increase in the resonance frequency is observed, contrary to the expected reduction due to mass added by adsorption. The study explores the variations in the elastic modulus vis-à-vis the adsorbed mass of cadaverine and derives the resonance frequency to the adsorbed mass response function. We advance a blended technique involving the analysis of atomic force microscopy (AFM) force-distance (f-d) curves and fitting of the quartz crystal microbalance (QCM) impedance response spectrum to deduce the adsorption-induced changes in the viscoelastic properties of the functionalization layer. The findings obtained are subsequently employed in modeling the response function for a structurally nonhomogenous PD-MC, highlighting the significance of the functionalization layer to the global elastic properties. The structural composition of the PD-MC beam adopted herein features a trapezoidal base hosting the actuating piezoelectric stratum and a rectangular free end with a functionalization layer. The Euler-Bernoulli beam theory coupled with Hamilton's principle is used to develop the equation of motion, which is subsequently discretized into a set of nonlinear ordinary differential equations via Galerkin expansion, and the solutions to the first fundamental mode of vibration are determined using the method of multiple scales. The obtained solutions provide a basis for deducing the nonlinear response function model to the adsorbed mass. The derived model is validated by recorded resonance frequency changes resulting from exposure to known concentrations of cadaverine. We demonstrate that the increase in resonance frequency for low concentrations of cadaverine is due to the dominance of the variation of the elastic modulus of the functionalization layer originating from the initial binder-analyte interactions over damping due to added mass. It is concluded that the developed nonlinear response function model can reliably be used to quantify the cadaverine concentration at low concentrations with an elevated Limit of Detection.