Size-dependent Process Research Articles

Exploring the cellular antioxidant mechanism against cytotoxic silver nanoparticles: a Raman spectroscopic analysis.

Silver nanoparticles (AgNPs) hold great promise for several different applications, from colorimetric sensors to antimicrobial agents. Despite their widespread incorporation in consumer products, limited understanding of the detrimental effects and cellular antioxidant responses associated with AgNPs at sublethal concentrations persists, raising concerns for human and ecological well-being. To address this gap, we synthesized AgNPs of varying sizes and evaluated their cytotoxicity against human dermal fibroblasts (HDF). Our study revealed that toxicity of AgNPs is a time- and size-dependent process, even at low exposure levels. AgNPs exhibited low short-term cytotoxicity but high long-term impact, particularly for the smallest NPs tested. Raman microspectroscopy was employed for in-time investigations of intracellular molecular variations during the first 24 h of exposure to AgNPs of 35 nm. Subtle protein and lipid degradations were detected, but no discernible damage to the DNA was observed. Signals associated with antioxidant proteins, such as superoxide dismutase (SOD), catalase (CAT) and metallothioneins (MTs), increased over time, reflecting the heightened production of these defense agents. Fluorescence microscopy further confirmed the efficacy of overexpressed antioxidant proteins in mitigating ROS formation during short-term exposure to AgNPs. This work provides valuable insights into the molecular changes and remedial strategies within the cellular environment, utilizing Raman microspectroscopy as an advanced analytical technique. These findings offer a novel perspective on the cytotoxicity mechanism of AgNPs, contributing to the development of safer materials and advice on regulatory guidelines for their biomedical applications.

Crown die-back of peri-urban forests after combined heatwave and drought was species-specific, size-dependent, and also related to tree neighbourhood characteristics

The Rhine River valley of Germany has been facing recurrent and intense spells of drought and heatwaves threatening the health of trees in peri-urban forests. Crown damage intensified by climate change accelerates tree mortality, threatening its ecological, economic, and social benefits; however, the pattern of crown die-back in peri-urban forests remained unclear. We performed a field inventory to estimate the crown die-back of 2578 trees of 51 species from 68 randomly selected peri-urban forest plots in Karlsruhe region on the right bank of the Rhine, after the catastrophic summer heatwave and drought of 2018. We related crown die-back to species-specific drought tolerance, wood anatomical traits, tree size, canopy surface temperature, tree density, Shannon's diversity and Gini coefficient for tree height. Regression results indicate that small-size trees were found to be more susceptible to canopy damage than large trees, with a 1-meter increase in tree height associated with a 0.8 % reduction in crown die-back. This size-dependent process is also species-specific. Among the 12 species with significant (p < 0.05) linear relationship between height and die-back, 9 species demonstrated negative correlations and 3 species showed positive relationships. Species tolerant to drought or cavitation (e.g., trees with diffuse porous xylem, 21 species) had significantly lower crown dieback. For example, with a 1-point-scale increase in drought tolerance crown die-back declined 14.35 %. Trees that experienced high canopy surface temperature and grew with high tree density and species diversity (Shannon's diversity) had more crown die-back. However, high structural diversity (Gini coefficient) was related to lower crown die-back. Our results suggested that future research should focus more on tree species-specific hydraulic and thermal traits and tree density and structure management to improve tree health and species selection in peri-urban forests under future climate change.

Advances in dry hopping for industrial brewing: a review

highly hopped and dry hopped beer production and consumption has increased steadily for the last twenty years, following the rise of craft breweries in the United States of America and the trend they set over the world. This overuse of hops offers some environmental, technological, and economic challenges for the beer industry. Researchers have been studying several ways to make beer more ecofriendly by promoting reuse of spent hops and increasing extraction yields. Dry hopping is a size-dependent process, making it feasible for craft breweries with their small scale production, but quite a challenge for larger tanks and breweries. Based on the literature and industrial experience from brewers, the aim of this research was to analyze and discuss different dry hopping methodologies for the brewing industry and how the parameters affect the final product. In order to shed light on this trending topic and to better aid brewers in choosing the most suitable, efficient, and environmental-friendly dry hopping process for their brewery, this work approaches the main variables that promote aroma transfer from hops into beer and how to optimize it.

Proteomic analysis of descending thoracic aorta identifies unique and universal signatures of aneurysm and dissection

ObjectiveVery few clinical predictors of descending thoracic aorta dissection have been determined. Although aneurysms can dissect in a size-dependent process, most descending dissections will occur without prior enlargement. We compared the proteomic profiles of normal, dissected, aneurysm, and both aneurysm and dissected descending thoracic aortas to identify novel biomarkers and further understand the molecular pathways that lead to tissue at risk of dissection. MethodsWe performed proteomic profiling of descending thoracic aortas with four phenotypes: normal (n = 46), aneurysm (n = 22), dissected (n = 12), and combined aneurysm and dissection (n = 8). Pairwise differential protein expression analyses using a Bayesian approach were then performed to identify common proteins that were dysregulated between each diseased tissue type and control aorta and to uncover unique proteins between aneurysmal and dissected aortas. Network and Markov cluster algorithms of differentially expressed proteins were used to find enriched ontology processes. A convex analysis of mixtures was also performed to identify the molecular subtypes within the different tissue types. ResultsThe diseased aortas had 71 common differentially expressed proteins compared with the control, including higher amounts of the protein thrombospondin 1. We found 42 differentially expressed proteins between the aneurysm and dissected tissue, with an abundance of apolipoproteins in the former and higher quantities of extracellular matrix proteins in the latter. The convex analysis of mixtures showed enhancement of a molecular subtype enriched in contractile proteins within the control tissue compared with the diseased tissue, in addition to increased proportions of molecular subtypes enriched in inflammation and red blood cell expression in the aneurysmal compared with the dissected tissue. ConclusionsWe found some overlapping differentially expressed proteins in aneurysmal and nonaneurysmal descending thoracic aortas at risk of dissection compared with normal aortas. However, we also found uniquely altered molecular pathways that might uncover mechanisms for dissection.

Vesicles From Vibrio cholerae Contain AT-Rich DNA and Shorter mRNAs That Do Not Correlate With Their Protein Products.

Extracellular vesicles secreted by Gram-negative bacteria have proven to be important in bacterial defense, communication and host–pathogen relationships. They resemble smaller versions of the bacterial mother cell, with similar contents of proteins, LPS, DNA, and RNA. Vesicles can elicit a protective immune response in a range of hosts, and as vaccine candidates, it is of interest to properly characterize their cargo. Genetic sequencing data is already available for vesicles from several bacterial strains, but it is not yet clear how the genetic makeup of vesicles differ from that of their parent cells, and which properties may characterize enriched genetic material. The present study provides evidence for DNA inside vesicles from Vibrio cholerae O395, and key characteristics of their genetic and proteomic content are compared to that of whole cells. DNA analysis reveals enrichment of fragments containing ToxR binding sites, as well as a positive correlation between AT-content and enrichment. Some mRNAs were highly enriched in the vesicle fraction, such as membrane protein genes ompV, ompK, and ompU, DNA-binding protein genes hupA, hupB, ihfB, fis, and ssb, and a negative correlation was found between mRNA enrichment and transcript length, suggesting mRNA inclusion in vesicles may be a size-dependent process. Certain non-coding and functional RNAs were found to be enriched, such as VrrA, GcvB, tmRNA, RNase P, CsrB2, and CsrB3. Mass spectrometry revealed enrichment of outer membrane proteins, known virulence factors, phage components, flagella and extracellular proteins in the vesicle fraction, and a low, negative correlation was found between transcript-, and protein enrichment. This result opposes the hypothesis that a significant degree of protein translation occurs in vesicles after budding. The abundance of viral-, and flagellar proteins in the vesicle fraction underlines the importance of purification during vesicle isolation.

On the lifetime of a size-dependent branching process

We discuss lifetimes for a family of population-dependent branching processes. The attenuation factor (due to environment or competition, for example) is of Ricker type, i.e., the probability of an individual having offspring at all is of the form if the total population is n. Equivalently we can write the probability as where the carrying capacity K is the inverse of the attenuating factor. It is well known that the expected lifetime of such a process is exponential in K. If the carrying capacities vary much over time, for instance, if they are i.i.d. with a heavy-tailed distribution, the extinction scenario may change to a growth-catastrophe one with expected lifetimes much shorter. In addition to Ricker’s model, production functions of the Beverton–Holt and Hassell types are also discussed.

Determination of size dependent carrier capture in InGaN/GaN quantum nanowires by femto-second transient absorption spectroscopy: effect of optical phonon, electron–electron scattering and diffusion

Understanding the ultrafast processes corresponding to carrier capture, thermalization and relaxation is essential to design high speed optoelectronic devices. Here, we have investigated a size dependent carrier capture process in InGaN/GaN 20, 50 nm nanowires and quantum well systems. Femto-second transient absorption spectroscopy reveals that the carrier capture is a two-step process. The carriers are captured in the barrier by polar optical phonon (POP) scattering. They further scatter into the active region by electron–electron and POP scatterings. The capture is found to slow down for quantum confined structures. A significant number of carriers are found to disappear from the barrier during the diffusion process. All the experimental observations are explained in a simulation framework depicting various scattering mechanisms.

Reproductive allometry in four annual weeds

Differences in plant biomass/plant seed production relationship imply that plants suppressed by competition to the same extent, may not suffer the same reduction in seed number setting. This size-dependent process evidenced by the quantitative relationship between plant growth and allocation to reproductive structures can be considered from an allometric perspective. The aim of this study was to describe the reproductive allometry of four annual weed species of the Pampas cropping systems by modelling the plant biomass/plant seed production relationship in Digitaria sanguinalis, Amaranthus hybridus, Setaria verticillata and Chenopodium album. To achieve this goal, two experiments developed during two consecutive growing periods (Experiments 1 and 2) were set up under greenhouse conditions. Weed species were grown in monocultures and in binary mixtures, with each other and with soybean crop, to obtain plants of different size after the effect of intra and interspecific competition. Data per plant regarding biomass versus seed number production considering monocultures and mixtures from Experiments 1 and 2 were analysed for each species using linear regression. Parameters of the linear functions fitted for C. album, S. verticillata and D. sanguinalis did not differ between experiments and data were pooled. Thus, three single specific models were obtained with the same intercept of zero (y-axis intercept when x = 0 was zero) and different slopes, 1122, 69 and 130 seeds g plant biomass–1 respectively. In the case of A. hybridus, the slopes were different in Experiments 1 (123 seeds g plant biomass–1) and 2 (74 seeds g plant biomass–1). Moreover, reproductive allocation changed allometrically under highly competitive stress since small plants failed to set seeds, unless a plant biomass threshold was attained (x-axis intercept when y = 0 was positive). Besides the ecological interpretation in reproductive output, implications in weed management are considered.

The stochastic transition from size dependent to size independent yield strength in metallic glasses

It has been an enduring and heated debate whether the yield strength of metallic glasses (MGs) is size dependent or size independent. In this work, we first develop a micromechanical model by taking into account the stochasticity for shear band initiation in microcompression. Our modeling is subsequently verified through the extensive in-situ and ex-situ microcompression experiments. Through the efforts of combined experiments and modeling, we show a size-controlled stochastic transition from the size dependent to the size independent yield strength in the MG micropillars. Such a stochastic transition is featured with a strong fluctuation in the measured yield strengths when the micropillar size is near an intrinsic length scale which varies with the chemical composition of MGs. In contrast, such a size-controlled transition appear deterministic with little data scattering in tension. At the fundamental level, our results unfold a size dependent shear band initiation process in MGs, which may be applicable to other amorphous materials of technological importance.

Strong Size Dependency on the Carrier and Photon Dynamics in InGaN/GaN Single Nanowalls Determined Using Photoluminescence and Ultrafast Transient Absorption Spectroscopy.

Here, we have demonstrated strong size dependency of quasi-equilibrium and nonequilibrium carrier and photon dynamics in InGaN/GaN single nanowalls using photoluminescence and transient absorption spectroscopy. We demonstrate that two-dimensional carrier confinement, strain relaxation, and modified density of states lead to a reduced Stokes shift, smaller full width at half-maxima, increased exciton binding energy, and reduced nonradiative recombination. The ultrafast transient spectroscopy shows that carrier capture is a two-step process dominated by optical phonons and carrier-carrier scattering in succession. The carrier capture is a strongly size-dependent process and becomes slower due to modulation of the density of available states for progressively decreasing nanowall sizes. The slowest process is the electron-hole recombination, which is also extremely size-dependent and the rate increases by almost an order of magnitude in comparison to that of quantum-well structures. Electron-hole wave function overlap and modified density of states are among the key aspects in determining all the properties of these structures.

Crater density differences: Exploring regional resurfacing, secondary crater populations, and crater saturation equilibrium on the moon

The global population of lunar craters >20 km in diameter was analyzed by Head et al., (2010) to correlate crater distribution with resurfacing events and multiple impactor populations. The work presented here extends the global crater distribution analysis to smaller craters (5–20 km diameters, n = 22,746). Smaller craters form at a higher rate than larger craters and thus add granularity to age estimates of larger units and can reveal smaller and younger areas of resurfacing. An areal density difference map generated by comparing the new dataset with that of Head et al., (2010) shows local deficiencies of 5–20 km diameter craters, which we interpret to be caused by a combination of resurfacing by the Orientale basin, infilling of intercrater plains within the nearside highlands, and partial mare flooding of the Australe region. Chains of 5–30 km diameter secondaries northwest of Orientale and possible 8–22 km diameter basin secondaries within the farside highlands are also distinguishable. Analysis of the new database indicates that craters 57–160 km in diameter across much of the lunar highlands are at or exceed relative crater densities of R = 0.3 or 10% geometric saturation, but nonetheless appear to fit the lunar production function. Combined with the observation that small craters on old surfaces can reach saturation equilibrium at 1% geometric saturation (Xiao and Werner, 2015), this suggests that saturation equilibrium is a size-dependent process, where large craters persist because of their resistance to destruction, degradation, and resurfacing.

Scaling copepod grazing in a coastal upwelling system: the importance of community size structure for phytoplankton C flux

Crustacean zooplankton, often dominated by copepods and euphausiids, are the major phytoplankton grazers in coastal upwelling systems. It has been argued that grazing by zooplankton is a size-dependent process, such that models incorporating the size structure of zooplankton are appropriate for describing herbivore C-transfer. Here, b ased on the size-spectrum theory and on gut-fluorescence experiments, conducted with numerically dominant copepods from two upwelling sites off the Chilean coast , we show that C-specific ingestion rates of copepods are size-dependent. We further show that the size structure of the copepod community, synthesized by the slope of the normalized size spectrum, determines the impact of grazing on phytoplankton. C-specific ingestion rates, depending on species size, were in the range of 0.02-8.40 (µg C x µg C -1 d -1 ). A modelled normalized biomass-spectra of a copepod community in the size range of 0.5 to 74.0 µg C showed that C-specific grazing impact can increase by a factor of 4 when small-sized species (0.1-10 µg C indiv -1 ), such as Paracalanus cf. indicus , Acartia tonsa , Oncaea spp. and Corycaeus spp., dominate the community in terms of biomass. By contrast, when larger-sized copepods dominate (10-100 µg C indiv -1 ), such as Calanus chilensis , Calanoides patagoniensis and Rhyncalanus nasutus , total zooplankton biomass may increase, but with a sharp decrease in the efficiency of C transfer via herbivores. Our findings indicate that processes affecting the size structure of zooplankton communities can substantially impact on phytoplankton C flux through the pelagic food web, thus controlling production of higher trophic levels.

Extension of discrete tribocharging models to continuous size distributions.

Triboelectric charging, the phenomenon by which electrical charge is exchanged during contact between two surfaces, has been known to cause significant charge separation in granular mixtures, even between chemically identical grains. This charging is a stochastic size-dependent process resulting from random collisions between grains. The prevailing models and experimental results suggest that, in most cases, larger grains in a mixture of dielectric grains acquire a positive charge, while smaller grains charge negatively. These models are typically restricted to mixtures of two discrete grain sizes, which are not representative of most naturally occurring granular mixtures, and neglect the effect of grain size on individual charging events. We have developed a model that predicts the average charge distribution in a granular mixture, for any continuous size distribution of dielectric grains of a single material. Expanding to continuous size distributions enables the prediction of charge separation in many natural granular phenomena, including terrestrial dust storms and industrial powder handling operations. The expanded model makes predictions about the charge distribution, including specific conditions under which the usual size-dependent polarity is reversed such that larger grains charge negatively.

Comparative evaluation of the impact on endothelial cells induced by different nanoparticle structures and functionalization.

In the research field of nanoparticles, many studies demonstrated a high impact of the shape, size and surface charge, which is determined by the functionalization, of nanoparticles on cell viability and internalization into cells. This work focused on the comparison of three different nanoparticle types to give a better insight into general rules determining the biocompatibility of gold, Janus and semiconductor (quantum dot) nanoparticles. Endothelial cells were subject of this study, since blood is the first barrier after intravenous nanoparticle application. In particular, stronger effects on the viability of endothelial cells were found for nanoparticles with an elongated shape in comparison to spherical ones. Furthermore, a positively charged nanoparticle surface (NH2, CyA) leads to the strongest reduction in cell viability, whereas neutral and negatively charged nanoparticles are highly biocompatible to endothelial cells. These findings are attributed to a rapid internalization of the NH2-functionalized nanoparticles in combination with the damage of intracellular membranes. Interestingly, the endocytotic pathway seems to be a size-dependent process whereas nanoparticles with a size of 20 nm are internalized by caveolae-mediated endocytosis and nanoparticles with a size of 40 nm are taken up by clathrin-mediated internalization and macropinocytosis. Our results can be summarized to formulate five general rules, which are further specified in the text and which determine the biocompatibility of nanoparticles on endothelial cells. Our findings will help to design new nanoparticles with optimized properties concerning biocompatibility and uptake behavior with respect to the respective intended application.

Spontaneous formation of Au-Pt alloyed nanoparticles using pure nano-counterparts as starters: a ligand and size dependent process.

In this work we investigate the formation of PtAu monodisperse alloyed nanoparticles by ageing pure metallic Au and Pt small nanoparticles (sNPs), nanoparticle size <5 nm, under certain conditions. We demonstrate that those bimetallic entities can be obtained by controlling the size of the initial metallic sNPs separately prepared and by selecting their appropriate capping agents. The formation of this spontaneous phenomenon was studied using HR-STEM, EDS, ionic conductivity, UV-Vis spectroscopy and cyclic voltammetry. Depending on the type of capping agent used and the size of the initial Au sNPs, three different materials were obtained: (i) AuPt bimetallic sNPs showing a surface rich in Au atoms, (ii) segregated Au and Pt sNPs and (iii) a mixture of bimetallic nanoparticles as well as Pt sNPs and Au NPs. Surface segregation energies and the nature of the reaction environment are the driving forces to direct the distribution of atoms in the bimetallic sNPs. PtAu alloyed nanoparticles were obtained after 150 h of reaction at room temperature if a weak capping agent was used for the stabilization of the nanoparticles. It was also found that Au atoms diffuse towards Pt sNPs, producing a surface enriched in Au atoms. This study shows that even pure nanoparticles are prone to be modified by the surrounding nanoparticles to give rise to new nanomaterials if atomic diffusion is feasible.

Investigation the complex dynamic evolvement mechanism of particle cluster and surface integrity in the chemical mechanical planarization

The surface planarization in the chemical mechanical planarization is mainly realized by the mechanical effect which depends on the micro-tribology behavior of nanoparticles. The material removal rate is decreased and micro-scratch is generated in the wafer surface due to the agglomeration of particles. The slurry particles hold definite energy level and microstructure which makes the classical materials processing theory unable to give reasonable explanation about this process. Large-scale classical molecular dynamic simulation of interaction among nanoparticles and solid surface has been carried out to investigate the evolvement mechanism of particle cluster and surface planarization. It is showed that the particle aggregation behavior is a size-dependent process because of the high ratio of surface atoms to bulk atoms which leads to the active reactivity and catalytic activity of nanoparticles. The substrate materials (nanoparticle) become transforming from low-energy stable system to high-energy unstable system after the two-body collision which is favorable for aggregation process. There exists obvious geometry boundary between the particle elements in the large aggregates and only the dendritic aggregates formed. The larger particles have definite microstructure and additional internal degree of freedom which can be used to take up, store, and transfer energy, thus lower the activity of chemical reaction which weaken the particle aggregation process.

Analysing SANS data to determine magnetisation reversal processes in composite perpendicular magnetic recording media using TEM images

Abstract Perpendicular magnetic recording media based on CoCrPt – SiOx thin-films have been studied with polarised small angle neutron scattering (SANSPOL) to probe the local (sub-10 nm) granular structure and its magnetisation distribution. SANSPOL is sensitive to the direction of the magnetisation vector in the grains over a size range of 1 – 100 nm. This allows the grain size dependent magnetic reversal process to be probed in the recording layer. SANSPOL data can be analysed both using numerical models and through comparison with the granular structure determined using transmission electron microscopy. In this paper we compare these two methods in detail and demonstrate that both approaches arrive at very similar conclusions.

Size-dependent thermal oxidation of copper: single-step synthesis of hierarchical nanostructures

Thermal oxidation of copper is a simple and scalable method to produce copper oxide nanowires. We report for the first time the formation of nanowires on copper powder during thermal oxidation and the resulting nanowire coverage that is dependent on the initial particle size. Systematic thermogravimetric analysis (TGA) and in situ X-ray diffraction (XRD) studies of thermal oxidation of particles of different sizes provide insights into the size-dependent process and evolution of the various phases of copper and copper oxide with time. Furthermore, we find that a large void is formed within these particles after oxidation and propose a mechanism based on the Kirkendall effect. The unique tunability of hierarchical features and hollow interior can be used to create new scalable structures for applications in a variety of areas including thermal management and catalysis.

Strong size-dependent characteristics of carrier injection in quantum-confined silicon nanocrystals

We report the strong size-dependent carrier injection process in quantum-confined silicon nanocrystals embedded in silicon nitride films. As the diameter of silicon nanocrystals increases, the threshold voltage for carrier injection decreases whereas the number of injected carriers increases due to the quantum size effect. The tunneling time for the carrier injection is decreased by two orders of magnitude when the diameter of silicon nanocrystals is increased from 3.4 to 5.0 nm, and this is attributed to the enhanced nonresonant tunneling in the larger silicon nanocrystals.

Mathematical Models for a Closed-Circuit Grinding

New continuous and discrete mathematical models are elaborated for describing some types of closed-circuit grinding mill-classifier systems. Based on the discrete model computer simulation is also developed for investigation of grinding processes. The starting point in developing the model is the continuous grinding equation for the open-circuit grinding which is a partial integro-differential equation describing axial mixing and breakage of particles in the grinding mill. The convective flow in the mill is modeled as particle size-dependent process. The boundary conditions at the inlet and outlet of the mill, the initial conditions, and the equations describing the operation of the classifier and its mass balance are the additional equations of the model. The properties and capabilities of the new computer model are demonstrated and analyzed by simulation developed in Matlab environment. The effects of all parameters of the grinding process, among others of parameters of the classifier, are studied via simulation. The main statistical characteristics of the steady states, the hold-up of the grinding device and the operation of the classifier are also studied. The models presented appear to be very flexible and useful tools for analysis and design of closed-circuit grinding processes, and are suitable for the deeper understanding of the aimed processes.