Nucleation Events Research Articles

Evidence of nitrate-based nighttime atmospheric nucleation driven by marine microorganisms in the South Pacific.

Our understanding of ocean-cloud interactions and their effect on climate lacks insight into a key pathway: do biogenic marine emissions form new particles in the open ocean atmosphere? Using measurements collected in ship-borne air-sea interface tanks deployed in the Southwestern Pacific Ocean, we identified new particle formation (NPF) during nighttime that was related to plankton community composition. We show that nitrate ions are the only species for which abundance could support NPF rates in our semicontrolled experiments. Nitrate ions also prevailed in the natural pristine marine atmosphere and were elevated under higher sub-10 nm particle concentrations. We hypothesize that these nucleation events were fueled by complex, short-term biogeochemical cycling involving the microbial loop. These findings suggest a new perspective with a previously unidentified role of nitrate of marine biogeochemical origin in aerosol nucleation.

Development and Numerical Testing of a Model of Equiaxed Alloy Solidification Using a Phase Field Formulation

A computational framework is developed to understand the transient behavior of isothermal and non-isothermal transformation between liquid and solid phases in a binary alloy using a phase-field method. The non-isothermal condition was achieved by applying a thermal gradient along the computational domain. The bulk solid and liquid phases were treated as regular solutions, along with introducing an order parameter (phase field) as a function of space and time to describe the interfacial region between the two phases. An antitrapping flux term was integrated into the present phase-field model to mitigate the amount of solute trapping, which is characterized by the non-equilibrium partitioning of the solute. The governing equations for the phase field and the solute composition were solved by the cell-centered finite volume method using the open-source computational tool OpenFOAM. Simulations were carried out for the evolution of equiaxed dendrites inside an undercooled melt of a binary alloy, considering the effect of various computational parameters such as interface thickness, strength of crystal anisotropy, stochastic noise amplitude, and initial orientation. The simulated results show that the solidification morphology is sensitive to the magnitude of anisotropy as well as the amplitude of noise. A strong influence of interface thickness on the growth morphology and solute redistribution during solidification was observed. Incorporating antitrapping flux resulted in the solute partitioning close to the equilibrium value. Simulations show that the grain shape is unaffected by changes to crystallographic orientation with respect to the Cartesian computational grid. Thermal gradients exerted discernible effects on the solute distribution and the dendritic growth pattern. Starting with multiple nucleation events the model predicted realistic polycrystalline solidification and as-solidified microstructure.

Microstructure evolution and constitutive analysis of nuclear grade AISI-316H austenitic stainless steel during thermal deformation

Compression experiments were performed on AISI-316H austenitic stainless steel using Gleeble-3800 at temperatures ranging from 900 °C and 1200 °C and strain rates ranging from 0.01 and 10 s−1, up to the actual strain of 0.69. The tests aimed to examine the material’s microstructure evolution and flow stress behavior. Based on OM and EBSD studies, it was found that thermal deformation mostly induces discontinuous dynamic recrystallization (DDRX). The proportion of recrystallization nucleation increases steadily with increasing deformation temperature, while the impact of strain rate on recrystallization is complex. At the same deformation temperature, the recrystallization volume fraction initially declines and rises as the strain rate rises. In low strain rate regime, the longer (deformation) time available for grain boundary migration, the higher recrystallization volume fraction. In high strain rate regime, the higher stored energy (and thus the increased boundary velocity) raises the probability of nucleation events, stimulating twin formation. As a result, the twin promotes a dynamic recrystallization (DRX) process. An abundance of Σ3 twins was notably observed in uniformly refined recrystallized grains at a true strain of 0.69, at a temperature of 1200 °C, and a strain rate of 10 s−1. As a result, it was discovered that DRX occurs at higher strain rates and deformation temperatures. In addition, the flow stress curves were modified to account for adiabatic heating at strain rates exceeding 1 s−1. The findings demonstrated that adiabatic heating increased when strain level and strain rate increased and deformation temperature decreased. The strain compensation Arrhenius model is developed following the given stress–strain curve while considering strain. The model exhibits high accuracy, with a correlation value of 0.986. According to a kinetic study, the average activation energy for hot deformation of the tested steel was 444.994 kJ/mol. These findings provide fundamental insights into the microstructure control technology and the outstanding mechanical properties of the austenitic stainless steel AISI-316H.

Molecular simulation approaches to study crystal nucleation from solutions: Theoretical considerations and computational challenges

AbstractNucleation is the initial step in the formation of crystalline materials from solutions. Various factors, such as environmental conditions, composition, and external fields, can influence its outcomes and rates. Indeed, controlling this rate‐determining step toward phase separation is critical, as it can significantly impact the resulting material's structure and properties. Atomistic simulations can be exploited to gain insight into nucleation mechanisms—an aspect difficult to ascertain in experiments—and estimate nucleation rates. However, the microscopic nature of simulations can influence the phase behavior of nucleating solutions when compared to macroscale counterparts. An additional challenge arises from the inadequate timescales accessible to standard molecular simulations to simulate nucleation directly; this is due to the inherent rareness of nucleation events, which may be apparent in silico at even high supersaturations. In recent decades, molecular simulation methods have emerged to circumvent length‐ and timescale limitations. However, it is not always clear which simulation method is most suitable to study crystal nucleation from solution. This review surveys recent advances in this field, shedding light on typical nucleation mechanisms and the appropriateness of various simulation techniques for their study. Our goal is to provide a deeper understanding of the complexities associated with modeling crystal nucleation from solution and identify areas for further research. This review targets researchers across various scientific domains, including materials science, chemistry, physics and engineering, and aims to foster collaborative efforts to develop new strategies to understand and control nucleation.This article is categorized under: Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods Molecular and Statistical Mechanics > Free Energy Methods Theoretical and Physical Chemistry > Statistical Mechanics

DETECTION OF VOID NUCLEATION, COALESCENCE AND COLLAPSE IN ATOMISTIC SIMULATIONS

Extraction of required information from atomic configurations is crucial for efficient use of molecular dynamics (MD) simulations, and automating this process allows the collection of statistical data to develop and validate physical models and data-driven approaches. Here we update the previously developed pore searching algorithm to automatically detect the events of void nucleation, collapse and coalescence by comparing pairs of atomic configurations. We calculate an intersection matrix, which shows common regions between voids of current and previous time frames, and analysis of this intersection matrix gives a numerical criterion for determination of the considered events. The updated algorithm is verified in the case of small MD system and further used to analyze a large MD system with many hundreds of voids. The predominance of void collapse is confirmed in the case of uniform triaxial tension of solid aluminum, while void coalescence instead of collapse is detected in the case of a more complex loading with axial compression and lateral tension. This dependence of the predominant mechanism on the loading path correlates with previous finite element analysis in the literature. Another interesting finding is a continuing nucleation and collapse of voids far beyond the fracture beginning at a level of negative pressure much lower than the spall strength, which can be attributed to a developed defect structure of material produced by plastic growth of voids.

Impact of local chemical ordering on deformation mechanisms in single-crystalline CuNiCoFe high-entropy alloys: a molecular dynamics study

High-entropy alloys (HEAs), composed of multiple constituent elements with concentrations ranging from 5% to 35%, have been considered ideal solid solution of multi-principal elements. However, recent experimental and computational studies have demonstrated that complex enthalpic interactions among constituents lead to a wide variety of local chemical ordering (LCO) at lower temperatures. HEAs containing Cu typically decompose by forming of Cu-rich phases during annealing, thus affecting mechanical properties. In this study, CuNiCoFe HEA was chosen as a model with a tendency for Cu segregation at low temperatures. The formation of LCO and its impact on the deformation behaviors in the single-crystalline CuNiCoFe HEA were studied via molecular dynamics simulations. Our results demonstrate that CuNiCoFe HEA decomposes by Cu clustering, in agreement with prior experimental and computational studies, owing to insufficient configuration entropy to compete against the mixing enthalpy at lower temperatures. A softening in ultimate stress in the LCO models was observed compared to the random solid solution models. The softening is due to the lower unstable stacking fault energy, which determines the nucleation event of dislocations, thereby rationalizing the dislocation nucleation in the Cu-rich regions and the softening of the overall ultimate strength in the LCO models. Additionally, the inhomogeneous FCC–BCC transformation is closely associated with concentration inhomogeneity. CuNiCoFe HEA with LCO can be regarded as composites, consisting of clusters with different properties. Consequently, concentration inhomogeneity induced by LCO profoundly impacts the mechanical properties and deformation behaviors of the HEA. This study provides insights into the effect of LCO on the mechanical properties of CuNiCoFe HEAs, which is crucial for developing HEAs with tailored properties for specific applications.

Freeze-Induced Phase Transition and Local Pressure in a Phospholipid/Water System: Novel Insights Were Obtained from a Time/Temperature Resolved Synchrotron X-ray Diffraction Study.

Water-to-ice transformation results in a 10% increase in volume, which can have a significant impact on biopharmaceuticals during freeze-thaw cycles due to the mechanical stresses imparted by the growing ice crystals. Whether these stresses would contribute to the destabilization of biopharmaceuticals depends on both the magnitude of the stress and sensitivity of a particular system to pressure and sheer stresses. To address the gap of the "magnitude" question, a phospholipid, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), is evaluated as a probe to detect and quantify the freeze-induced pressure. DPPC can form several phases under elevated pressure, and therefore, the detection of a high-pressure DPPC phase during freezing would be indicative of a freeze-induced pressure increase. In this study, the phase behavior of DPPC/water suspensions, which also contain the ice nucleation agent silver iodide, is monitored by synchrotron small/wide-angle X-ray scattering during the freeze-thaw transition. Cooling the suspensions leads to heterogeneous ice nucleation at approximately -7 °C, followed by a phase transition of DPPC between -11 and -40 °C. In this temperature range, the initial gel phase of DPPC, Lβ', gradually converts to a second phase, tentatively identified as a high-pressure Gel III phase. The Lβ'-to-Gel III phase transition continues during an isothermal hold at -40 °C; a second (homogeneous) ice nucleation event of water confined in the interlamellar space is detected by differential scanning calorimetry (DSC) at the same temperature. The extent of the phase transition depends on the DPPC concentration, with a lower DPPC concentration (and therefore a higher ice fraction), resulting in a higher degree of Lβ'-to-Gel III conversion. By comparing the data from this study with the literature data on the pressure/temperature Lβ'/Gel III phase boundary and the lamellar lattice constant of the Lβ' phase, the freeze-induced pressure is estimated to be approximately 0.2-2.6 kbar. The study introduces DPPC as a probe to detect a pressure increase during freezing, therefore addressing the gap between a theoretical possibility of protein destabilization by freeze-induced pressure and the current lack of methods to detect freeze-induced pressure. In addition, the observation of a freeze-induced phase transition in a phospholipid can improve the mechanistic understanding of factors that could disrupt the structure of lipid-based biopharmaceuticals, such as liposomes and mRNA vaccines, during freezing and thawing.

Resolving Temperature-Dependent Hydrate Nucleation Pathway: The Role of "Transition Layer".

Understanding the nucleation of natural gas hydrate (NGH) at different conditions has important implications to NGH recovery and other industrial applications, such as gas storage and separation. Herein, vast numbers of hydrate nucleation events are traced via molecular dynamics (MD) simulations at different degrees of supercooling (or driving forces). Specifically, to precisely characterize a hydrate nucleus from an aqueous system during the MD simulation, we develop an evolutionary order parameter (OP) to recognize the nucleus size and shape. Subsequently, the free energy landscapes of hydrate during nucleation are explored by using the newly developed OP. The results suggest that at 270 K (or 0.92 Tm supercooling, where Tm is the melting point), the near-rounded nucleus prevails during the nucleation, as described from the classical nucleation theory. In contrast, at relatively strong driving forces of 0.85 and 0.88 Tm, nonclassical nucleation events arise. Specifically, the pathway toward an elongated nucleus becomes as important as the pathway toward a near-rounded nucleus. To explain the distinct nucleation phenomena at different supercoolings, a notion of a "transition layer" (or liquid-blob-like layer) is proposed. Here, the transition layer is to describe the interfacial region between the nucleus and aqueous solution, and this layer entails two functionalities: (1) it tends to retain CH4 depending on the degrees of supercooling and (2) it facilitates collision among CH4, which thus promote the incorporation of CH4 into nucleus. Our simulation indicates that compared to the near-rounded nucleus, the transition layer surrounding the elongated nucleus is more evident with the higher collision rate among CH4 molecules. As such, the transition layer tends to promote the elongated nucleus pathway, while offsetting the cost of larger surface free energy associated with the elongated nucleus. At 0.92 Tm, however, the transition layer gradually disappears, and classical nucleation events dominate. Overall, the notion of "transition layer" offers deeper insight into the NGH nucleation at different degrees of supercooling and could be extended to describe other types of hydrate nucleation.

Effects of process parameters on the microstructure of Inconel 718 during powder bed fusion based on cellular automata approach

ABSTRACT Using numerical simulation methods in additive manufacturing (AM) processes can effectively reduce the cost of process exploration. This study presents a multi-scale simulation study based on the powder bed model for grain growth in the laser powder bed fusion (L-PBF) process of the Inconel 718 material. The finite volume method (FVM) and cellular automaton (CA) model were used to reproduce the process. The simulation results were consistent with the experimental results in terms of melt pool morphology, grain structure, and average grain size. The processes of the competitive and epitaxial growth of grains were discussed. The effects of laser power, scanning speed, hatch distance, and scanning strategy on microstructure were further analyzed through pole figure, grain area distribution, CA nucleation and capture event. The results demonstrated the feasibility of this method in predicting the evolution of microstructures in the L-PBF process and provide a reference for future research.

The C-terminal domain of the antiamyloid chaperone DNAJB6 binds to amyloid-β peptide fibrils and inhibits secondary nucleation

The DNAJB6 chaperone inhibits fibril formation of aggregation-prone client peptides through interaction with aggregated and oligomeric forms of the amyloid peptides. Here, we studied the role of its C-terminal domain (CTD) using constructs comprising either the entire CTD or the first two or all four of the CTD β-strands grafted onto a scaffold protein. Each construct was expressed as WT and as a variant with alanines replacing five highly conserved and functionally important serine and threonine residues in the first β-strand. We investigated the stability, oligomerization, antiamyloid activity, and affinity for amyloid-β (Aβ42) species using optical spectroscopy, native mass spectrometry, chemical crosslinking, and surface plasmon resonance technology. While DNAJB6 forms large and polydisperse oligomers, CTD was found to form only monomers, dimers, and tetramers of low affinity. Kinetic analyses showed a shift in inhibition mechanism. Whereas full-length DNAJB6 activity is dependent on the serine and threonine residues and efficiently inhibits primary and secondary nucleation, all CTD constructs inhibit secondary nucleation only, independently of the serine and threonine residues, although their dimerization and thermal stabilities are reduced by alanine substitution. While the full-length DNAJB6 inhibition of primary nucleation is related to its propensity to form coaggregates with Aβ, the CTD constructs instead bind to Aβ42 fibrils, which affects the nucleation events at the fibril surface. The retardation of secondary nucleation by DNAJB6 can thus be ascribed to the first two β-strands of its CTD, whereas the inhibition of primary nucleation is dependent on the entire protein or regions outside the CTD.

In search of a precursor for crystal nucleation of hard and charged colloids.

The interplay between crystal nucleation and the structure of the metastable fluid has been a topic of significant debate over recent years. In particular, it has been suggested that even in simple model systems such as hard or charged colloids, crystal nucleation might be foreshadowed by significant fluctuations in local structure around the location where the nucleus first arises. We investigate this using computer simulations of spontaneous nucleation events in both hard and charged colloidal systems. To detect local structural variations, we use both standard and unsupervised machine learning methods capable of finding hidden structures in the metastable fluid phase. We track numerous nucleation events for the face-centered cubic and body-centered cubic crystals on a local level and demonstrate that all signs of crystallinity emerge simultaneously from the very start of the nucleation process. We thus conclude that we observe no precursor for the crystal nucleation of hard and charged colloids.

Bringing the photoplastic effect in ZnO to light: A photoindentation study on pyramidal slip

The external light environment has been reported to have a pronounced influence on the dislocation-based plasticity in various inorganic semiconductors. Herein, with a specific focus on the pyramidal slip in wurtzite structures, photoindentation tests were performed on the (0001) plane of ZnO crystal to activate the pyramidal slip and evaluate the effects of light on dislocation behaviors. Statistical analyses of the first pop-in events suggested that the corresponding maximum shear stresses in darkness were slightly smaller than those in 405 nm light, indicating a minor effect of light on dislocation nucleation event. Regarding nanoindentation creep tests, light illumination was found to suppress the indentation depth. Further transmission electron microscopy observations demonstrated that indentation-induced pyramidal dislocations were present deeper in darkness than in 405 nm light, revealing a suppressive effect of light illumination on the pyramidal slip in ZnO for the first time.

Reduction of anthropogenic emissions enhanced atmospheric new particle formation: Observational evidence during the Beijing 2022 Winter Olympics

Strictly restrictions on anthropogenic emissions during the Beijing 2022 Winter Olympics Game (WOG) provided a distinctive chance to investigate the behavior of new particle formation events in highly polluted atmosphere under reduced primary emission conditions. In this study, comprehensive observations focus of nucleation events and their gaseous precursor were conducted before and after WOG. Our results showed that nucleation events were enhanced during the WOG and the Winter Paralympics Game (WPG) period, with much higher frequencies of NPF event (52.4%; 38.5%) compared with those before WOG (Pre-WOG: 25.0%), and after WOG (Post-WOG: 27.8%) which mainly caused by lower CS. In addition, the average formation rate (J3) during WOG (6.4 ± 4.1 cm−3·s−1) and WPG (6.1 ± 2.9 cm−3·s−1) was also higher than those in Pre-WOG (5.6 ± 2.9 cm−3·s−1) and Post-WOG (5.7 ± 3.1 cm−3·s−1), while the growth rate (GR) (2.3 ± 1.8 nm·h−1, 2.7 ± 1.4 nm·h−1) was slightly higher compared with Pre-WOG (2.1 ± 1.5 nm·h−1) and Post-WOG (2.2 ± 1.6 nm·h−1). We find that the higher J3 during WOG and WPG would be contributed by the higher amines, considering lower concentrations in sulfuric acid (SA) and ammonia was observed. Further evidence comes from the observed correlations between log J3 and SA was highly consistent with CLOUD experimental results which suggested sulfuric acid nucleation enhanced by amines. Sulfuric acid was found to be contributed over 20% to GR3–7nm, while the contribution from organic compounds increased rapidly when particles grow above 10 nm, especially during the WOG and WPG when atmospheric oxidative capacity was largely enhanced. In addition, ammonium nitrate was also found to play an important role in NPF-initiated haze episodes, characterized by higher nitrate production in late growth stage of NPF event during Post-WOG than that of WPG, suggested control measures on the emissions of NH3 and NO2 would benefit for reducing the PM2.5 pollution caused by the new particle formation and growth events.

Metal Binding of Alzheimer's Amyloid-β and Its Effect on Peptide Self-Assembly.

ConspectusMetal ions have been identified as key factors modulating the aggregation of amyloid-β peptide (Aβ) implicated in Alzheimer's disease (AD). The presence of elevated levels of metal ions in the amyloid plaques in AD patients supports the notion that the dysfunction of metal homeostasis is connected to the development of AD pathology. Here, recent findings from high- and low-resolution biophysical techniques are put into perspective, providing detailed insights into the molecular structures and dynamics of metal-bound Aβ complexes and the effect of metal ions on the Aβ aggregation process. In particular, the development of theoretical kinetic models deducing different microscopic nucleation events from the macroscopic aggregation behavior has enabled deciphering of the effect of metal ions on specific nucleation processes. In addition to these macroscopic measurements of bulk aggregation to quantify microscopic rates, recent NMR studies have revealed details about the structures and dynamics of metal-Aβ complexes, thereby linking structural events to bulk aggregation. Interestingly, transition-metal ions, such as copper, zinc, and silver ions, form a compact complex with the N-terminal part of monomeric Aβ, respectively, where the metal-bound "folded" state is in dynamic equilibrium with an "unfolded" state. The rates and thermodynamic features of these exchange dynamics have been determined by using NMR relaxation dispersion experiments. Additionally, the application of specifically tailored paramagnetic NMR experiments on the Cu(II)-Aβ complex has been fruitful in obtaining structural constraints within the blind sphere of conventional NMR experiments. This enables the determination of molecular structures of the "folded" Cu(II)-coordinated N-terminal region of Aβ. Furthermore, the discussed transition-metal ions modulate Aβ self-assembly in a concentration-dependent manner, where low metal ion concentrations inhibit Aβ fibril formation, while at high metal ion concentrations other processes occur, resulting in amorphous aggregate formation. Remarkably, the metal-Aβ interaction predominately reduces one specific nucleation step, the fibril-end elongation, whereas primary and surface-catalyzed secondary nucleation mechanisms are less affected. Specific inhibition of fibril-end elongation theoretically predicts an enhanced generation of Aβ oligomers, which is an interesting contribution to understanding metal-Aβ-associated neurotoxic effects. Taken together, the metal binding process creates a metal-bound Aβ complex, which is seemingly inert to aggregation. This process hence efficiently reduces the aggregation-prone peptide pool, which on the macroscopic level is reflected as slower aggregation kinetics. Thus, the specific binding of metals to the Aβ monomer can be linked to the macroscopic inhibitory effect on Aβ bulk aggregation, providing a molecular understanding of the Aβ aggregation mechanism in the presence of metal ions, where the metal ion can be seen as a minimalist agent against Aβ self-assembly. These insights can help to target Aβ aggregation in vivo, where metal ions are key factors modulating the Aβ self-assembly and Aβ-associated neurotoxicity.

Enhanced Electrical Conductivity of (001) Oriented Sr0.9La0.1TiO3 Microplatelets for Thermoelectric Applications.

Two-dimensional perovskite microplatelets have played an important role in various applications, especially acting as a template to guide grains' epitaxial growth in the preparation of textured ceramics. The (001) oriented Sr0.9La0.1TiO3 microplatelets with a high aspect ratio of ∼20 were synthesized and obtained from Aurivillius Bi4Ti3O12 precursors. To reveal the mechanism of topochemical microcrystal conversion of Bi4Ti3O12 to Sr0.9La0.1TiO3, the reaction interface, morphology development, and phase composition evolution of the (001) oriented Sr0.9La0.1TiO3 microplatelets were investigated. When the temperature of the molten salt is above 753 °C, multiple Sr0.9La0.1TiO3 topological nucleation events took place. At 950 °C, the polycrystalline aggregate of (001)-oriented Sr0.9La0.1TiO3 crystallites grew in place of the original single crystal Bi4Ti3O12 platelets. When the temperature reached 1150 °C, the Sr0.9La0.1TiO3 platelets preserved the shape of a high aspect ratio and exhibited not only enhanced electrical conductivity with a carrier concentration of 3.518 × 1020 cm-3 and carrier mobility of 8.460 cm2·V-1·s-1 but also significantly decreased thermal conductivity ranging from 5.65 W·m-1·K-1 at 300 K to 2.54 W·m-1·K-1 at 1073 K. It can be widely applied in the field of template grain growth methods for preparing textured thermoelectric ceramics to improve their thermoelectric properties.

Microstructural mechanisms of hysteresis and transformation width in NiTi alloy from molecular dynamics simulations

Martensitic transformations in shape memory alloys are often accompanied by thermal hysteresis, and engineering this property is of prime scientific interest. The martensitic transformation can be characterized as thermoelastic, where the extent of the transformation is determined by a balance between thermodynamic driving force and stored elastic energy. Here we used molecular dynamics simulations of the NiTi alloy to explore hysteresis-inducing mechanisms and thermoelastic behavior by progressively increasing microstructural constraints from single crystals to bi-crystals to polycrystals. In defect-free single crystals, the austenite-martensite interface moves unimpeded with a high velocity. In bi-crystals, grain boundaries act as significant obstacles to the transformation and produce hysteresis by requiring additional nucleation events. In polycrystals, the transformation is further limited by the thermoelastic balance. The stored elastic energy can be converted to mechanisms of non-elastic strain accommodation, which also produce hysteresis. We further demonstrated that the thermoelastic behavior can be controlled by adjusting microstructural constraints.

Droplet freezing assays using a nanoliter osmometer

The ability to accurately record the temperature at which ice nucleation occurs is critical for studying biological ice nucleators. Several instruments have been designed and custom built to make such measurements, but they are not yet on the market. Here we reproducibly measure ice nucleation temperatures down close to the homogeneous nucleation temperature of −38 °C with a commercially available nanoliter osmometer, which we routinely use to assay the thermal hysteresis activity of antifreeze proteins. This instrument has both a wide operating temperature range and fine temperature control, while the oil immersion format on 12-well grids prevents droplet evaporation and surface nucleation events. The results obtained are consistent with those reported on other instruments in common use.

Pre‐Eruptive Outgassing and Pressurization, and Post‐Fragmentation Bubble Nucleation, Recorded by Vesicles in Breadcrust Bombs From Vulcanian Activity at Guagua Pichincha Volcano, Ecuador

AbstractBreadcrust bombs formed during Vulcanian eruptions are assumed to originate from the shallow plug or dome. Their rim to core texture reflects the competition between cooling and degassing timescales, which results in a dense crust with isolated vesicles contrasting with a highly vesicular vesicle network in the interior. Due to relatively fast quenching, the crust can shed light on pre‐ and syn‐eruptive conditions prior to or during fragmentation, whereas the interior allows us to explore post‐fragmentation vesiculation. Investigation of pre‐ to post‐fragmentation processes in breadcrust bombs from the 1999 Vulcanian activity at Guagua Pichincha, Ecuador, via 2D and 3D textural analysis reveals a complex vesiculation history, with multiple, spatially localized nucleation and growth events. Large vesicles (Type 1), present in low number density in the crust, are interpreted as pre‐eruptive bubbles formed by outgassing and collapse of a permeable bubble network during ascent or stalling in the plug. Haloes of small, syn‐fragmentation vesicles (Type 2), distributed about large vesicles, are formed by pressurization and enrichment of volatiles in these haloes. The nature of the pressurization process in the plug is discussed in light of seismicity and ground deformation signals, and previous textural and chemical studies. A third population (Type 3) of post‐fragmentation small vesicles appears in the interior of the bomb, and growth and coalescence of Type 2 and 3 vesicles causes the transition from isolated to interconnected bubble network in the interior. We model the evolution of viscosity, bubble growth rate, diffusion timescales, bubble radius and porosity during fragmentation and cooling. These models reveal that thermal quenching dominates in the crust whereas the interior undergoes a viscosity quench caused by degassing, and that the transition from crust to interior corresponds to the onset of percolation and development of permeability in the bubble network.

In Vitro Investigation Unveiling New Insights into the Antimalarial Mechanism of Chloroquine: Role in Perturbing Nucleation Events during Heme to β-Hematin Transformation.

Malaria parasites generate toxic heme during hemoglobin digestion, which is neutralized by crystallizing into inert hemozoin (β-hematin). Chloroquine blocks this detoxification process, resulting in heme-mediated toxicity in malaria parasites. However, the exact mechanism of chloroquine's action remains unknown. This study investigates the impact of chloroquine on the transformation of heme into β-hematin. The results show that chloroquine does not completely halt the transformation process but rather slows it down. Additionally, chloroquine complexation with free heme does not affect substrate availability or inhibit β-hematin formation. Scanning electron microscopy (SEM) and X-ray powder diffraction (XRD) studies indicate that the size of β-hematin crystal particles and crystallites increases in the presence of chloroquine, suggesting that chloroquine does not impede crystal growth. These findings suggest that chloroquine delays hemozoin production by perturbing the nucleation events of crystals and/or the stability of crystal nuclei. Thus, contrary to prevailing beliefs, this study provides a new perspective on the working mechanism of chloroquine.

Source Apportionment of Cloud Nuclei at 260 m and Ground Level in Urban Beijing

AbstractCloud condensation nuclei (CCN) is a critical parameter for simulating aerosol‐cloud interaction and aerosol indirect effects. Here we characterize the vertical differences of CCN number concentration (NCCN) between ground level and 260 m based on field measurements on a meteorological tower in Beijing. The observed ground aerosol number concentration was about 16% higher than 260 m, unexpectedly, the ground NCCN was on average 20% lower than 260 m within the atmospheric typical supersaturation (S) range of 0.1%–0.4%. Using positive matrix factorization analysis, we clarified that the higher NCCN at 260 m was primarily due to increased contributions from both regional transport and secondary processes. The aerosol particles from the regional transport contributed 20%–50% and 31%–57% of CCN respectively at ground and 260 m within typical S, with higher proportions at smaller S. The secondary processes contributed generally about the equal amount CCN between ground (42%–55%) and 260 m (37%–52%). The total contribution of regional transport and secondary processes, as the main sources, contributed 72%–94% CCN during the campaign. While, nucleation events and local primary sources accounted for the smallest proportion of NCCN at both heights. Under polluted conditions, the vertical difference was further enlarged. The results suggest that surface observations under clean conditions may well represent cloud nuclei aloft. However, the NCCN measured at ground may be unexpectedly much lower than the tower height in polluted conditions, likely leading to an underestimation on cloud nuclei aloft during the field campaign.