Extensive Fragmentation Research Articles

Updating the distribution of Nothofagus alessandrii: Impact of deforestation, fragmentation and connectivity

Nothofagus alessandrii forests in the Mediterranean region of Chile face significant threats from deforestation, fragmentation, wildfires, and climate change. This study investigated the temporal and spatial dynamics of N. alessandrii populations and their implications for habitat fragmentation and connectivity. Using remote sensing data and geographic information system analysis, we assessed deforestation patterns, fragmentation metrics, and connectivity indices for different scenarios between 2009 and 2022. A reduction in the N. alessandrii forest area, extensive fragmentation, and decreased connectivity were observed over time, with wildfires exacerbating these trends. Reforestation simulations showed the potential of targeted restoration efforts to improve connectivity, especially when focusing on proximate patches. However, careful consideration of seed dispersal distances and wildfire risk is essential for effective reforestation planning. Overall, our findings underscore the urgent need for conservation interventions to preserve N. alessandrii forests and their biodiversity in Chile's coastal mountain ecosystems. A proactive and collaborative approach is essential to ensure the survival of these forests for future generations.

Atmospheric Pressure Photoionization with Halogen Anion Attachment for Mass Spectrometric Analysis of Hydrocarbons and Hydrocarbon-Based Polymers.

Aliphatic hydrocarbons and hydrocarbon-based synthetic polymers are of interest in many fields, but their characterization by mass spectrometric methods is generally limited due to their poor ionizability. Recently, atmospheric pressure photoionization (APPI), combined with halogen anion attachment in negative-ion mode, has drawn attention as a potential method for ionizing various polymers without extensive fragmentation or other unwanted side reactions. In this work, the applicability of halogen anion attachment with APPI was studied using several synthetic polymers, including polyethylene, polypropylene, polyisoprene, and polystyrene, as well as simple n-alkanes of various chain lengths. For hydrocarbon-based polymers, the method produced clear distributions of intact polymer adduct ions when different halogen anions were used. It was found that increasing the halogen anion size decreased ionization efficiency, particularly in the absence of π-bonds in the polymer structure. Testing with simple n-alkanes showed that only molecules containing fifty or more carbon atoms formed detectable halogen adducts, possibly due to the low gas-phase stabilities of the lighter n-alkane adduct ions. In conclusion, halogen anion attachment with negative-ion APPI appears to be a highly promising method for polymer analysis, providing structural data and clean polymer mass spectra with minimal fragmentation, which can be useful for the identification of unknown samples.

Effect of explosives charges types on the jet characteristics, penetration performance and fragmentation patterns of shaped charges

Different explosive materials have been studied numerically and experimentally to assess the efficiency of a small diameter shaped charge in terms of produced jet characteristics and penetration depth into RHA steel targets. 26 different explosives have been simulated numerically using Autodyn hydrocode, whereas recommended explosives have been loaded into small diameter shaped charges by pressing technique and tested by static firing against RHA targets in order to validate the numerical calculations. The numerical analysis has presented an intensive global view about the variation of the shaped charge jets as a potential of the loaded explosive charge efficiencies. A successful trial has been performed to measure the shaped charge jet velocity using detonation velocity VOD 812 apparatus, where its measured value was only 3.6% different from the numerical one for HMX-V5 explosive. Besides, TITAN (L3) flash X-ray radiograph has also been implemented to explore the jet profile using the same explosive type and to measure its jet tip velocity, which has only 2.1% different from that estimated numerically. Extensive fragmentation analysis has been presented, which showed increase in both the fragment number and the fragment speed when the used explosive charge is of high detonation velocity. CL-20 explosive exhibited the largest jet tip velocity and its scaled collapse velocity was found to be 140% of TNT explosive. The calculated average fragment speed has been validated and the measured fragment speed has only 2.3% difference when compared to the SPH calculations.

Spatiotemporal variations and driving factors of fine-scale habitat use by the Yangtze finless porpoise population in the Yangtze River.

The Yangtze finless porpoise (Neophocaena asiaeorientalis asiaeorientalis) is critically endangered and has suffered from extensive habitat loss and fragmentation. Knowledge of its habitat preference could assist the conservation of the species and associated ecosystem. In the present study, spatiotemporal variations and driving factors of habitat use of a Yangtze finless porpoise population were studied in a 30-km section of the Yangtze mainstream. Seasonal variation in porpoise occurrences was observed based on visual surveys conducted from 2022 to 2023, with five surveys during the dry season and seven surveys during the wet season. Biological and environmental factors were synchronously sampled in both seasons. The maximum entropy model (MaxEnt) was applied to get the effects of biological and environmental variables on porpoise habitat preference. Within the study area, high-suitability habitats of the finless porpoises accounted for 19.0% and 15.4% of the area during the dry and wet seasons, respectively. The high-suitability habitat shifted from the mainstream in the dry season to the sandbar head and tributary area in the wet season. In the dry season, variables influencing the distribution were phytoplankton biomass, water velocity, and zooplankton biomass, which contributed 97.05% variation in the MaxEnt modeling. In the wet season, water depth, surface water temperature, and zooplankton biomass accounted for 97.69% variation of the distribution. Above results highlight that food availability plays an important role in porpoises distribution regardless of seasons, particularly in the dry season. This is because plankton is the primary food source for filter-feeding and omnivorous fish, especially those in the upper-middle layer which are frequently preyed on by finless porpoises. Suitable areas for finless porpoises, particularly those with high suitability, differed significantly across seasons at a fine-scale in the Yangtze mainstream. Seasonal variations in habitat were driven by different factors. But food availability plays an important role in porpoises distribution regardless of seasons, particularly in the dry season. These results suggest prioritizing conservation of the finless porpoise in the dry season when fish resources are relatively scarce. Measures including monitoring and evaluating prey resources should be considered. More attention should also be paid on management of shipping in the dry season given that the high-suitability habitat of the finless porpoises shifts to the mainstream.

Empirical Approach to Quantifying Sensitivity in Different Chemical Ionization Techniques for Organonitrates and Nitroaromatics Constrained by Ion-Molecule Reaction and Transmission Efficiency.

Accurate identification and quantification of nitro-containing species are of great significance to understanding their chemical behaviors in the atmosphere. By optimizing the operational conditions of the H3O+ and NO+ ionization modes in a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) and evaluating the performance of an iodide chemical ionization mass spectrometer (I- CIMS), this study leveraged the individual advantages of each ionization mode to effectively detect a diverse array of nitroaromatics and organonitrates (ONs). The H3O+ ionization mode largely fulfilled the criteria for real-time monitoring of gas-phase alkyl-, aryl-, and hydroxy-nitrates, and nitrophenols, albeit its reduced sensitivity toward ONs due to extensive fragmentation. In contrast, the NO+ mode demonstrated enhanced sensitivity for ONs with less fragmentation than the H3O+ mode. The I- CIMS featured distinguished sensitivity toward oxidized compounds containing polar functional groups, particularly increasing with the incorporation of hydroxyl, carboxyl, or nitrate groups. Further, we developed a calibration-based semiquantitative framework to enhance the accuracy of sensitivity estimation, constrained by ion-molecule reaction, transmission efficiency, along with possible decomposition of ion-clusters, with uncertainties ranging from 21% to 41% for H3O+ and 21-43% for NO+. Given considerable discrepancies (up to 1 order of magnitude) between measured and predicted sensitivity in I- CIMS using previously reported log-linear fitting, a declustering voltage (dV50)-based categorization approach was introduced, leading to a 5-fold improvement in measurement accuracy and an overall uncertainty of I- CIMS in quantifying nitro-containing species varying from 27% to 60%.

Dynamic behavior of fractured gabbro treated by high temperatures

Rock masses in deep engineering are often subjected to high geothermal effect, and blasting is a key technique for deep rock excavation. It is crucial to study the dynamic characteristics of fractured rock masses under high geothermal conditions and blasting excavation. This paper focuses on fractured gabbro, examining the effects of high temperatures on its surface chromaticity and mass. Dynamic splitting tests were conducted using a Split Hopkinson Pressure Bar (SHPB) apparatus, and the microstructure was analyzed with scanning electron microscopy (SEM). The results indicate that: (1) High temperatures significantly affect the surface chromaticity and mass of gabbro samples. (2) Elevated temperatures lead to the progression from a microstructure with no noticeable microcracks to the development of extensive microcracks and mineral particle fragmentation. (3) The impacts of high temperatures on the splitting strength, peak strain, and dynamic elastic modulus of gabbro samples reach a critical point around 500 °C. At this temperature, the strengthening effect of high temperature is evident, whereas at 800 °C, these properties significantly decrease due to extensive mineral crystal fragmentation and microcrack expansion, weakening the sample's strength, stiffness, and deformation resistance. (4) From 25 °C to 600 °C, the fissure angle significantly influences the splitting strength, peak strain, and dynamic elastic modulus of gabbro. Although the fissure angle still impacts these properties at 800 °C, the overall effect of high temperature is more pronounced. (5) The failure of fractured gabbro samples is primarily characterized by tensile and shear failures, with the crack initiation angle closely related to the fissure angle.

Advancing Protein Analysis: A Low-Pressure Drift Tube Orbitrap Mass Spectrometer for Ultraviolet Photodissociation-Based Structural Characterization.

Owing to its ability to generate extensive fragmentation of proteins, ultraviolet photodissociation (UVPD) mass spectrometry (MS) has emerged as a versatile ion activation technique for the structural characterization of native proteins and protein complexes. Interpreting these fragmentation patterns provides insight into the secondary and tertiary structures of protein ions. However, the inherent complexity and diversity of proteins often pose challenges in resolving their numerous conformations. To address this limitation, we combined UVPD-MS with drift tube ion mobility, offering potential to acquire conformationally selective MS/MS information. A low-pressure drift tube (LPDT) Orbitrap mass spectrometer equipped with 193 nm UVPD capabilities enables the analysis of protein conformers through the analysis of arrival time distributions (ATDs) of individual fragment ions. ATDs of fragment ions are compared for different backbone cleavage sites of the protein or different precursor charge states to give information about regions of potential folding or elongation. This integrated platform offers promise for advancing our understanding of protein structures in the gas phase.

Bimolecular photodissociation of interstellar 1-Cyanonaphthalene via Intermolecular Coulombic decay

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in space and govern the interstellar chemistry. The two isomers of cyanonaphthalene (1-CNN and 2-CNN) were the first PAHs to be recently identified in the Taurus Molecular Cloud (TMC-1). Their large abundance is attributed to high photostability with nearly no photofragmentation at photon energies above the ionization potential. Here, we show that at ambient light and at densities akin to dense molecular clouds and the upper atmosphere of planets and moons, 1-CNN could undergo extensive fragmentation through a new mechanism leading to daughter cations. On UV photoexcitation, at a photon energy way below the ionization threshold, 1-CNN monomers form photoexcited dimer units. Intermolecular Coulombic decay between the two photoexcited units of the dimer leads to ionization, and the subsequent molecular rearrangements form new daughter cations. These daughter cations could react further, contributing to rich bottom-up astrochemistry, and could play a pivotal role in developmental astrobiology. Photofragmentation in atmospheric and astrophysical environments is hitherto known to be unimolecular, while the present results point a pathway involving bimolecular photofragmentation.

EDGE EFFECTS ON THE ABUNDANCE OF THE CRAB Ucides cordatus (DECAPODA: OCYPODIDAE) IN A NEOTROPICAL MANGROVE

Mangroves are among the most productive and biologically important ecosystems in the world and are currently undergoing extensive habitat loss and fragmentation. Such habitat loss and fragmentation result in the creation of edges, which can cause edge effects on the remaining habitat, resulting in changes in abiotic conditions, alterations in ecosystem functioning, and loss of biodiversity. The crab Ucides cordatus (Linnaeus, 1763), locally known as “caranguejo-uçá,” is a species of great economic and ecological importance in these environments. This species is also considered an important indicator of environmental quality, being sensitive to various pollutants. Therefore, we evaluated how anthropogenic edges affect the U. cordatus population in a mangrove area and compared these patterns to those observed at natural edges. We found a positive effect of edge creation on crab abundance for the total number of burrows and the number of open burrows, but no effect on the number of closed burrows. Conversely, we detected a negative effect of natural edges on the quantity of closed burrows. Our findings suggest that anthropogenic edges may alter crab abundances, becoming the preferred habitat for young crabs. However, we emphasize that the interior of the mangrove is also crucial for species maintenance, especially for adult crabs and juveniles during molting.

Niche-dependent forest and savanna fragmentation in Tropical South America during the Last Glacial Maximum

The refugia hypothesis, often used to explain Amazonia’s high biodiversity, initially received ample support but has garnered increasing criticism over time. Palynological, phylogenetic, and vegetation model reconstruction studies have been invoked to support the opposing arguments of extensive fragmentation versus a stable Amazonian Forest during Pleistocene glacial maxima. Here, we test the past existence of forest fragments and savanna connectivity by bias-correcting vegetation distributions from a Dynamic Vegetation Model (DVM) driven by paleoclimate simulations for South America during the Last Glacial Maximum (LGM). We find evidence for fragmented forests akin to refugia with extensive tropical humid forests to the west and forest islands in central/southern Amazonia. Drier ecosystems of Northern Llanos, Caatinga and Cerrado may have merged into continuous savanna/grasslands that dominated the continent. However, our reconstructions suggest taller, dense woodland/tropical savanna vegetation and areas of similar bioclimate connected disparate forest fragments across Amazonia. This ecotonal biome may have acted as a corridor for generalist forest and savanna species, creating connectivity that allows for range expansion during glacial periods. Simultaneously, it could have served as a barrier for specialists, inducing diversification through the formation of ‘semi-refugia’.

Do linear clearings in boreal peatlands recover? Comparing taxonomic, phylogenetic, and functional plant diversity

Land-use changes and anthropogenic disturbances are major threats to biodiversity, affecting ecosystem function and recovery. In boreal Alberta, Canada, petroleum development has led to extensive landscape fragmentation, notably through linear clearings created for seismic exploration that remove surface vegetation and microtopography. Despite partial recovery on forested seismic lines, peatland recovery is often arrested, impacting wildlife and carbon dynamics. Restoration efforts employ silviculture techniques to create microtopography and foster tree growth, but the efficacy of restoration treatments in restoring peatland plant diversity remains uncertain. We compared taxonomic, phylogenetic, and functional diversity of understory plant communities across treated and untreated seismic lines, alongside reference sites in treed bogs and fens. Treated lines generally had a twofold increase in plant height, leaf dry matter content, and foliar nitrogen and phosphorus contents compared to reference sites. In bogs, treated lines differed from reference conditions driven by increases in herbaceous taxa, while fens displayed disparities mainly in taxonomic and phylogenetic diversity. Differential responses of bogs and fens underline the necessity for tailored management strategies. Changes in plant diversity away from restoration targets have implications for ecosystem recovery, emphasizing the importance of long-term monitoring to evaluate the effectiveness of silviculture techniques in restoring boreal peatland plant communities.

The Impact of Gel Parameters on the Dispersal and Fragmentation of Hyaluronic Acid Gel Fillers within an Artificial Model of Arterial Embolism.

Accidental arterial embolization of hyaluronic acid (HA) fillers can lead to severe complications, including skin ischemia, blindness, and stroke. Currently, the intra-arterial dispersal and fragmentation behavior of HA gels is unknown but critical to our understanding of the pathomechanism of these injuries. This work introduces the Pulsatile Unit for the Laboratory Simulation of Arterio-embolic Restrictions (PULSAR) and evaluates the intravascular behavior of different HA gels. The fragmentation and dispersal behaviors of four HA gels with distinct rheological properties were evaluated via high-resolution videography and ImageJ particle size and morphology analysis. The gels' elastic modulus (G'), loss modulus (G″), tan(δ), and HA concentration were subsequently correlated with their intra-arterial behaviors. This study effectively confirms the extensive fragmentation of HA gels upon arterial inoculation, with particle sizes ranging from <50 µm to >1 mm. Gel particle size and morphology correlated most significantly with tan(δ). Conversely, arterial flow rates did not significantly influence gel fragmentation behavior, though the probability of proximal, macrovascular obstruction was affected. Overall, this study validates the PULSAR model for simulation of arterial dynamics and the testing of intravascular filler kinematics. The findings demonstrate the ability of gels to microfragment and disseminate distally, as well as induce partial proximal occlusion depending on gel rheology and arterial flow parameters.

Application of the EBSD Technique in the Study of Porosity and Permeability in Deformation Bands in Sandstone.

Deformation bands are common constituents of porous clastic fluid reservoirs. Various techniques have been used to study deformation band structure and the associated changes in porosity and permeability. However, the use of electron backscatter diffraction technique is limited. Thus, more information is needed regarding the crystallographic relationships between detrital crystals, which can significantly impact reservoir rock quality. We employ microscopic and microstructural investigation techniques to analyze the influence of cataclastic deformation bands on pore space. Porosity measurements of the Cretaceous Ilhas Group sandstone in NE Brazil, obtained through computerized microtomography, indicate that the undeformed domains exhibit a total porosity of up to 13%. In contrast, this porosity is slightly over 1% in the deformation bands. Scanning electron microscopy analyses revealed the presence of grain fragmentation and dissolution microstructures, along with cement-filling pre-existing pores. The electron backscatter diffraction analyses indicated extensive grain fragmentation and minimal contribution from intracrystalline plasticity as a deformation mechanism. However, the c axes of quartz crystals roughly align parallel to the orientation of the deformation band. In summary, we have confirmed and quantified the internal changes in a deformation band cluster, with grain size reduction and associated compaction as the main mechanism supported by quartz cementation.

A comparative study of the cell wall level delignification behaviour of four Nordic hardwoods during kraft pulping

Abstract Wood is a heterogeneous material with significant variation among species. This inherent complexity poses a challenge to the continuous expansion of our understanding of the kraft process; yet previous pulping research has mainly been limited to a few species. This study investigates variations among some less studied species and their cell wall level delignification behaviour during kraft pulping. Ground wood of birch, beech, aspen, and alder were pulped at near-constant composition and temperature conditions. Minor, yet significant, differences in the rates of their delignification were observed: aspen had a pronounced fast rate during the initial stage, whereas alder delignified more slowly relative to its high initial lignin content. The dissolution of xylan was substantially faster for birch. In contrast, no substantial differences were detected between the species in the molecular weight and structure of the dissolved wood components, suggesting that the different delignification behaviours stem from variations in the residual phase. The molecular weight distribution of dissolved lignin was uniform during the initial stage of pulping, which is indicative of rapid and extensive fragmentation. Subsequently, the weight increased continuously for the remainder of the process, suggesting that the mass transfer within the cell wall influenced the overall delignification kinetics.

Improvements in recovery of rare earth elements (REEs) from coal via fluidized-bed combustion: Thermal alteration of REE mineralogy and its impact on element extractability

The extraction of rare earth elements (REE) from coal ash has attracted significant attention, but satisfactory solutions have not yet been achieved. Indeed, the REE extractability is largely determined by the transformation behavior of REE during coal combustion. This study found that the controlled combustion conditions of circulated fluidized-bed boiler (CFB) can both utilize the heating value and enhance the recovery of REE from coal. Tests were conducted using a bituminous coal with REE concentration of approximately 149 ppm in an industrial 35 t/h CFB boiler with controlled boiler loads and coal sources. Advanced automated image analysis by scanning electron microscopy (AIA-SEM) and sequential leaching procedure were employed to clarify the speciation transformation behavior of REE in boilers and investigate the effects of these transformations on the leachability of REE. Approximately 75 % of REE partitioned into fly ash and enriched in particles < 45 μm (∼710 ppm) after combustion. Acid leaching tests under mild conditions (1 M HCl at 60 ℃ and S/L = 1:25) performed on coal, bulk ashes, and sieved ashes revealed an improvement in REE leaching ratio from coal (21.34 %) to fly ash (71.07 %). Particle size played a crucial role in acid extractability, particularly for middle and heavy REE in cyclone ash but had no influence on those in fly ash. The dominant forms of REE in coal including Ca-REE fluorocarbonates (36.7 %), aluminophosphates (12.0 %), and organic-bound REE (approximately 20 %) significantly decreased, contributing to the formation of leachable rare earth oxides (∼65 %) in ash. Furthermore, the small size of REE mineral grains in coal (over 50 % below 5 μm) and extensive mineral fragmentation occurring in boiler resulted in the enrichment and enhanced REY leachability in fine ash.

Current Concepts in Management of Distal Femur Fractures

Recent studies report the overall incidence of distal femur fractures as 8.7/100,000/year. This incidence is expected to rise with high energy motor vehicle collisions and elderly osteoporotic fractures in native and prosthetic knees keep increasing. These fractures are more common in males in the younger age spectrum while females predominate for elderly osteoporotic fractures. Surgical treatment is recommended for these fractures to maintain articular congruity, enable early joint motion and assisted ambulation. Over the last two decades, development of minimally invasive and quadriceps sparing surgical approaches, availability of angle stable implants have helped achieve predictable healing and early return to function in these patients. Currently, laterally positioned locked plate is the implant of choice across all fracture patterns. Retrograde with capital implantation of intramedullary nails with provision for multiplanar distal locking is preferred for extra-articular and partial articular fractures. Even with these advancements, nonunion after distal femur fracture fixation can be as high as 19%. Further recent research has helped us understand the biomechanical limitations and healing problems with lateral locked plate fixation and intramedullary nails. This has lead to development of more robust constructs such as nail-plate and double plate constructs aiming for improved construct strength and to minimise failures. Early results with these combination constructs have shown promise in high risk situations such as fractures with extensive metaphyseal fragmentation, osteoporosis and periprosthetic fractures. These constructs however, run the risk of being over stiff and can inhibit healing if not kept balanced. The ideal stiffness that is needed for fracture healing is not clearly known and current research in this domain has lead to the development of smart implants which are expected to evolve and may help improve clinical results in future.

Top-Down Characterization of Bacterial Lipopolysaccharides and Lipooligosaccharides Using Activated-Electron Photodetachment Mass Spectrometry.

Lipopolysaccharides (LPS) and lipooligosaccharides (LOS) are located in the outer membrane of Gram-negative bacteria and are comprised of three distinctive parts: lipid A, core oligosaccharide (OS), and O-antigen. The structure of each region influences bacterial stability, toxicity, and pathogenesis. Here, we highlight the use of targeted activated-electron photodetachment (a-EPD) tandem mass spectrometry to characterize LPS and LOS from two crucial players in the human gut microbiota, Escherichia coli Nissle and Bacteroides fragilis. a-EPD is a hybrid activation method that uses ultraviolet photoirradiation to generate charge-reduced radical ions followed by collisional activation to produce informative fragmentation patterns. We benchmark the a-EPD method for top-down characterization of triacyl LOS from E. coli R2, then focus on characterization of LPS from E. coli Nissle and B. fragilis. Notably, a-EPD affords extensive fragmentation throughout the backbone of the core OS and O-antigen regions of LPS from E. coli Nissle. This hybrid approach facilitated the elucidation of structural details for LPS from B. fragilis, revealing a putative hexuronic acid (HexA) conjugated to lipid A.

Synergistic enhancement of strength and ductility in novel solid-stir continuous extrusion: Influence of heterogeneous microstructure and alloy chemistry

Friction stir-derived solid-state processes leverage the synergistic effect of frictional heating and intense shear deformation to achieve localized microstructural modification for the improvement of mechanical properties. In the present work, a novel processing route called solid-stir extrusion (SSE) has been explored for continuous, high-rate extrusion of a high strength non-age-hardenable-AlMgSc alloy. In the current study, loss of strength associated with frictional heating during the process is mitigated as elevated strength is observed in as-extruded condition, thereby eliminating the need for post process heat treatment. The effect of process attributes on mechanical property and microstructure evolution was investigated. The SSE process caused extensive grain refinement and fragmentation of thermally stable Al3Sc intermetallic periodically at shear bands, which contributes to the elevated mechanical strength. The spatial variation in mechanical properties and microstructural heterogeneity was characterized using nanoindentation and microstructural correlation. The current findings indicate the significance of the process-specific alloy design approach to increase performance of material in as-processed condition.

Characterization of Phosphorylated Peptides by Electron-Activated and Ultraviolet Dissociation Mass Spectrometry: A Comparative Study with Collision-Induced Dissociation.

Mass-spectrometry-based methods have made significant progress in the characterization of post-translational modifications (PTMs) in peptides and proteins; however, room remains to improve fragmentation methods. Ideal MS/MS methods are expected to simultaneously provide extensive sequence information and localization of PTM sites and retain labile PTM groups. This collection of criteria is difficult to meet, and the various activation methods available today offer different capabilities. In order to examine the specific case of phosphorylation on peptides, we investigate electron transfer dissociation (ETD), electron-activated dissociation (EAD), and 193 nm ultraviolet photodissociation (UVPD) and compare all three methods with classical collision-induced dissociation (CID). EAD and UVPD show extensive backbone fragmentation, comparable in scope to that of CID. These methods provide diverse backbone fragmentation, producing a/x, b/y, and c/z ions with substantial sequence coverages. EAD displays a high retention efficiency of the phosphate modification, attributed to its electron-mediated fragmentation mechanisms, as observed in ETD. UVPD offers reasonable retention efficiency, also allowing localization of the PTM site. EAD experiments were also performed in an LC-MS/MS workflow by analyzing phosphopeptides spiked in human plasma, and spectra allow accurate identification of the modified sites and discrimination of isomers. Based on the overall performance, EAD and 193 nm UVPD offer alternative options to CID and ETD for phosphoproteomics.

Enhanced Biocompatibility by Evaluating the Cytotoxic and Genotoxic Effects of Magnetic Iron Oxide Nanoparticles and Chitosan on Hepatocellular Carcinoma Cells (HCC)

Hepatocellular carcinoma (HCC), the fifth most prevalent cancer worldwide, is influenced by a myriad of clinic-pathological factors, including viral infections and genetic abnormalities. This study delineates the synthesis, characterization, and the biological efficacy of iron oxide nanoparticles (Fe3O4) and chitosan-coated iron oxide nanoparticles (Fe3O4-CS) against HCC. Analytical methods confirmed the successful synthesis of both nanoparticles, with Fe3O4-CS demonstrating a smaller, uniform spherical morphology and distinct surface and magnetic properties attributable to its chitosan coating. The prepared materials were analyzed using various techniques, and their potential cytotoxic effects on HepG2 cancer cells line for HCC were investigated. In biological evaluations against HepG2 cells, a notable distinction in cytotoxicity was observed. Fe3O4 showed modest anticancer activity with an IC50 of 383.71 ± 23.9 µg/mL, whereas Fe3O4 exhibited a significantly enhanced cytotoxic effect, with a much lower IC50 of 39.15 ± 39.2 µg/mL. The Comet assay further evidenced Fe3O4-CS potent DNA damaging effect, showcasing its superior ability to induce apoptosis through extensive DNA fragmentation. Biochemical analyses integrated into our results reveal that Fe3O4-CS not only induces significant DNA damage but also markedly alters oxidative stress markers. Compared to control and Fe3O4-treated cells, Fe3O4-CS exposure significantly elevated levels of oxidative stress markers: superoxide dismutase (SOD) increased to 192.07 U/ml, catalase (CAT) decreased to 0.03 U/L, glutathione peroxidase (GPx) rose dramatically to 18.76 U/gT, and malondialdehyde (MDA) levels heightened to 30.33 nmol/gT. These results underscore the potential of Fe3O4-CS nanoparticles not only in inducing significant DNA damage conducive to cancer cell apoptosis but also in altering enzymatic activities and oxidative stress markers, suggesting a dual mechanism of action that may underpin their therapeutic advantage in cancer treatment. Our findings advocate for the further exploration of Fe3O4-CS nanoparticles in the development of anticancer drugs, emphasizing their capability to trigger oxidative stress and enhance antioxidant defense mechanisms.