Low-mass Fragments Research Articles

Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Poly(methyl methacrylate).

The development of cleavable comonomers (CCs) with suitable copolymerization reactivity paves the way for the introduction of backbone deconstructability into polymers. Recent advancements in thionolactone-based CCs, exemplified by dibenzo[c,e]-oxepine-5(7H)-thione (DOT), have opened promising avenues for the selective deconstruction of multiple classes of vinyl polymers, including polyacrylates, polyacrylamides, and polystyrenics. To date, however, no thionolactone CC has been shown to copolymerize with methacrylates to an appreciable extent to enable polymer deconstruction. Here, we overcome this challenge through the design of a new class of benzyl-functionalized thionolactones (bDOTs). Guided by detailed mechanistic analyses, we find that the introduction of radical-stabilizing substituents to bDOTs enables markedly increased and tunable copolymerization reactivity with methyl methacrylate (MMA). Through iterative optimizations of the molecular structure, a specific bDOT, F-p-CF3PhDOT, is discovered to copolymerize efficiently with MMA. High molar mass deconstructable PMMA-based copolymers (dPMMA, Mn > 120 kDa) with low percentages of F-p-CF3PhDOT (1.8 and 3.8 mol%) are prepared using industrially relevant bulk free radical copolymerization conditions. The thermomechanical properties of dPMMA are similar to PMMA; however, the former is shown to degrade into low molar mass fragments (<6.5 kDa) under mild aminolysis conditions. This work presents the first example of a radical ring-opening CC capable of nearly random copolymerization with MMA without the possibility of cross-linking and provides a workflow for the mechanism-guided design of deconstructable copolymers in the future.

Direct Performance of Triple-Stage Tandem Mass Spectrometry Analysis Using Dual-Direction Dipolar Excitation in a Digital Linear Ion Trap.

The ion trap mass spectrometer offers a unique advantage over other mass spectrometers by enabling multistage tandem mass spectrometry analysis with a single mass analyzer. It is employed to generate fragment ions through collision-induced dissociation (CID) usually by applying alternating current (AC) signals to a pair of electrodes for dipole excitation. The process of achieving double-stage tandem mass spectrometry analysis (MS/MS) in the mass spectrometer involves successive stages of injection, cooling, isolation, excitation, and scanning. For triple-stage tandem mass spectrometry analysis (MS/MS/MS), additional stages of isolation, cooling, and excitation need to be added based on the MS/MS analysis, resulting in a complex and time-consuming mass spectrometry workflow. In this study, a digital ion trap technology with the method of simultaneously applying dipole excitation signals to two pairs of electrodes in the ion trap was developed. This allows fragmentation of the precursor ion in one direction while exciting the first-generation product ions in the other direction, enabling direct acquisition of MS/MS/MS spectra. This approach simplifies the process of tandem mass spectrometry, as demonstrated by experimental studies on methamphetamine, which show that dual-direction excitation effectively reduces workflow and enhances the intensity of product ions. Additionally, the method of direct MS/MS/MS spectra achieved through dual-direction excitation in a digital ion trap mass spectrometer allows for a lower q value of the precursor ion owing to a pseudopotential well depth that is 1.648 times greater than that of a traditional sinusoidal ion trap. The experiments of analyzing high concentration n-butyl acetate and isobutyl acetate have shown that the implementation of MS/MS/MS analysis using dual-direction excitation can provide more mass spectral information and effectively distinguish between the two isomeric samples. The results of direct triple-stage spectra obtained by this technique for several typical volatile hazardous chemicals demonstrate the method's capability for rapid analysis and detection of such substances. In summary, the developed method of dual-directional excitation coupled with digital ion trap technology enables direct performance of triple-stage tandem mass spectrometry analysis, improving fragment ion intensities and providing more valuable mass spectral information. It offers advantages such as simplified workflows, faster analysis, and enhanced accuracy for analyzing compounds with low mass fragment ions.

Experimental and Theoretical Analysis of Tricyclic Antidepressants by Ultraviolet Picosecond Laser Desorption Post-Ionization Mass Spectrometry.

Imipramine class tricyclic antidepressants have low ionization efficiencies that make them difficult to detect by using secondary ion mass spectrometry. Ultraviolet picosecond laser desorption postionization (ps-LDPI-MS) is examined here for the detection of four tricyclic antidepressants: imipramine, desipramine, amitriptyline, and clomipramine. About 30 ps laser pulses at either 213 nm (5.8 eV) or 355 nm (3.5 eV) are used for desorption of samples under vacuum, 7.9 eV (157 nm) fluorine laser pulses are used for post-ionization, and the ions so formed are detected by time-of-flight mass spectrometry. Detection of imipramine by 213 nm ps-LDPI-MS shows less fragmentation than either 355 nm ps-LDPI-MS or prior results from 800 nm fs-LDPI-MS. Ionization energies of imipramine, desipramine, amitriptyline, and clomipramine are predicted using density functional theory calculations and used to explain the corresponding ps-LDPI-MS data for these four compounds as resulting from single-photon ionization. The experimental observation of low-mass amine-containing fragments with calculated ionization energies below 7.9 eV is attributed mostly to dissociation during laser desorption, followed by single-photon ionization of the neutral fragments rather than the more traditional mechanism of unimolecular dissociation following single-photon ionization of the parent molecule.

A schematic representation of pyrolysis and oxidative decomposition paths of more environmentally friendly, high chemical and solvent resistant poly(geranyl methacrylate)-co-poly(benzyl methacrylate) copolymers studied by the TG/FTIR/QMS

A schematic representation of pyrolysis and oxidative decomposition paths of poly(geranyl methacrylate)-co-poly(benzyl methacrylate) copolymers (GM-co-BM) using a simultaneous TG/FTIR/QMS analysis has been evaluated, for the first time. The tested polymers are more environmentally friendly, high chemical and solvent resistant materials with a glass transition temperature below 47 °C. Their pyrolysis took place in one main stage visible from 220 °C± 3–245 °C± 2–440–500 °C, depending on their composition. The pyrolysis was connected with the emission of benzyl methacrylate, methacrylic acid, myrcene, geraniol, citral, H2O and some low molecular mass fragments. In turn, the oxidative decomposition of the tested copolymers run in two main stages. The first stage from 205 °C± 5–230 °C± 4–340–380 °C was visible. This was connected with the emission of benzyl methacrylate, myrcene, citral, low molecular mass alkenes and ketones, CO2, H2O and CO. The second stage occurred from 340° to 380–520 °C. Mainly, the formation of CO2, H2O and CO and some low molecular mass fragments was observed. The type of the formed volatiles indicated that the pyrolysis and oxidative decomposition were initiated by a radical mechanism. The symmetric cleavage of the C-C and C-O bonds in the main and side macromolecular chains of the studied GM-co-BM materials (inert conditions) and additional chemical reactions of the formed fragments with oxygen and/or residues (oxidative conditions) were confirmed.

Synchronized Reverse Scan Collision Induced Dissociation in Digital Ion Trap Mass Spectrometer for Improving Fragment Ion Detection

Development of fragment ion detection methods is of great importance for mass spectrometer advancement or substance identification. To date, collision induced dissociation (CID) remains the most commonly used ion activation method in MS/MS experiments, and the effectiveness of CID in an ion trap mass spectrometer is limited by low mass cutoff and weak fragmentation yields. Theoretically, controlling the q value is the key to maintain the fragment efficiency and trapping efficiency of MS/MS, thus improving the detection of fragment ion, while currently reported techniques usually require complex circuitry and often produce different CID patterns. In this paper, with the developed synchronized reversed scanning-collision induced dissociation (SRS-CID) technique, we demonstrate its effective improvement in fragment ion detection. The SRS-CID is implemented on a digital ion trap mass spectrometer (DITMS) by reverse scanning the q values during CID process, or specifically, the frequency is increased during the CID process. With the SRS-CID technique, the fragmentation efficiency of precursor ions can be slightly improved. For reserpine analyte, the trapping efficiency for low-mass fragment ions is improved at least 3 times, and for YGGFL, the trapping efficiency for low-mass fragment ions is improved at least 9 times. These experimental results can also be validated by simulations, and the kinetic energy variation plot suggests consecutive fragmentation occurs. In any case, the SRS-CID provides a solution to the low efficiency of fragment ion detection during tandem MS analysis, which will certainly be useful in the future.

A Lower Bound on the Mass of Compact Objects from Dissipative Dark Matter

We study the fragmentation scale of dark gas formed in dissipative dark-matter halos and show that the simple atomic-dark-matter model consistent with all current observations can create low-mass fragments that can evolve into compact objects forbidden by stellar astrophysics. We model the collapse of the dark halo’s dense core by tracing the thermochemical evolution of a uniform-density volume element under two extreme assumptions for density evolution: hydrostatic equilibrium and pressure-free collapse. We then compute the opacity-limited minimum fragment mass from the minimum temperature achieved in these calculations. The results indicate that much of the parameter space is highly unstable to small-scale fragmentation.

Linking high- and low-mass star formation

Context. Astronomers have yet to establish whether high-mass protostars form from high-mass prestellar cores, similar to their lower-mass counterparts, or from lower-mass fragments at the heart of a pre-protostellar cluster undergoing large-scale collapse. Part of the uncertainty is due to a shortage of envelope structure data on protostars of a few tens of solar masses, where we expect to see a transition from intermediate-mass star formation to the high-mass process. Aims. We sought to derive the masses, luminosities, and envelope density profiles for eight sources in Cygnus-X, whose mass estimates in the literature placed them in the sampling gap. Combining these sources with similarly evolved sources in the literature enabled us to perform a meta-analysis of protostellar envelope parameters over six decades in source luminosity. Methods. We performed spectral energy distribution fitting on archival broadband photometric continuum data from 1.2 to 850 μm to derive bolometric luminosities for our eight sources plus initial mass and radius estimates for modelling density and temperature profiles with the radiative-transfer package Transphere. Results. The envelope masses, densities at 1000 AU, outer envelope radii, and density power law indices as functions of bolometric luminosity all follow established trends in the literature spanning six decades in luminosity. Most of our sources occupy an intermediate to moderately high range of masses and luminosities, which helps to more firmly establish the continuity between low- and high-mass star formation mechanisms. Our density power law indices are consistent with observed values in the literature, which show no discernible trends with luminosity, and have a mean p = −1.4 ± 0.4. However, our sub-sample, with a mean power law index of −1.1 ± 0.3, is slightly flatter than would be expected for spherical envelopes in free fall (p = −1.5). Conclusions. We attribute flattened density profiles for our eight sources to one or more of the following: ongoing accretion from their natal filaments, convolution of sources with neighbours or the larger filament, spherical averaging of asymmetric features (for example fragments), or inflation of the envelope by a moderate far-ultraviolet field. Finally, we show that the trends in all of the envelope parameters for high-mass protostars are statistically indistinguishable from trends in the same variables for low-mass protostars.

Dynamics of Molecules Observed at Crude-Oil-Gas Interfaces by Time-of-Flight Secondary Ion Mass Spectrometry Imaging.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging provides molecular speciation at the micrometer scale, while the penetration depth of the primary ion beam is limited to the top-layers of a sample. These combined properties make TOF-SIMS potentially an ideal technique to study oil–gas interfaces. TOF-SIMS spectra of three crude oils were evaluated, and only low-mass fragment ions could be assigned to molecular structures unambiguously. Films of crude oils were incubated under air, oil vapor, or water vapor for various times. TOF-SIMS images of a polar crude oil revealed feeble structures of ∼10 μm large round patches that grew to ∼30 μm large crystals when incubated under air and oil vapor, respectively. Principal component analysis of the images showed that the continuous phase had typical aromatic signatures, while the patches and crystals had alkane-like characteristics. No features showed up when the oil film was incubated under water vapor, which indicated that saturated water vapor prevented the accumulation of nonpolar alkane-like compounds at the oil–gas interface. These examples showed that crude oils do not behave as dead fluids but that their constituents accumulate at the oil–gas interfaces in a dynamic way.

A comparison of electron ionization mass spectra obtained at 70 eV, low electron energies, and with cold EI and their NIST library identification probabilities

Electron ionization (EI) mass spectra of 46 compounds from several different compound classes were measured. Their molecular ion abundances were compared as obtained with 70-eV EI, with low eV EI (such as 14 eV), and with EI mass spectra of vibrationally cold molecules in supersonic molecular beams (Cold EI). We further compared these mass spectra in their National Institute of Standards and Technology (NIST) library identification probabilities. We found that Low eV EI is not a soft ionization method, and it has little or no influence on the molecular ion relative abundances for large molecules and those with weak or no molecular ions. Low eV EI for compounds with abundant or dominant molecular ions in their 70 eV mass spectra results in the reduction of low mass fragment ions abundances thereby reducing their NIST library identification probabilities thus rarely justifies its use in real-world applications. Cold EI significantly enhances the relative abundance of the molecular ions particularly for large compounds; yet, it retains the low mass fragment ions; hence, Cold EI mass spectra can be effectively identified by the NIST library. Different standard EI ion sources provide different 70 eV EI mass spectra. Among the Agilent technologies ion sources, the "Extractor" exhibits relatively abundant molecular ions compared with the "Inert" ion source, while the "High efficiency source" (HES) provides mass spectra with depleted molecular ions compared with the "Inert" ion source or NIST library mass spectra. These conclusions are demonstrated and supported by experimental data in nine figures and two tables.

Macrophage-stimulating activities of a novel low molecular weight saccharide fragment prepared from ascophyllan with alginate lyase

• Sulphated polysaccharide ascophyllan can be degraded by alginate lyase, EC 4.2.2.3. • A novel low molecular mass fragment LMWAs-L is purified from enzymolysis products. • LMWAs-L is a low fucose- and sulphate-containing saccharide fragment. • LMWAs-L exhibits significant macrophage-stimulating activities in vitro . • The proposal structure of LMWAs-L was established. In this study, the polysaccharide ascophyllan, isolated from Ascophyllum nodosum, was degraded using alginate lyase (EC 4.2.2.3) to prepare low-molecular-weight fragments. LMWAs-L, an extremely low-molecular-weight saccharide (6.71 kDa) with low fucose- and sulphate-contents, was purified by gel filtration chromatography. LMWAs-L exhibited significant macrophage-stimulating activities, similar to ascophyllan, through intracellular signalling pathways. Methylation and GC/MS analyses indicated that the main glycosidic linkages of LMWAs-L were 1,2-linked-Glc p A, followed by T -linked-Glc p , 1,3,6-linked-Gal p , 1,3-linked-Fuc p , 1,4-linked-Xyl p , and 1,4-linked-Man p A at a molar ratio of 3.37: 1.13: 1.11: 1.00: 0.96: 0.61. The proposal repeating structure of LMWAs-L was shown to be →2)-α-D-Glc p A-(1 → 2)-α-D-Glc p A-(1 → 6)-α-D-Gal p -(1 → 2)-α-D-Glc p A-(1→ as main chain, branched by T -α-D-Glc p -(1 → 4)-β-D-Xyl p -(1 → 3)-α-L-Fuc p 4S-(1→ at the O -3 of 3,6)-α-D-Gal p -(1→ residues. 4-deoxy-L- erythro -hex-4-enuronosyluronate-4-β-D-Man p A-(1→ and →4)-β-D-Man p A red residues were attached to the ends of main chain as non-reducing end residue and reducing end residue, respectively. Our results suggest that the fragment LMWAs-L contain an essential structural element of ascophyllan that is responsible for the macrophage-stimulating activities.

High-energy ionizing radiation influence on the fragmentation of glutamine

Both experimentally, by using the mass-spectrometric technique, and theoretically, by applying Becke’s three-parameter hybrid density functional approach, the yield of the ionic products of both single- and dissociative ionization of the glutamine molecule (C5H10N2O3) under high-energy (11.5 MeV) electron impact has been studied. The experimental mass spectra measured at different irradiation doses (i.e., 0, 5, 10, and 20 kGy) have been identified and analyzed. It has been shown that high-energy electrons cause irreversible changes in the structure of the molecule under study, accompanied by a transition to the zwitterionic/deprotonated form, which may cause a change in the fragment ion production at the interatomic distance variation. It has been shown that the yield of the low-mass fragments from the zwitterionic glutamine molecular structure may increase due to an increase in the isobaric ion yield.

Higher Energy Collisional Dissociation Mass Spectrometry of Sulfated O-Linked Oligosaccharides.

Sulfation is the final decoration of mucin-type O-linked oligosaccharides before mucins are released into the lumen of the gastrointestinal, respiratory, and genital tracts. Because only a fraction of oligosaccharides undergo this type of modifications in the Golgi apparatus, sometimes also only by dedicated cells, the glycobiology of these low abundant sulfated oligosaccharides is often overlooked. At the same time, the technology to consistently identify and characterize them has been lagging. We adopted higher energy collisional dissociation to characterize sulfated oligosaccharides from porcine gastric and human salivary MUC5B mucins. With this approach we could generate conclusive spectra up to nonasaccharides. Both singly and doubly sulfated oligosaccharides were characterized. By comparing the fragmentation of low-mass fragments of m/ z 100-320 with standards for six-linked and three-linked sulfate, it could be shown that characteristic fragmentation exists, verifying that porcine gastric mucin contains mostly six-linked sulfate to GlcNAc, whereas human MUC5B contains mostly three-linked Gal. When performing ion-trap MS2 fragmentation, these low-molecular-mass fragments are usually not detected. Hence it can be concluded that to be able to address biological questions of sulfation low-mass fragments are important for the assignment of sulfate position.

Synthesis, spectroscopic and structural characterization of Co(II)-pullulan complexes by UV-Vis, ATR-FTIR, MALDI-TOF/TOF MS and XRD

Complexes of Co(II) ion with reduced low-molar pullulan (RLMP) (Mw 6000 g/mol) were synthesized in aqueous solutions at boiling temperature in the pH range from 7.5 to 13.5. Obtained Co(II)-RLMP complexes, with cobalt content ∼2–8% (AAS), were characterized by UV-Vis spectrophotometry, FTIR spectroscopy (ATR-FTIR, FT-IRIS), MALDI-TOF/TOF MS, and XRD. Tetragonally distorted Oh coordination of Co(II) ions with O ligand atoms in synthesized complexes is suggested based on the spectrophotometric data. No influence of complexation process on the 4C1 chair conformation of the d-glucopyranose units of pullulan was detected by ATR-FTIR measurements and FT-IRIS showed high homogeneity of synthesized complexes. Some additional depolymerization of pullulan during complex synthesis was indicated by MALDI-TOF/TOF MS but it also revealed good stability of complexes with much weaker binding of Co(II) ion in low molar mass fragments. Even in complexes with highest Co(II) ion content a low degree of crystallinity was detected by XRD analysis.

Lignin-First Biorefining of Lignocellulose: the Impact of Process Severity on the Uniformity of Lignin Oil Composition

In lignin-first biorefining via reductive processes, lignocellulosic materials are deconstructed by the solvent extraction of lignin in the presence of a hydrogenation catalyst. This approach provides a route to the successful extraction and reductive passivation of lignin fragments to produce low molar mass lignin oils together with high-quality pulps. Herein, we present an investigation into the impact of process severity (i.e., cooking temperature) on the reductive processes taking place on the lignin fragments and uniformity of the product mixture. In addition to improving overall delignification yields (up to 87%) and producing low molar mass fragments, higher process temperatures led to the preferential cleavage of hydroxyl groups in monolignol sidechains via hydrodeoxygenation, yielding oils with lower oxygen content. By comparing products from both lignin-first biorefining and organosolv processes at various temperatures, we elucidate key performance differences and outline routes to increased chemical uniformity in lignin streams. Overall, this study outlines clearly the importance of process temperature in the deconstruction of lignocellulose by lignin-first biorefining when producing highly depolymerized lignin products. This study points out a trade-off in the effect of temperature upon delignification and increase in product mixture complexity, which needs to be carefully optimized for the scale-up of lignin-first technologies.

Characterizations of PLA-PEG blends involving organically modified montmorillonite

In this study, organically modified montmorillonite composites of poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) blends involving 10,15 and 20wt% PEG were prepared. The characterization of the composite systems was conducted with various techniques such as gel permeation chromatography (GPC), X-ray diffractometry (XRD), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), and direct pyrolysis mass spectrometry (DP-MS) in addition to tensile testing. PLA-PEG blend nanocomposites showed improved tensile strength and modulus upon incorporation of organoclay into the blend. The plasticization effect of PEG was detected in DSC analyses. DP-MS analyses pointed out that loss of low mass fragments occurred at low temperatures, leaving thermally stable chains crosslinked by the chemical interactions between PLA and PEG which were enhanced in the presence of C30B.

To Be or Not to Be? Five Guidelines to Avoid Misassignments in Cross-Linking/Mass Spectrometry.

The number of publications in the field of chemical cross-linking/mass spectrometry (MS) for deriving protein 3D structures and for probing protein/protein interactions has largely increased during the last years. MS analysis of the large cross-linking data sets requires an automated data analysis by dedicated software tools, but applying scoring procedures with statistical methods does not eliminate the fundamental problems of a misassignment of cross-linked products. In fact, we have observed a significant rate of misassigned cross-links in a number of publications, mainly due to the presence of isobaric cross-linked species, an incomplete fragmentation of cross-linked products, and low-mass accuracy fragment ion data. These false assignments will eventually lead to wrong conclusions on the structural information derived from chemical cross-linking/MS experiments. In this contribution, we examine the most common sources for misassigning cross-linked products. We propose and discuss rational criteria and suggest five guidelines that might be followed for a reliable and unambiguous identification of cross-links, independent of the software used for data analysis. In the interest of the cross-linking/MS approach, it should be ensured that only high-quality data enter the structural biology literature. Clearly, there is an urgent need to define common standards for data analysis and reporting formats of cross-linked products.

Characterizing the Performance of Pipe Bombs.

Pipe bombs of steel or PVC fragment in reproducible patterns when similarly configured. The power of the explosion correlates with number, mass, and size of the fragments recovered, where a large number of small, low-mass fragments indicate a high-power event and vice versa. In discussing performance, describing pipe fragmentation pattern by fragment weight distribution mapping (FWDM) or fragment surface area distribution mapping (FSADM) was useful. When fillers detonated, detonation velocities of ~4.4 mm/μs were measured. In such cases, side walls of the pipe were thrown first; the average fragment velocity was ~1000 km/s. In deflagrations, the end cap was first thrown; fragment velocities were only ~240 km/s. Blast overpressures varied; at 10 feet, 2 × 12 inch steel pipes containing ~550 g of detonable mixture produced overpressures of 5-6 psi; similar nondetonating pipes produced less than 2 psi. Maximum fragment throw distances were 250-300 m, with an average of ~100 m.

Rapid detection of bacterial endotoxins in ophthalmic viscosurgical device materials by direct analysis in real time mass spectrometry

Bacterial endotoxins are lipopolysaccharides bound to the bacterial cell wall and released when bacteria rupture or disintegrate. Possible contamination of endotoxin in ophthalmic devices can cause a painful eye inflammation or result in toxic anterior segment syndrome after cataract surgery. Measurement of bacterial endotoxin in medical device materials is difficult since endotoxin binds with polymer matrix and some of the materials are very viscous and non-water soluble, where traditional enzyme-based Limulus amebocyte lysate (LAL) assay cannot be applied. Here we propose a rapid and high throughput ambient ionization mass spectrometric (MS) method using direct analysis in real time (DART) for the evaluation of endotoxin contamination in medical device materials. Large and structurally complex endotoxin instantaneously breaks down into low-mass characteristic fragment ions using DART and is detected by MS in both positive and negative ion modes. This method enables the identification and separation of endotoxin from medical materials with a detection limit of 0.03 ng mL−1 endotoxins in aqueous solution. Ophthalmic viscosurgical device materials including sodium hyaluronate (NaHA), non-water soluble perfluoro-n-octane (PFO) and silicone oil (SO) were spiked with different known concentrations of endotoxin and analyzed by DART MS, where the presence of endotoxin was successfully detected and featured small mass fragment ions were generated for NaHA, PFO and SO as well. Current findings showed the feasibility of measuring endotoxin contamination in medical device materials using DART-MS, which can lead to a one-step analysis of endotoxins in different matrices, avoiding any potential contamination during sample pre-treatment steps.

Ejection of gaseous clumps from gravitationally unstable protostellar disks

We investigate the dynamics of gaseous clumps formed via gravitational fragmentation in young protostellar disks, focusing on the fragments that are ejected from the disk via many-body gravitational interaction. Numerical hydrodynamics simulations were employed to study the evolution of young protostellar disks formed from the collapse of rotating pre-stellar cores with mass in the 1.1-1.6 M_sun range. Protostellar disks formed in our models undergo gravitational fragmentation driven by continuing mass loading from parental collapsing cores. A few fragments can be ejected from the disk during the early evolution, but the low-mass fragments (< 15~M_Jup) disperse creating spectacular bow-type structures while passing through the disk and collapsing core. The least massive fragment that survived the ejection (21 M_Jup) straddles the planetary-mass limit, while the most massive ejected fragments (145 M_Jup) can break up into several pieces, leading to the ejection of wide separation binary clumps in the brown-dwarf mass range. About half of the ejected fragments are gravitationally bound, the majority is supported by rotation against gravity, and all fragments have the specific angular momentum that is much higher than that expected for brown dwarfs. We found that the internal structure of the ejected fragments is distinct from what would be expected for gravitationally contracting clumps formed via cloud core fragmentation, which can help to differentiate their origin. The ejection of fragments is an important process inherent to massive protostellar disks, which produces freely-floating pre-brown dwarf cores, regulates the disk and stellar masses, and potentially enriches the intracluster medium with processed dust and complex organics.

The properties of bound and unbound molecular cloud populations formed in galactic disc simulations

We explore the effect of galactic environment on properties of molecular clouds. Using clouds formed in a large-scale galactic disc simulation, we measure the observable properties from synthetic column density maps. We confirm that a significant fraction of unbound clouds forms naturally in a galactic disc environment and that a mixed population of bound and unbound clouds can match observed scaling relations and distributions for extragalactic molecular clouds. By dividing the clouds into inner and outer disc populations, we compare their distributions of properties and test whether there are statistically significant differences between them. We find that clouds in the outer disc have lower masses, sizes, and velocity dispersions as compared to those in the inner disc for reasonable choices of the inner/outer boundary. We attribute the differences to the strong impact of galactic shear on the disc stability at large galactocentric radii. In particular, our Toomre analysis of the disc shows a narrowing envelope of unstable masses as a function of radius, resulting in the formation of smaller, lower mass fragments in the outer disc. We also show that the star formation rate is affected by the environment of the parent cloud, and is particularly influenced by the underlying surface density profile of the gas throughout the disc. Our work highlights the strengths of using galaxy-scale simulations to understand the formation and evolution of cloud properties - and the star formation within them - in the context of their environment.