Polymerization-induced self-assembly (PISA) has become a widely used technique for the rational design of diblock copolymer nano-objects in concentrated aqueous solution. Depending on the specific ...PISA formulation, reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization typically provides straightforward access to either spheres, worms, or vesicles. In contrast, RAFT aqueous emulsion polymerization formulations often lead to just kinetically-trapped spheres. This limitation is currently not understood, and only a few empirical exceptions have been reported in the literature. In the present work, the effect of monomer solubility on copolymer morphology is explored for an aqueous PISA formulation. Using 2-hydroxybutyl methacrylate (aqueous solubility = 20 g dm–3 at 70 °C) instead of benzyl methacrylate (0.40 g dm–3 at 70 °C) for the core-forming block allows access to an unusual “monkey nut” copolymer morphology over a relatively narrow range of target degrees of polymerization when using a poly(methacrylic acid) RAFT agent at pH 5. These new anisotropic nanoparticles have been characterized by transmission electron microscopy, dynamic light scattering, aqueous electrophoresis, shear-induced polarized light imaging (SIPLI), and small-angle X-ray scattering.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
High-latitude regions are experiencing rapid and extensive changes in ecosystem composition and function as the result of increases in average air temperature. Increasing air temperatures have led to ...widespread thawing and degradation of permafrost, which in turn has affected ecosystems, socioeconomics, and the carbon cycle of high latitudes. Here we overcome complex interactions among surface and subsurface conditions to map near-surface permafrost through decision and regression tree approaches that statistically and spatially extend field observations using remotely sensed imagery, climatic data, and thematic maps of a wide range of surface and subsurface biophysical characteristics. The data fusion approach generated medium-resolution (30-mpixels) maps of near-surface (within 1m) permafrost, active-layer thickness, and associated uncertainty estimates throughout mainland Alaska. Our calibrated models (overall test accuracy of ~85%) were used to quantify changes in permafrost distribution under varying future climate scenarios assuming no other changes in biophysical factors. Models indicate that near-surface permafrost underlies 38% of mainland Alaska and that near-surface permafrost will disappear on 16 to 24% of the landscape by the end of the 21st Century. Simulations suggest that near-surface permafrost degradation is more probable in central regions of Alaska than more northerly regions. Taken together, these results have obvious implications for potential remobilization of frozen soil carbon pools under warmer temperatures. Additionally, warmer and drier conditions may increase fire activity and severity, which may exacerbate rates of permafrost thaw and carbon remobilization relative to climate alone. The mapping of permafrost distribution across Alaska is important for land-use planning, environmental assessments, and a wide-array of geophysical studies.
•Novel-baseline assessment of permafrost properties in Alaska•Mapping permafrost in Alaska using Landsat and empirical modeling•Approximately 85% overall accuracy for near-surface permafrost distribution•Projected 16 to 24% loss of frozen ground in Alaska during 21st Century•Spatially explicit estimates of uncertainty and probability
Full text
Available for:
GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
A range of amphiphilic statistical copolymers is synthesized where the hydrophilic component is either methacrylic acid (MAA) or 2-(dimethylamino)ethyl methacrylate (DMAEMA) and the hydrophobic ...component comprises methyl, ethyl, butyl, hexyl, or 2-ethylhexyl methacrylate, which provide a broad range of partition coefficients (log P). Small-angle X-ray scattering studies confirm that these amphiphilic copolymers self-assemble to form well-defined spherical nanoparticles in an aqueous solution, with more hydrophobic copolymers forming larger nanoparticles. Varying the nature of the alkyl substituent also influenced self-assembly with more hydrophobic comonomers producing larger nanoparticles at a given copolymer composition. A model based on particle surface charge density (PSC model) is used to describe the relationship between copolymer composition and nanoparticle size. This model assumes that the hydrophilic monomer is preferentially located at the particle surface and provides a good fit to all of the experimental data. More specifically, a linear relationship is observed between the surface area fraction covered by the hydrophilic comonomer required to achieve stabilization and the log P value for the hydrophobic comonomer. Contrast variation small-angle neutron scattering is used to study the internal structure of these nanoparticles. This technique indicates partial phase separation within the nanoparticles, with about half of the available hydrophilic comonomer repeat units being located at the surface and hydrophobic comonomer-rich cores. This information enables a refined PSC model to be developed, which indicates the same relationship between the surface area fraction of the hydrophilic comonomer and the log P of the hydrophobic comonomer repeat units for the anionic (MAA) and cationic (DMAEMA) comonomer systems. This study demonstrates how nanoparticle size can be readily controlled and predicted using relatively ill-defined statistical copolymers, making such systems a viable attractive alternative to diblock copolymer nanoparticles for a range of industrial applications.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
The detection of low-mass transiting exoplanets in multiple systems brings new constraints to planetary formation and evolution processes and challenges the current planet formation theories. ...Nevertheless, only a mere fraction of the small planets detected by Kepler and K2 have precise mass measurements, which are mandatory to constrain their composition. We aim to characterise the planets that orbit the relatively bright star K2-138. This system is dynamically particular as it presents the longest chain known to date of planets close to the 3:2 resonance. We obtained 215 HARPS spectra from which we derived the radial-velocity variations of K2-138. Via a joint Bayesian analysis of both the K2 photometry and HARPS radial-velocities (RVs), we constrained the parameters of the six planets in orbit. The masses of the four inner planets, from b to e, are 3.1, 6.3, 7.9, and 13.0 M⊕ with a precision of 34, 20, 18, and 15%, respectively. The bulk densities are 4.9, 2.8, 3.2, and 1.8 g cm−3, ranging from Earth to Neptune-like values. For planets f and g, we report upper limits. Finally, we predict transit timing variations of the order two to six minutes from the masses derived. Given its peculiar dynamics, K2-138 is an ideal target for transit timing variation (TTV) measurements from space with the upcoming CHaracterizing ExOPlanet Satellite (CHEOPS) to study this highly-packed system and compare TTV and RV masses.
Full text
Available for:
FMFMET, NUK, UL, UM, UPUK
Anti-PD1/PD-L1 directed immune checkpoint inhibitors (ICI) are widely used to treat patients with advanced non-small-cell lung cancer (NSCLC). The activity of ICI across NSCLC harboring oncogenic ...alterations is poorly characterized. The aim of our study was to address the efficacy of ICI in the context of oncogenic addiction.
We conducted a retrospective study for patients receiving ICI monotherapy for advanced NSCLC with at least one oncogenic driver alteration. Anonymized data were evaluated for clinicopathologic characteristics and outcomes for ICI therapy: best response (RECIST 1.1), progression-free survival (PFS), and overall survival (OS) from ICI initiation. The primary end point was PFS under ICI. Secondary end points were best response (RECIST 1.1) and OS from ICI initiation.
We studied 551 patients treated in 24 centers from 10 countries. The molecular alterations involved KRAS (n=271), EGFR (n=125), BRAF (n=43), MET (n=36), HER2 (n=29), ALK (n=23), RET (n=16), ROS1 (n=7), and multiple drivers (n=1). Median age was 60years, gender ratio was 1:1, never/former/current smokers were 28%/51%/21%, respectively, and the majority of tumors were adenocarcinoma. The objective response rate by driver alteration was: KRAS=26%, BRAF=24%, ROS1=17%, MET=16%, EGFR=12%, HER2=7%, RET=6%, and ALK=0%. In the entire cohort, median PFS was 2.8months, OS 13.3months, and the best response rate 19%. In a subgroup analysis, median PFS (in months) was 2.1 for EGFR, 3.2 for KRAS, 2.5 for ALK, 3.1 for BRAF, 2.5 for HER2, 2.1 for RET, and 3.4 for MET. In certain subgroups, PFS was positively associated with PD-L1 expression (KRAS, EGFR) and with smoking status (BRAF, HER2).
: ICI induced regression in some tumors with actionable driver alterations, but clinical activity was lower compared with the KRAS group and the lack of response in the ALK group was notable. Patients with actionable tumor alterations should receive targeted therapies and chemotherapy before considering immunotherapy as a single agent.
Full text
Available for:
GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Abstract
We investigate planetary migration in the dead zone of a protoplanetary disk where there is a set of spiral waves propagating inward due to the turbulence in the active zone and the Rossby ...wave instability, which occurs at the transition between the dead and active zones. We perform global 3D unstratified magnetohydrodynamical simulations of a gaseous disk with the FARGO3D code, using weak gradients in the static resistivity profiles that trigger the formation of a vortex at the outer edge of the dead zone. We find that once the Rossby vortex develops, spiral waves in the dead zone emerge and interact with embedded, migrating planets by wave interference, which notably changes their migration. The inward migration becomes faster depending on the mass of the planet, due mostly to the constructive (destructive) interference between the outer (inner) spiral arm of the planet and the destruction of the dynamics of the horseshoe region by means of the set of background spiral waves propagating inward. The constructive wave interference produces a more negative Lindblad differential torque, which inevitably leads to an inward migration. Lastly, for massive planets embedded in the dead zone, we find that the spiral waves can create an asymmetric, wider, and deeper gap than in the case of
α
-disks and can prevent the formation of vortices at the outer edge of the gap. The latter could generate a faster or slower migration compared to the standard type-II migration.
A combination of statistical and triblock copolymer properties is explored to produce stable aqueous polymer dispersions suitable for the film formation. In order to perform an extensive structural ...characterization of the products in the dissolved, dispersed, and solid states, a wide range of symmetrical poly(acrylic acid-stat-styrene) x -block-poly(butyl acrylate) y -block-poly(acrylic acid-stat-styrene) x , poly(AA-st-St) x -b-PBA y -b-poly(AA-st-St) x , (x = 56, 108 and 140, y = 100–750; the AA:St molar ratio is 42:58) triblock copolymers were synthesized by reversible addition–fragmentation chain transfer (RAFT) solution polymerization using a bifunctional symmetrical RAFT agent. It is demonstrated that the amphiphilic statistical outer blocks can provide sufficient stabilization to largely hydrophobic particles in aqueous dispersions. Such a molecular design provides an advantage over copolymers composed only of homoblocks, as a simple variation of the statistical block component ratio provides an efficient way to control the hydrophilicity of the stabilizer block, which ultimately affects the copolymer morphology in solutions and solid films. It was found by small-angle X-ray scattering (SAXS) that the copolymers behaved as dissolved chains in methylethylketone (MEK) but self-assembled in water into stable and well-defined spherical particles that increased in size with the length of the hydrophobic PBA block. These particles possessed an additional particulate surface structure formed by the statistical copolymer stabilizer block, which self-folded through the hydrophobic interactions between the styrene units. SAXS and atomic force microscopy showed that the copolymer films cast from the MEK solutions formed structures predicted by self-consistent field theory for symmetrical triblock copolymers, while the aqueous dispersions formed structural morphologies similar to a close-packed spheres, as would be expected for copolymer particles trapped kinetically due to the restricted movement of the blocks in the initial aqueous dispersion. A strong correlation between the structural morphology and mechanical properties of the films was observed. It was found that the properties of the solvent cast films were highly dependent on the ratios of the hard poly(AA-st-St) and soft (PBA) blocks, while the aqueous cast films did not show such a dependence. The continuous phase of hard blocks, always formed in the case of the aqueous cast films, produced films with a higher elastic modulus and a lower extension-to-break in a comparison with the solvent-cast films.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
Abstract
The Atacama Large Millimeter/submillimeter Array (ALMA) Survey of Star Formation and Evolution in Massive Protoclusters with Blue Profiles (ASSEMBLE) aims to investigate the process of mass ...assembly and its connection to high-mass star formation theories in protoclusters in a dynamic view. We observed 11 massive (
M
clump
≳ 10
3
M
⊙
), luminous (
L
bol
≳ 10
4
L
⊙
), and blue-profile (infall signature) clumps by ALMA with resolution of ∼2200–5500 au (median value of 3500 au) at 350 GHz (870
μ
m). We identified 248 dense cores, including 106 cores showing protostellar signatures and 142 prestellar core candidates. Compared to early stage infrared dark clouds (IRDCs) by ASHES, the core mass and surface density within the ASSEMBLE clumps exhibited a significant increment, suggesting concurrent core accretion during the evolution of the clumps. The maximum mass of prestellar cores was found to be 2 times larger than that in IRDCs, indicating that evolved protoclusters have the potential to harbor massive prestellar cores. The mass relation between clumps and their most massive core (MMCs) is observed in ASSEMBLE but not in IRDCs, which is suggested to be regulated by multiscale mass accretion. The mass correlation between the core clusters and their MMCs has a steeper slope compared to that observed in stellar clusters, which can be due to fragmentation of the MMC and stellar multiplicity. We observe a decrease in core separation and an increase in central concentration as protoclusters evolve. We confirm primordial mass segregation in the ASSEMBLE protoclusters, possibly resulting from gravitational concentration and/or gas accretion.
In a time of accelerating sea level rise and increasingly intensifying storms, the world’s sandy beaches and dunes have never been more crucial to protecting coastal environments. Yet, in order to ...meet the demands of large-scale construction projects, sand mining is stripping beaches and dunes, destroying environments, and exploiting labor in the process. The authors of Vanishing Sands track the devastating impact of legal and illegal sand mining over the past twenty years, ranging from Africa, Asia, and the Caribbean to South America and the eastern United States. They show how sand mining has reached crisis levels: beach, dune, and river ecosystems are in danger of being lost forever, while organized crime groups use deadly force to protect their illegal mining operations. Calling for immediate and widespread resistance to sand mining, the authors demonstrate that its cessation is paramount for saving not only beaches, dunes, and associated environments but also lives and tourism economies everywhere.
A major feature of Alzheimer's disease is the accumulation of amyloid-β peptide (Aβ) in the brain both in the form of plaques in the cerebral cortex and in blood vessel as cerebral amyloid angiopathy ...(CAA). Experimental models and human clinical trials have shown that accumulation of Aβ plaques can be reversed by immunotherapy. In this study, we hypothesized that Aβ in plaques is solubilized by antibodies generated by immunization and drains via the perivascular pathway, detectable as an increase in cerebrovascular Aβ. We have performed a follow up study of Alzheimer's disease patients immunized against Aβ42. Neuropathological examination was performed on nine patients who died between four months and five years after their first immunization. Immunostaining for Aβ40 and Aβ42 was quantified and compared with that in unimmunized Alzheimer's disease controls (n = 11). Overall, compared with these controls, the group of immunized patients had approximately 14 times as many blood vessels containing Aβ42 in the cerebral cortex (P<0.001) and seven times more in the leptomeninges (P = 0.013); among the affected blood vessels in the immunized cases, most of them had full thickness and full circumference involvement of the vessel wall in the cortex (P = 0.001), and in the leptomeninges (P = 0.015). There was also a significantly higher level of cerebrovascular Aβ40 in the immunized cases than in the unimmunized cases (cortex: P = 0.009 and leptomeninges: P = 0.002). In addition, the immunized patients showed a higher density of cortical microhaemorrhages and microvascular lesions than the unimmunized controls, though none had major CAA-related intracerebral haemorrhages. The changes in cerebral vascular Aβ load did not appear to substantially influence the structural proteins of the blood vessels. Unlike most of the immunized patients, two of the longest survivors, four to five years after first immunization, had virtually complete absence of both plaques and CAA, raising the possibility that, given time, Aβ is eventually cleared from the cerebral vasculature. The findings are consistent with the hypothesis that Aβ immunization results in solubilization of plaque Aβ42 which, at least in part, exits the brain via the perivascular pathway, causing a transient increase in the severity of CAA. The extent to which these vascular alterations following Aβ immunization in Alzheimer's disease are reflected in changes in cognitive function remains to be determined.
PDF
