Resourceful Actors, Not Weak Victims: Reframing Refugees' Stigmatized Identity Enhances Long-Term Academic Engagement.

Refugees suffer from a stigmatized identity portraying them as weak, unskilled victims. We developed a brief (~10-min) intervention that reframed refugees' identity as being, by its very nature, a source of strength and skills. Reading and writing exercises, provided by a university, highlighted how refugees' experiences helped them acquire skills such as perseverance and the ability to cope with adversity, which could help them succeed in a new country. In Experiment 1 (N = 93), the intervention boosted refugees' (a) confidence in their ability to succeed at an imagined university and (b) challenge seeking: Participants were 70% more likely to take on an academic exercise labeled as difficult. In Experiment 2, the intervention, delivered to refugees entering an online university (N = 533), increased engagement in the online-learning environment by 23% over the subsequent year. There was also evidence of greater course completion. It is possible to reframe stigmatized individuals' identity as inherently strong and resourceful, helping them put their strengths to use.

Correction: A convenient, bio-inspired approach to the synthesis of multi-functional, stable fluorescent silica nanoparticles using poly(ethylene-imine).

Correction for 'A convenient, bio-inspired approach to the synthesis of multi-functional, stable fluorescent silica nanoparticles using poly(ethylene-imine)' by Christina A. Bauer, et al., Nanoscale, 2017, 9, 6509-6520.

A convenient, bio-inspired approach to the synthesis of multi-functional, stable fluorescent silica nanoparticles using poly(ethylene-imine).

Branched poly(ethylene-imine) can be tagged with luminescent dyes (e.g., fluorescein isothiocyanate and tetramethylrhodamine isothiocyanate) and used to precipitate spherical silica particles from 10s-to-100s of nm diameter size under mild conditions. These dye-PEI/SiO2 nanoparticles are highly compatible with polar solvents to give bright fluorescent suspensions, and detailed photophysical characterization reveals well-separated dye moieties with an approximately homogeneous dispersion of dye-PEI conjugate throughout the SiO2 matrix. Reaction of PEI amine groups incorporated at the particle surface affords a simple method for post-synthesis functionalization of these materials, and the formation of FITC/Eosin-Y fluorescence resonance energy transfer pair-tagged particles and SiO2@Au core-shell nanocomposites using this strategy is demonstrated. This bio-inspired approach to multi-functional SiO2 nanoparticles provides a range of potential advantages over traditional "inorganic" syntheses of similar materials, as it proceeds through a scalable, single-step reaction using inexpensive reagents, enables efficient incorporation of luminescent species into the resulting particles with very limited dye aggregation, and provides nanoparticles that do not require post-synthesis modification for further conjugation with species of interest. The method offers a simple means to generate complex nanocomposites, whereby a host of desired species can be incorporated both inside and on the surface of biocompatible SiO2 nanoparticles.

Control of Grafting Density and Distribution in Graft Polymers by Living Ring-Opening Metathesis Copolymerization.

Control over polymer sequence and architecture is crucial to both understanding structure-property relationships and designing functional materials. In pursuit of these goals, we developed a new synthetic approach that enables facile manipulation of the density and distribution of grafts in polymers via living ring-opening metathesis polymerization (ROMP). Discrete endo,exo-norbornenyl dialkylesters (dimethyl DME, diethyl DEE, di-n-butyl DBE) were strategically designed to copolymerize with a norbornene-functionalized polystyrene (PS), polylactide (PLA), or polydimethylsiloxane (PDMS) macromonomer mediated by the third-generation metathesis catalyst (G3). The small-molecule diesters act as diluents that increase the average distance between grafted side chains, generating polymers with variable grafting density. The grafting density (number of side chains/number of norbornene backbone repeats) could be straightforwardly controlled by the macromonomer/diluent feed ratio. To gain insight into the copolymer sequence and architecture, self-propagation and cross-propagation rate constants were determined according to a terminal copolymerization model. These kinetic analyses suggest that copolymerizing a macromonomer/diluent pair with evenly matched self-propagation rate constants favors randomly distributed side chains. As the disparity between macromonomer and diluent homopolymerization rates increases, the reactivity ratios depart from unity, leading to an increase in gradient tendency. To demonstrate the effectiveness of our method, an array of monodisperse polymers (PLAx-ran-DME1-x)n bearing variable grafting densities (x = 1.0, 0.75, 0.5, 0.25) and total backbone degrees of polymerization (n = 167, 133, 100, 67, 33) were synthesized. The approach disclosed in this work therefore constitutes a powerful strategy for the synthesis of polymers spanning the linear-to-bottlebrush regimes with controlled grafting density and side chain distribution, molecular attributes that dictate micro- and macroscopic properties.

Homo- and heterometallic luminescent 2-D stilbene metal-organic frameworks.

Metal-organic frameworks (MOFs) can provide a matrix for the assembly of organic chromophores into well-defined geometries, allowing for tuning of the material properties and study of structure-property relationships. Here, we report on the effect of the coordinated metal ion on the luminescence properties of eight isostructural MOFs having the formula M(1)2M(2)L3(DMF)2 (M(1) = M(2) = Zn (1), Cd (2), Mn (3), Co (4); M(1) = Zn, M(2) = Cd (5), Mn (6), Co (7); M(1) = Co, M(2) = Mn (8); L = trans-4,4'-stilbene dicarboxylate), synthesized by reaction of the appropriate metal nitrate or mixtures of metal nitrates with LH2 in DMF. The crystal structures of 2, 3 and 5-8 were determined by X-ray diffraction to be composed of trinuclear metal clusters linked by stilbene dicarboxylate linkers in a paddlewheel geometry, extending to form a 2-D layered structure. In the mixed-metal cases, the larger metal ion was found to occupy the octahedral site in the cluster while the smaller ion occupies the tetrahedral positions, suggesting a selective, ligand-directed assembly process for the mixed-metal species. Variable temperature magnetic measurements for paramagnetic MOFs 3 and 6-8 were consistent with the site occupancies determined crystallographically, and indicated weak intra-cluster antiferromagnetic coupling for 3 and 8. Comparison between the crystal structures of 2, 3 and 5-8 and those reported for 1 and 4 in the literature reveal close resemblances between linker environments, with important intermolecular stilbene-stilbene geometries that are comparable in all cases. Interestingly, pale-colored 1-3 and 5-7 display very similar emission profiles upon excitation at λ(ex) = 350 nm, whereas dark-colored 4 and 8 do not exhibit detectable emission spectra. The bright, well-resolved luminescence of 1, 2 and 5 is ascribed to rigidification of the linker upon coordination to the d(10) metal ions, whereas the weaker emission observed for 3, 6 and 7 is presumably a result of quenching due to close proximity of the linker to one or more paramagnetic ions. Time-resolved measurements for 1, 2, 5 and 6 reveal biexponential emission decays, where the lifetime of the longer-lived state corresponds to observed variations in the nearest-neighbor cofacial stilbene-stilbene distances in their crystal structures. For 3, a monoexponential decay with shorter lifetime was determined, indicating significant paramagnetic quenching of its emissive state.

Diastereoselective heterogeneous bromination of stilbene in a porous metal-organic framework.

Postsynthetic modification of a porous MOF, Zn(4)O(trans-4,4'-stilbene dicarboxylate)(3), with Br(2) results in diastereoselective bromination of the stilbene units. This is a heterogeneous process, with the stereocontrol originating in the rigidity of the coordinated ligand and the porous nature of the MOF, which allows "solution-like" access to reactive sites. X-ray diffraction and N(2) sorption studies suggest that partial bromination serves to increase the stability of this interpenetrated MOF structure.

Influence of connectivity and porosity on ligand-based luminescence in zinc metal-organic frameworks.

Applications of metal-organic frameworks (MOFs) require close correlation between their structure and function. We describe the preparation and characterization of two zinc MOFs based on a flexible and emissive linker molecule, stilbene, which retains its luminescence within these solid materials. Reaction of trans-4,4'-stilbene dicarboxylic acid and zinc nitrate in N,N-dimethylformamide (DMF) yielded a dense 2-D network, 1, featuring zinc in both octahedral and tetrahedral coordination environments connected by trans-stilbene links. Similar reaction in N,N-diethylformamide (DEF) at higher temperatures resulted in a porous, 3-D framework structure, 2. This framework consists of two interpenetrating cubic lattices, each featuring basic zinc carboxylate vertices joined by trans-stilbene, analogous to the isoreticular MOF (IRMOF) series. We demonstrate that the optical properties of both 1 and 2 correlate with the local ligand environments observed in the crystal structures. Steady-state and time-resolved spectroscopic measurements reveal that the stilbene linkers in the dense structure 1 exhibit a small degree of interchromophore coupling. In contrast, the stilbenoid units in 2 display very little interaction in this low-density 3-D framework, with excitation and emission spectra characteristic of monomeric stilbenes, similar to the dicarboxylic acid in dilute solution. In both cases, the rigidity of the stilbene linker increases upon coordination to the inorganic units through inhibition of torsion about the central ethylene bond, resulting in luminescent crystals with increased emission lifetimes compared to solutions of trans-stilbene. The emission spectrum of 2 is found to depend on the nature of the incorporated solvent molecules, suggesting use of this or related materials in sensor applications.

Ultrafast energy migration in chromophore shell-metal nanoparticle assemblies.

A multifunctional ligand-coated nanoparticle system containing approximately 2000 highly two-photon absorptive chromophores has been investigated by means of steady-state and femtosecond time-resolved spectroscopy. This system with a high local concentration of chromophores showed remarkably low self-quenching and a high fluorescence quantum yield, which is important for a variety of two-photon sensing and imaging applications. We have observed evidence for ultrafast energy migration in these chromophore shell-metal nanoparticle systems. Time-resolved experiments also showed non-zero residual anisotropy after the initial fast decay, which can be interpreted as due to the formation of the specific domains on the metal surfaces. This investigation opens new avenues toward the development of multi-chromophoric efficient TPA fluorescence sensing/imaging systems with large numbers of chromophores per one metal particle nanoparticle.

Ultrabright supramolecular beacons based on the self-assembly of two-photon chromophores on metal nanoparticles.

Silver nanoparticles coated with a self-assembled layer of approximately 2500 chromophoric alkylthiol ligands, that exhibit a huge per particle two-photon absorption cross section (2.7 x 10-45 cm4 s photon-1) and a high fluorescence quantum yield (0.33), are reported. Polyfunctionalized variants of these nanoparticles have been produced that show reasonable solubility in water/ethanol mixtures. By virtue of the large number of tethered chromophores, these particles act as strongly two-photon absorbing nanobeacons and may have applications in fluorescence imaging and sensing.