Hybrid Bonding Bottlebrush Polymers Grafted from a Supramolecular Polymer Backbone.

Bottlebrush polymers, macromolecules consisting of dense polymer side chains grafted from a central polymer backbone, have unique properties resulting from this well-defined molecular architecture. With the advent of controlled radical polymerization techniques, access to these architectures has become more readily available. However, synthetic challenges remain, including the need for intermediate purification, the use of toxic solvents, and challenges with achieving long bottlebrush architectures due to backbone entanglements. Herein, we report hybrid bonding bottlebrush polymers (systems integrating covalent and noncovalent bonding of structural units) consisting of poly(sodium 4-styrenesulfonate) (p(NaSS)) brushes grafted from a peptide amphiphile (PA) supramolecular polymer backbone. This was achieved using photoinitiated electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization in water. The structure of the hybrid bonding bottlebrush architecture was characterized using cryogenic transmission electron microscopy, and its properties were probed using rheological measurements. We observed that hybrid bonding bottlebrush polymers were able to organize into block architectures containing domains with high brush grafting density and others with no observable brushes. This finding is possibly a result of dynamic behavior unique to supramolecular polymer backbones, enabling molecular exchange or translational diffusion of monomers along the length of the assemblies. The hybrid bottlebrush polymers exhibited higher solution viscosity at moderate shear, protected supramolecular polymer backbones from disassembly at high shear, and supported self-healing capabilities, depending on grafting densities. Our results demonstrate an opportunity for novel properties in easily synthesized bottlebrush polymer architectures built with supramolecular polymers that might be useful in biomedical applications or for aqueous lubrication.

Biopolymer-supramolecular polymer hybrids for photocatalytic hydrogen production.

Solar generation of H2 is a promising strategy for dense energy storage. Supramolecular polymers composed of chromophore amphiphile monomers containing perylene monoimide (PMI) have been reported as crystalline light-harvesting assemblies for aqueous H2-evolving catalysts. Gelation of these supramolecular polymers with multivalent ions creates hydrogels with high diffusivity but insufficient mechanical stability and catalyst retention for reusability. We report here on using sodium alginate (SA) biopolymer to both induce supramolecular polymerization of PMI and co-immobilize them with catalysts in a robust hydrogel with high diffusivity that can also be 3D-printed. Faster mass transfer was achieved by controlling the material macrostructure by reducing gel diameter and microstructure by reducing biopolymer loading. Optimized gels produce H2 at rates rivaling solution-based PMI and generate H2 for up to 6 days. The PMI assemblies in the SA matrix create a percolation network capable of bulk-electron transfer under illumination. These PMI-SA materials were then 3D-printed on conductive substrates to create 3D hydrogel photoelectrodes with optimized porosity. The design of these versatile hybrid materials was bioinspired by the soft matter environment of natural photosynthetic systems and opens the opportunity to carry out light-to-fuel conversion within soft matter with arbitrary shapes and particular local environments.

Photocatalytically Active Graphitic Carbon Nitride as an Effective and Safe 2D Material for In Vitro and In Vivo Photodynamic Therapy.

Thanks to its photocatalytic property, graphitic carbon nitride (g-C3 N4 ) is a promising candidate in various applications including nanomedicine. However, studies focusing on the suitability of g-C3 N4 for cancer therapy are very limited and possible underlying molecular mechanisms are unknown. Here, it is demonstrated that photoexcitation of g-C3 N4 can be used effectively in photodynamic therapy, without using any other carrier or additional photosensitizer. Upon light exposure, g-C3 N4 treatment kills cancer cells, without the need of any other nanosystem or chemotherapeutic drug. The material is efficiently taken up by tumor cells in vitro. The transcriptome and proteome of g-C3 N4 and light treated cells show activation in pathways related to both oxidative stress, cell death, and apoptosis which strongly suggests that only when combined with light exposure, g-C3 N4 is able to kill cancer cells. Systemic administration of the mesoporous form results in elimination from urinary bladder without any systemic toxicity. Administration of the material significantly decreases tumor volume when combined with local light treatment. This study paves the way for the future use of not only g-C3 N4 but also other 2D nanomaterials in cancer therapy.

Concise, Single-Step Synthesis of Sulfur-Enriched Graphene: Immobilization of Molecular Clusters and Battery Applications.

The concise synthesis of sulfur-enriched graphene for battery applications is reported. The direct treatment of graphene oxide (GO) with the commercially available Lawesson's reagent produced sulfur-enriched-reduced GO (S-rGO). Various techniques, such as X-ray photoelectron spectroscopy (XPS), confirmed the occurrence of both sulfur functionalization and GO reduction. Also fabricated was a nanohybrid material by using S-rGO with polyoxometalate (POM) as a cathode-active material for a rechargeable battery. Transmission electron microscopy (TEM) revealed that POM clusters were individually immobilized on the S-rGO surface. This battery, based on a POM/S-rGO complex, exhibited greater cycling stability for the charge-discharge process than a battery with nanohybrid materials positioned between the POM and nonenriched rGO. These results demonstrate that the use of sulfur-containing groups on a graphene surface can be extended to applications such as the catalysis of electrochemical reactions and electrodes in other battery systems.

Tuning the Carbon Nanotube Selectivity: Optimizing Reduction Potentials and Distortion Angles in Perylenediimides.

Different water-soluble perylenediimides (PDIs) have been used to individualize and stabilize single-walled carbon nanotubes (SWCNTs) in aqueous media. A key feature of the PDIs is that they can be substituted at the bay positions via the addition of two and/or four bromines. This enables control over structural and electronic PDI characteristics, which prompted us to conduct comparative assays with focus on SWCNTs' chirality and charge transfer. Electrochemical, microscopic, and spectroscopic experiments were used to investigate the SWCNT chiral selectivity of PDIs, on the one hand, and charge-transfer reactions between SWCNTs and PDIs, on the other hand.

On-Demand Release of Hydrosoluble Drugs from a Paramagnetic Porous Collagen-Based Scaffold.

The design of a collagen scaffold containing iron oxide nanostructures capped by a TiO2 (anatase) layer is reported. The TiO2 shell is proposed to perform a dual role: 1) as an innovative and biocompatible cross-linker agent, providing binding sites to the protein moiety, through the well-known TiO2 chemical affinity towards carboxyl groups, and 2) as a protective surface layer for the paramagnetic core against oxidation. Simultaneously, the presence of the nanostructures confers to the collagen gel sensitivity to an external stimulus; that is, the application of a magnetic field. The hybrid biomaterial was demonstrated to be nontoxic and is proposed as a smart scaffold for the release of bioactive compounds on demand. The tuneable release of a model protein (myoglobin) upon application of a magnetic field was investigated. Myoglobin was loaded in the microporous material and discharge was induced by consecutive magnet applications, leading to release of the protein with high spatio-temporal and dosage control.

Altered serum fatty acid composition in geriatric depression.

Fatty acids (FA), mainly polyunsaturated (PUFA) of n-3 or n-6 types, may influence neuropsychobiological processes. Decreased levels of n-3 PUFA have been shown to be related to major depression and supplementation of n-3 PUFA seems to contribute to improved depression treatment outcome. The profiles of serum FA profiles in patients with geriatric depression have not been thoroughly studied yet. The present study investigated the FA profiles of patients with geriatric depression and of mentally healthy elderly individuals. Serum FA profiles of 36 inpatients with geriatric depression who fulfilled DSM-IV criteria for unipolar major depression were compared with those of 37 control subjects. Patients with geriatric depression, irrespective of gender, exhibited lower total FAs, as well as significantly lower concentrations of total n-3 PUFA and eicosapentaenoic acid, though the groups did not differ with regard to Body Mass Index. The findings of the present study point to an association between lower FA serum levels and geriatric depression. Further investigations with larger samples and dietetic interventions may provide deeper insights into the role of eicosapentaenoic acid and total n-3 PUFA in the development and treatment of geriatric depression.

Multichromophoric hybrid species made of perylene bisimide derivatives and Ru(ii) and Os(ii) polypyridine subunits.

Herein, the synthesis and the photophysical and redox properties of a new perylene bisimide (PBI) species (L), bearing two 1,10-phenanthroline (phen) ligands at the two imide positions of the PBI, and its dinuclear Ru(ii) and Os(ii) complexes, [(bpy)2Ru(µ-L)Ru(bpy)2](PF6)4 (Ru2; bpy = 2,2'-bipyridine) and [(Me2-bpy)2Os(µ-L)Os(Me2-bpy)2](PF6)4 (Os2; Me2-bpy = (4,4'-dimethyl)-2,2'-bipyridine), are reported. The absorption spectra of the compounds are dominated by the structured bands of the PBI subunit due to the lowest-energy spin-allowed π-π* transition. The spin-allowed MLCT transitions in Ru2 and Os2 are inferred by the absorption at 350-470 nm, where the PBI absorption is negligible. The absorption band extends towards the red region for Os2 due to the spin-forbidden MLCT transitions, intensified by the heavy osmium center. The reduction processes of the compounds are dominated by two successive mono-electronic PBI-based processes, which in the metal complexes are slightly shifted compared to the free ligand. On oxidation, both metal complexes undergo an apparent bi-electronic process (at 1.31 V vs. SCE for Ru2 and 0.77 V for Os2), attributed to the simultaneous one-electron oxidation of the two weakly-interacting metal centers. In Ru2 and Os2, the intense fluorescence of L subunit (λmax, 535 nm; τ, 4.3 ns; Φ, 0.91) is fully quenched, mainly by photoinduced electron transfer from the metal centers, on the ps timescale (time constant, 11 ps in Ru2 and 3 ps in Os2). Such photoinduced electron transfer leads to the formation of a charge-separated state, which directly decays to the ground state in about 70 ps in Os2, but produces the triplet π-π* state of the PBI subunit in 35 ps in Ru2. The results provide information on the excited-state processes of the hybrid species combining two dominant classes of chromophore/luminophore species, the PBI and the metal polypyridine complexes, and can be used for future design on new hybrid species with made-to-order properties.

Modification of nanocrystalline WO3 with a dicationic perylene bisimide: applications to molecular level solar water splitting.

[(N,N'-Bis(2-(trimethylammonium)ethylene) perylene 3,4,9,10-tetracarboxylic acid bisimide)(PF6)2] (1) was observed to spontaneously adsorb on nanocrystalline WO3 surfaces via aggregation/hydrophobic forces. Under visible irradiation (λ > 435 nm), the excited state of 1 underwent oxidative quenching by electron injection (kinj > 10(8) s(-1)) to WO3, leaving a strongly positive hole (Eox ≈ 1.7 V vs SCE), which allows to drive demanding photo-oxidation reactions in photoelectrochemical cells (PECs). The casting of IrO2 nanoparticles (NPs), acting as water oxidation catalysts (WOCs) on the sensitized electrodes, led to a 4-fold enhancement in photoanodic current, consistent with hole transfer from oxidized dye to IrO2 occurring on the microsecond time scale. Once the interaction of the sensitizer with suitable WOCs is optimized, 1/WO3 photoanodes may hold potentialities for the straightforward building of molecular level devices for solar fuel production.

Biocompatible Collagen Paramagnetic Scaffold for Controlled Drug Release.

A porous collagen-based hydrogel scaffold was prepared in the presence of iron oxide nanoparticles (NPs) and was characterized by means of infrared spectroscopy and scanning electron microscopy. The hybrid scaffold was then loaded with fluorescein sodium salt as a model compound. The release of the hydrosoluble species was triggered and accurately controlled by the application of an external magnetic field, as monitored by fluorescence spectroscopy. The biocompatibility of the proposed matrix was also tested by the MTT assay performed on 3T3 cells. Cell viability was only slightly reduced when the cells were incubated in the presence of the collagen-NP hydrogel, compared to controls. The economicity of the chemical protocol used to obtain the paramagnetic scaffolds as well as their biocompatibility and the safety of the external trigger needed to induce the drug release suggest the proposed collagen paramagnetic matrices for a number of applications including tissue engeneering and drug delivery.

Carbon Nanodots: Supramolecular Electron Donor-Acceptor Hybrids Featuring Perylenediimides.

We describe the formation of charge-transfer complexes that feature electron-donating carbon nanodots (CND) and electron-accepting perylenediimides (PDI). The functionalities of PDIs have been selected to complement those of CNDs in terms of electrostatic and π-stacking interactions based on oppositely charged ionic head groups and extended π-systems, respectively. Importantly, the contributions from electrostatic interactions were confirmed in reference experiments, in which stronger interactions were found for PDIs that feature positively rather than negatively charged head groups. The electronic interactions between the components in the ground and excited state were characterized in complementary absorption and fluorescence titration assays that suggest charge-transfer interactions in both states with binding constants on the order of 8×10(4) M(-1) (25 L g(-1) ). Selective excitation of the two components in ultrafast pump probe experiments gave a 210 ps lived charge-separated state.

Microscopy and modelling investigations on the morphology of the biofilm exopolysaccharide produced by Burkholderia multivorans strain C1576.

Bacteria form very often biofilms where they embed in a self-synthesized matrix exhibiting a gel-like appearance. Matrices offer several advantages, including defence against external threats and the easiness of intercellular communication. In infections, biofilm formation enhances bacteria resistance against antimicrobials, causing serious clinical problems for patients' treatments. Biofilm matrices are composed of proteins, extracellular DNA, and polysaccharides, the latter being the major responsible for matrix architecture. The repeating unit of the biofilm polysaccharide synthesized by Burkholderia multivorans strain C1576 contains two mannoses and two sequentially linked rhamnoses, one of them 50 % methylated on C-3. Rhamnose, a 6-deoxysugar, has lower polarity than other common monosaccharides and its methylation further reduces polarity. This suggests a possible role of this polysaccharide in the biofilm matrix; in fact, computer modelling and atomic force microscopy studies evidenced intra- and inter-molecular non-polar interactions both within polysaccharides and with aliphatic molecules. In this paper, the polysaccharide three-dimensional morphology was investigated using atomic force microscopy in both solid and solution states. Independent evidence of the polymer conformation was obtained by transmission electron microscopy which confirmed the formation of globular compact structures. Finally, data from computer dynamic simulations were used to model the three-dimensional structure.

Artificial extracellular matrix scaffolds of mobile molecules enhance maturation of human stem cell-derived neurons.

Human induced pluripotent stem cell (hiPSC) technologies offer a unique resource for modeling neurological diseases. However, iPSC models are fraught with technical limitations including abnormal aggregation and inefficient maturation of differentiated neurons. These problems are in part due to the absence of synergistic cues of the native extracellular matrix (ECM). We report on the use of three artificial ECMs based on peptide amphiphile (PA) supramolecular nanofibers. All nanofibers display the laminin-derived IKVAV signal on their surface but differ in the nature of their non-bioactive domains. We find that nanofibers with greater intensity of internal supramolecular motion have enhanced bioactivity toward hiPSC-derived motor and cortical neurons. Proteomic, biochemical, and functional assays reveal that highly mobile PA scaffolds caused enhanced ß1-integrin pathway activation, reduced aggregation, increased arborization, and matured electrophysiological activity of neurons. Our work highlights the importance of designing biomimetic ECMs to study the development, function, and dysfunction of human neurons.

Multiwalled carbon nanotubes drive the activity of metal@oxide core-shell catalysts in modular nanocomposites.

Rational nanostructure manipulation has been used to prepare nanocomposites in which multiwalled carbon nanotubes (MWCNTs) were embedded inside mesoporous layers of oxides (TiO(2), ZrO(2), or CeO(2)), which in turn contained dispersed metal nanoparticles (Pd or Pt). We show that the MWCNTs induce the crystallization of the oxide layer at room temperature and that the mesoporous oxide shell allows the particles to be accessible for catalytic reactions. In contrast to samples prepared in the absence of MWCNTs, both the activity and the stability of core-shell catalysts is largely enhanced, resulting in nanocomposites with remarkable performance for the water-gas-shift reaction, photocatalytic reforming of methanol, and Suzuki coupling. The modular approach shown here demonstrates that high-performance catalytic materials can be obtained through the precise organization of nanoscale building blocks.

Polyaromatic cores for the exfoliation of popular 2D materials.

Two-dimensional (2D) nanomaterials have attracted interest from the scientific community due to their unique properties. The production of these materials has been carried out by diverse methodologies, the liquid phase exfoliation being the most promising one due to its simplicity and potential scalability. The use of several stabilizers allows to obtain dispersions of these 2D nanomaterials in solvents with low boiling points. Herein we describe a general exfoliation method for different 2D materials employing a biphasic water/dichloromethane system and two different (poly)aromatic hydrocarbons (PAHs). This method allows us to obtain dispersions of the exfoliated 2D materials with high concentrations in the organic solvent. Due to the low boiling point of dichloromethane, and therefore its easy removal, the obtained dispersions can be employed as additives for different composites. We corroborate that the exfoliation efficiency is improved due to the π-π and van der Waals interactions between the PAHs and the layers of the 2D materials.

Modeling Interactions within and between Peptide Amphiphile Supramolecular Filaments.

Many peptides are able to self-assemble into one-dimensional (1D) nanostructures, such as cylindrical fibers or ribbons of variable widths, but the relationship between the morphology of 1D objects and their molecular structure is not well understood. Here, we use coarse-grained molecular dynamics (CG-MD) simulations to study the nanostructures formed by self-assembly of different peptide amphiphiles (PAs). The results show that ribbons are hierarchical superstructures formed by laterally assembled cylindrical fibers. Simulations starting from bilayer structures demonstrate the formation of filaments, whereas other simulations starting from filaments indicate varying degrees of interaction among them depending on chemical structure. These interactions are verified by observations using atomic force microscopy of the various systems. The interfilament interactions are predicted to be strongest in supramolecular assemblies that display hydrophilic groups on their surfaces, while those with hydrophobic ones are predicted to interact more weakly as confirmed by viscosity measurements. The simulations also suggest that peptide amphiphiles with hydrophobic termini bend to reduce their interfacial energy with water, which may explain why these systems do not collapse into superstructures of bundled filaments. The simulations suggest that future experiments will need to address mechanistic questions about the self-assembly of these systems into hierarchical structures, namely, the preformation of interactive filaments vs equilibration of large assemblies into superstructures.

Carbon nanotube sidewall functionalization with carbonyl compounds--modified Birch conditions vs the organometallic reduction approach.

Covalent addition reactions turned out to be one of the most important functionalization techniques for a structural alteration of single walled carbon nanotube (SWCNT) scaffolds. During the last years, several reaction sequences based on an electrophilic interception of intermediately generated SWCNT(n-) carbanions, obtained via Birch reduction or by a nucleophilic addition of organometallic species, have been developed. Nevertheless, the scope and the variety of potential electrophiles is limited due to the harsh reaction conditions requested for a covalent attachment of the functional entities onto the SWCNT framework. Herein, we present a significant modification of the reductive alkylation/arylation sequence, the so-called Billups reaction, which extends the portfolio of electrophiles for covalent sidewall functionalization to carbonyl compounds--ketones, esters, and even carboxylic acid chlorides. Moreover, these carbonyl-based electrophiles can also be used as secondary functionalization reagents for anionic SWCNT intermediates, derived from a primary nucleophilic addition step. This directly leads to the generation of mixed functional SWCNT architectures, equipped with hydroxyl or carbonyl anchor groups, suitable for ongoing derivatization reactions. A correlated absorption and emission spectroscopic study elucidates the influence of the covalent sidewall functionalization degree onto the excitonic transition features of carbon nanotubes. The characterization of the different SWCNT adducts has been carried out by means of Raman, UV-vis/nIR, and fluorescence spectroscopy as well as by thermogravimetric analysis combined with mass spectrometry and X-ray photoelectron spectroscopy analysis.

Electronic properties of propylamine-functionalized single-walled carbon nanotubes.

We present resonant Raman measurements on single-walled carbon nanotubes (SWCNT) functionalized with propylamine groups at different degrees. Direct nucleophilic addition based on in situ generated primary amides is used for attaching n-propylamine to the sidewalls of SWCNTs. The influence of the amino functionalities on the electronic structure of the nanotubes is investigated. From the Raman resonance profiles of the radial breathing modes (RBMs), the chiral indices of the corresponding tubes are assigned. We observe significant redshifts of the transition energies and a broadening of the resonance windows due to chemical modification of SWCNTs. Similar redshifts are derived from the analysis of the NIR/Vis transmission spectrum. The relative Raman intensities of the functionalized samples and the evaluation of their transmission spectra indicate a diameter dependence of the reactivity as it has been observed for other moieties. By analyzing the defect induced D mode we observe a considerable degree of functionalization accompanied by an almost unharmed tube structure, which ensures that the observed effects are mainly driven by changes of the electronic structure.

Supramolecular Chiral Discrimination of D-Phenylalanine Amino Acid Based on a Perylene Bisimide Derivative.

The interaction between homochiral substituted perylene bisimide (PBI) molecule and the D enantiomer of phenylalanine amino acid was monitored. Spectroscopic transitions of PBI derivative in aqueous solution in the visible range were used to evaluate the presence of D-phenylalanine. UV-visible, fluorescence, FT-IR, and AFM characterizations showed that D-phenylalanine induces significant variations in the chiral perylene derivative aggregation state and the mechanism is enantioselective as a consequence of the 3D analyte structure. The interaction mechanism was further investigated in presence of interfering amino acid (D-serine and D-histidine) confirming that both chemical structure and its 3D structure play a crucial role for the amino acid discrimination. A D-phenylalanine fluorescence sensor based on perylene was proposed. A limit of detection (LOD) of 64.2 ± 0.38 nM was calculated in the range 10-7-10-5 M and of 1.53 ± 0.89 µM was obtained in the range 10-5 and 10-3 M.

Photoelectrochemical Properties of SnO2 Photoanodes Sensitized by Cationic Perylene-Di-Imide Aggregates for Aqueous HBr Splitting.

Perylene-sensitized mesoporous SnO2 films were used as electrodes for photoelectrochemical HBr splitting in aqueous solution. Upon AM 1.5 G illumination a 3-4 fold increase of the saturated photocurrent was observed when decreasing the pH of the aqueous solution from pH 3 to pH 0 (j max = 0.05 ± 0.01 mAcm-2 at pH 3 and 0.17 ± 0.02 mAcm-2 at pH 0, respectively). A detailed spectroscopic and electrochemical analysis of the hybrid material was carried out in order to address the impact of interfacial energetics on charge separation dynamics. UV/Vis spectroelectrochemical measurements showed that the energy of semiconductor states in such systems can be adjusted independently from the molecular levels by varying proton concentration. Photoelectrochemical measurements and ns-µs transient absorption spectroscopy reveal that pH-related changes of the interfacial energetics have only a minor impact on the charge injection rate. An increase of the proton concentration improves charge collection mainly by retarding recombination, which in the case of Br- oxidation is in critical competition with perylene regeneration. Control of the back recombination appears to be a key feature in heterogeneous molecular systems tasked to drive energetically demanding redox reactions.