Photochemical Strategies Enable the Synthesis of Tunable Azetidine-Based Energetic Materials.

Despite their favorable properties, azetidines are often overlooked as lead compounds across multiple industries. This is often attributed to the challenging synthesis of densely functionalized azetidines in an efficient manner. In this work, we report the scalable synthesis and characterization of seven azetidines with varying regio- and stereochemistry and their application as novel azetidine-based energetic materials, enabled by the visible-light-mediated aza Paternò-Büchi reaction. The performance and stark differences in the physical properties of these new compounds make them excellent potential candidates as novel solid melt-castable explosive materials, as well as potential liquid propellant plasticizers. This work highlights the scalability and utility of the visible-light aza Paternò-Büchi reaction and demonstrates the impact of stereochemical considerations on the physical properties of azetidine-based energetics. Considering the versatility and efficiency of the presented synthetic strategies, we expect that this work will guide the development of new azetidine-based materials in the energetics space as well as other industries.

Synthesis and Characterization of the Potential Energetic Propellant Plasticizer 3-Nitratoethyl-N-nitramino-5-nitratomethyl Isoxazole.

The synthesis of 3-(nitratoethyl-N-nitramino)-5-(nitratomethyl) isoxazole (C6 H7 N5 O9 , 1) is presented, and its energetic properties were ascertained and analyzed for energetic applications potential. 1 was found to be a solid without melting behavior, begins to decompose at 140 °C, and has a thermal onset decomposition temperature of 171.5 °C. 1 was synthesized in 5 steps from glyoxylic acid, and was found to exhibit acceptable sensitivities to impact, friction, and electrostatic discharge. The presence of the nitratoethyl nitramino (NENA) moiety, coupled with the high density (1.71 g cm-3 ) and superior calculated specific impulse (247.6 s) over the commonly employed gun propellant n-butyl NENA (density=1.22 g cm-3 , specific impulse=221 s), makes 1 a potential energetic plasticizer for next generation gun and rocket propellants. In addition, a modified procedure for the synthesis of dibromoformaldoxime (DBFO) was developed to provide this material in respectable yields on one mole scale. The safety considerations of DBFO are also highlighted, in which this compound sublimes, and must be handled with care, as it will cause burns upon contact with the skin.

Synthesis and Characterization of the Potential Melt-Castable Explosive 3-(1,2,4-Oxadiazolyl)-5-Nitratomethyl Isoxazole.

The synthesis of 3-(1,2,4-oxadiazolyl)-5-nitratomethyl isoxazole (C6 H4 N4 O5 ), its physical properties, and its theoretical performances are described. This energetic material was found to have a melting point range of 76.6-79.2 °C, and a thermal onset decomposition temperature of 184.5 °C. These thermal features put this material into the standalone melt-castable explosive class. The material was found to have TNT performance, and was found to be insensitive to impact, friction, and electrostatic discharge, despite having a nitric ester functionality. A critical reaction in making this molecule was the desymmetrization of diaminoglyoxime. The optimization of this transformation is described. Previous reports of this desymmetrization were found to be inaccurate, as the desymmetrization reaction produces a co-crystal of mono- and bi-1,2,4-oxadiazole products.

Bis(Nitroxymethylisoxazolyl) Furoxan: A Promising Standalone Melt-Castable Explosive.

The synthesis and crystal structure of the heterocyclic explosive bis(nitroxymethylisoxazolyl) furoxan, C10 H6 N6 O10 , are described. In addition, we report its physical properties and theoretical performance. This material was found to exhibit standalone melt-castable explosive properties, with a melting point of 89.8 °C and an onset decomposition temperature of 193.8 °C. Bis(nitroxymethylisoxazolyl) furoxan features an insensitive behavior to impact, friction, and electrostatic discharge, with a calculated detonation pressure about 25 % higher than the state-of-the-art melt-castable explosive TNT.

Impact of Stereo- and Regiochemistry on Energetic Materials.

The synthesis, physical properties, and calculated performances of six stereo- and regioisomeric cyclobutane nitric ester materials are described. While the calculated performances of these isomers, as expected, were similar, their physical properties were found to be extremely different. By alteration of the stereo- and regiochemistry, complete tunability in the form of low- or high-melting solids, stand-alone melt-castable explosives, melt-castable explosive eutectic compounds, and liquid propellant materials was obtained. This demonstrates that theoretical calculations should not be the main factor in driving the design of new materials and that stereo- and regiochemistry matter in the design of compounds of potential relevance to energetic formulators.

Molecular Dynamics Simulation Study of Adsorption of Bioinspired Oligomers on Alumina Surfaces.

The adsorption of small oligomers on a model metal oxide surface was studied with atomistically detailed molecular dynamics simulations. The oligomers consisted of two different repeat units: a maleimide, which contains a catechol functional group as in the dopamine residue found in marine adhesive proteins, and a methyl acrylate. A hydroxylated alumina surface was used as the model metal oxide surface. Adsorption interactions were investigated in aqueous as well as anhydrous conditions. In anhydrous conditions, the model oligomers displayed strong adsorption interactions with the surface. However, in aqueous conditions, the adsorption interactions were significantly weakened because of the competition with the water molecules for adsorption sites near the surface. Catechol functional groups in the model oligomers were found to play an important role in adsorption interactions with the alumina surface via hydrogen bonds. However, diverse adsorption properties were observed depending on compositions and sequences of two different repeat units and self-aggregations, indicating that the hydrogen bonding capability of catechol groups is not the sole factor determining adsorption properties.

Polydopamine and Polydopamine-Silane Hybrid Surface Treatments in Structural Adhesive Applications.

Numerous studies have focused on the remarkable adhesive properties of polydopamine, which can bind to substrates with a wide range of surface energies, even under aqueous conditions. This behavior suggests that polydopamine may be an attractive option as a surface treatment in structural bonding applications, where good bond durability is required. Here, we assessed polydopamine as a surface treatment for bonding aluminum plates with an epoxy resin. A model epoxy adhesive consisting of diglycidyl ether of bisphenol A (DGEBA) and Jeffamine D230 polyetheramine was employed, and lap shear measurements (ASTM D1002 10) were made (i) under dry conditions to examine initial bond strength and (ii) after exposure to hot/wet (63 °C in water for 14 days) conditions to assess bond durability. Surprisingly, our results showed that polydopamine alone as a surface treatment provided no benefit beyond that obtained by exposing the substrates to an alkaline solution of tris buffer used for the deposition of polydopamine. This implies that polydopamine has a potential Achilles' heel, namely, the formation of a weak boundary layer that was identified using X-ray photoelectron spectroscopy (XPS) of the fractured surfaces. In fact, for longer deposition times (2.5 and 18 h), the tris buffer-treated surface outperformed the polydopamine surface treatments, suggesting that tris buffer plays a unique role in improving adhesive performance even in the absence of polydopamine. We further showed that the use of polydopamine-3-aminopropyltriethoxysilane (APTES) hybrid surface treatments provided significant improvements in bond durability at extended deposition times relative to both polydopamine and an untreated control.

Plasmonic gold nanostars as optical nano-additives for injection molded polymer composites.

Nanoscale engineering of noble metal particles has provided numerous material configurations to selectively confine and manipulate light across the electromagnetic spectrum. Transitioning these materials to a composite form while maintaining the desired resonance properties has proven challenging. In this work, the successful integration of plasmon-focusing gold nanostars (GNSs) into polymer nanocomposites (PNCs) is demonstrated. Tailored GNSs are produced with over a 90% yield and methods to control the branching structures are shown. A protective silica capping shell is employed on the nanomaterials to facilitate survivability in the high temperate/high shear processing parameters to create optically-tuned injection molded PNCs. The developed GNS PNCs possess dichroic scattering and absorption behavior, opening up potential applications in the fields of holographic imaging, optical filtering and photovoltaics.

Protein catalyzed capture agents with tailored performance for in vitro and in vivo applications.

We report on peptide-based ligands matured through the protein catalyzed capture (PCC) agent method to tailor molecular binders for in vitro sensing/diagnostics and in vivo pharmacokinetics parameters. A vascular endothelial growth factor (VEGF) binding peptide and a peptide against the protective antigen (PA) protein of Bacillus anthracis discovered through phage and bacterial display panning technologies, respectively, were modified with click handles and subjected to iterative in situ click chemistry screens using synthetic peptide libraries. Each azide-alkyne cycloaddition iteration, promoted by the respective target proteins, yielded improvements in metrics for the application of interest. The anti-VEGF PCC was explored as a stable in vivo imaging probe. It exhibited excellent stability against proteases and a mean elimination in vivo half-life (T1/2 ) of 36 min. Intraperitoneal injection of the reagent results in slow clearance from the peritoneal cavity and kidney retention at extended times, while intravenous injection translates to rapid renal clearance. The ligand competed with the commercial antibody for binding to VEGF in vivo. The anti-PA ligand was developed for detection assays that perform in demanding physical environments. The matured anti-PA PCC exhibited no solution aggregation, no fragmentation when heated to 100°C, and > 81% binding activity for PA after heating at 90°C for 1 h. We discuss the potential of the PCC agent screening process for the discovery and enrichment of next generation antibody alternatives.

Synthesis and Characterization of Aminopropyltriethoxysilane-Polydopamine Coatings.

Polydopamine coatings are of interest due to the fact that they can promote adhesion to a broad range of materials and can enable a variety of applications. However, the polydopamine-substrate interaction is often noncovalent. To broaden the potential applications of polydopamine, we show the incorporation of 3-aminopropyltriethoxysilane (APTES), a traditional coupling agent capable of covalent bonding to a broad range of organic and inorganic surfaces, into polydopamine coatings. High energy X-ray photoelectron spectroscopy (HE-XPS), conventional XPS, near-edge X-ray absorption fine structure (NEXAFS), Fourier transform infrared-attenuated total reflectance (FTIR-ATR), and ellipsometry measurements were used to investigate changes in coating chemistry and thickness, which suggest covalent incorporation of APTES into polydopamine. These coatings can be deposited either in Tris buffer or by using an aqueous APTES solution as a buffer without Tris. APTES-dopamine hydrochloride deposition from solutions with molar ratios between 0:1 and 10:1 allowed us to control the coating composition across a broad range.

Highly Transparent and Toughened Poly(methyl methacrylate) Nanocomposite Films Containing Networks of Cellulose Nanofibrils.

Cellulose nanofibrils (CNFs) are a class of cellulosic nanomaterials with high aspect ratios that can be extracted from various natural sources. Their highly crystalline structures provide the nanofibrils with excellent mechanical and thermal properties. The main challenges of CNFs in nanocomposite applications are associated with their high hydrophilicity, which makes CNFs incompatible with hydrophobic polymers. In this study, highly transparent and toughened poly(methyl methacrylate) (PMMA) nanocomposite films were prepared using various percentages of CNFs covered with surface carboxylic acid groups (CNF-COOH). The surface groups make the CNFs interfacial interaction with PMMA favorable, which facilitate the homogeneous dispersion of the hydrophilic nanofibrils in the hydrophobic polymer and the formation of a percolated network of nanofibrils. The controlled dispersion results in high transparency of the nanocomposites. Mechanical analysis of the resulting films demonstrated that a low percentage loading of CNF-COOH worked as effective reinforcing agents, yielding more ductile and therefore tougher films than the neat PMMA film. Toughening mechanisms were investigated through coarse-grained simulations, where the results demonstrated that a favorable polymer-nanofibril interface together with percolation of the nanofibrils, both facilitated through hydrogen bonding interactions, contributed to the toughness improvement in these nanocomposites.

Mechanochemical strengthening of a synthetic polymer in response to typically destructive shear forces.

High shear stresses are known to trigger destructive bond-scission reactions in polymers. Recent work has shown that the same shear forces can be used to accelerate non-destructive reactions in mechanophores along polymer backbones, and it is demonstrated here that such mechanochemical reactions can be used to strengthen a polymer subjected to otherwise destructive shear forces. Polybutadiene was functionalized with dibromocyclopropane mechanophores, whose mechanical activation generates allylic bromides that are crosslinked in situ by nucleophilic substitution reactions with carboxylates. The crosslinking is activated efficiently by shear forces both in solvated systems and in bulk materials, and the resulting covalent polymer networks possess moduli that are orders-of-magnitude greater than those of the unactivated polymers. These molecular-level responses and their impact on polymer properties have implications for the design of materials that, like biological materials, actively remodel locally as a function of their physical environment.

Electrospun polycaprolactone scaffolds with tailored porosity using two approaches for enhanced cellular infiltration.

The impact of mat porosity of polycaprolactone (PCL) electrospun fibers on the infiltration of neuron-like PC12 cells was evaluated using two different approaches. In the first method, bi-component aligned fiber mats were fabricated via the co-electrospinning of PCL with polyethylene oxide (PEO). Variation of the PEO flow rate, followed by selective removal of PEO from the PCL/PEO mesh, allowed for control of the porosity of the resulting scaffold. In the second method, aligned fiber mats were fabricated from various concentrations of PCL solutions to generate fibers with diameters between 0.13 ± 0.06 and 9.10 ± 4.1 µm. Of the approaches examined, the variation of PCL fiber diameter was found to be the better method for increasing the infiltration of PC12 cells, with the optimal infiltration into the ca. 1.5-mm-thick meshes observed for the mats with the largest fiber diameters, and hence largest pore sizes.

Quantification of protein incorporated into electrospun polycaprolactone tissue engineering scaffolds.

The surface modification of synthetic tissue engineering scaffolds is essential to improving their hydrophilicity and cellular compatibility. Plasma treatment is an effective way to increase the hydrophilicity of a surface, but the incorporation of biomolecules is also important to control cellular adhesion and differentiation, among many other outcomes. In this work, oriented polycaprolactone (PCL) electrospun fibers were modified by air-plasma treatment, followed by the covalent attachment of laminin. The amount of protein incorporated onto the fiber surface was controlled by varying the reaction time and the protein solution concentration. The protein concentration and coverage were quantified using X-ray photoelectron spectroscopy (XPS), solid-state ultraviolet-visible spectroscopy (UV-vis) and two fluorescence-based assays. XPS results showed a nearly linear increase in protein coverage with increasing protein soaking solution concentration until a monolayer was formed. Results from XPS and the NanoOrange fluorescence assay revealed multilayer protein coverage at protein solution concentrations between 25 and 50 µg/mL, whereas the UV-vis assay demonstrated multilayer coverage at lower protein solution concentrations. The effect of protein concentration on the neurite outgrowth of neuron-like PC12 cells was evaluated, and outgrowth rates were found to be positively correlated to increasing protein concentration.

Coaxial electrospun poly(methyl methacrylate)-polyacrylonitrile nanofibers: atomic force microscopy and compositional characterization.

Poly(methyl methacrylate) (PMMA)-polyacrylonitrile (PAN) fibers were prepared using a conventional single-nozzle electrospinning technique. The as-spun fibers exhibited core-shell morphology as verified by transmission electron microscopy (TEM) and atomic force microscopy (AFM). AFM-phase and modulus mapping images of the fiber cross-section and X-ray photoelectron spectroscopy (XPS) analysis indicated that PAN formed the shell and PMMA formed the core material. XPS, thermogravimetric analysis (TGA), and elemental analysis were used to determine fiber compositional information. Soaking the fibers in solvent demonstrated removal of the core material, generating hollow PAN fibers.

Surface-modified nanofibrous biomaterial bridge for the enhancement and control of neurite outgrowth.

Biomaterial bridges constructed from electrospun fibers offer a promising alternative to traditional nerve tissue regeneration substrates. Aligned and unaligned polycaprolactone (PCL) electrospun fibers were prepared and functionalized with the extracellular matrix proteins collagen and laminin using covalent and physical adsorption attachment chemistries. The effect of the protein modified and native PCL nanofiber scaffolds on cell proliferation, neurite outgrowth rate, and orientation was examined with neuronlike PC12 cells. All protein modified scaffolds showed enhanced cellular adhesion and neurite outgrowth compared to unmodified PCL scaffolds. Neurite orientation was found to be in near perfect alignment with the fiber axis for cells grown on aligned fibers, with difference angles of less than 7° from the fiber axis, regardless of the surface chemistry. The bioavailability of PCL fibers with covalently attached laminin was found to be identical to that of PCL fibers with physically adsorbed laminin, indicating that the covalent chemistry did not change the protein conformation into a less active form and the covalent attachment of protein is a suitable method for enhancing the biocompatibility of tissue engineering scaffolds.

Controlling surface energy and wetability with Diels-Alder chemistry.

Reversible Diels-Alder chemistry was utilized to manipulate the surface energy of glass substrates. Hydrophobic dieneophiles were prepared and attached to glass slides and capillaries to yield a nonwetting surface. Thermal treatment of the surfaces cleaved the Diels-Alder linkage, and resulted in the fabrication of a hydrophilic surface. Preliminary analysis utilized contact angle (CA) measurements to monitor the change in surface energy, and observed a hydrophilic state (CA - 70 +/- 3 degrees) before attachment of the dieneophile to a hydrophobic state (CA - 101 +/- 9 degrees) followed by regeneration of the hydrophilic state (CA - 70 +/- 6 degrees) upon cleavage of the Diels-Alder linkage. The treatments were then applied to glass capillaries, with effective treatment confirmed by fluid column measurements. Patterned treatments were also demonstrated to provide effective flow gating. Finally, attempts to create self-pressurizing capillaries were unsuccessful due to pronounced contact angle hysteresis for the hydrophobic surface treatment.

Effect of hyperbranched surface-migrating additives on the electrospinning behavior of poly(methyl methacrylate).

Poly(methyl methacrylate) (PMMA) was electrospun in the presence of a low molecular weight, hyperbranched poly(ethylene imine) additive partially functionalized with perfluorinated and aliphatic end-groups (M(n) approximately 1600 g/mol). The additive exhibited surface segregation with an insignificant influence on the rheological behavior of PMMA solutions. A morphological transition from beaded electrospun fibers to uniform fibers was observed upon introduction of additive at low PMMA concentrations. XPS revealed a surface enrichment of fluorine and nitrogen, which are both present in the hyperbranched additive. Surface fluorine content depended primarily on the amount of additive in solution, and a dependency on the PMMA/additive weight ratio was not observed.

Optical Properties of Phthalocyanine and Naphthalocyanine Compounds.

Phthalocyanines, naphthalocyanins, and their derivatives are frequently used as light modulating materials. These compounds, with their stable planar square structure and highly delocalized π-electron system, are being used in numerous technological applications, such as pigments in chemical sensors, and more recently as photosensitizers for photodynamic therapy. The nonlinear optical properties (NLO) of these compounds are of particular importance. Using density functional method (DFT), we calculated the optical properties of phthalocyanine and naphthalocyanine complexes with Si as a central atom. We examined the effect of hydrophilic axial substituents and the size of polycyclic aromatic hydrocarbons surrounding the porphyrazine-Si kernel on the optical properties of title molecules. Both UV-vis and RSA spectra are calculated and are compared with available experimental results. The time-dependent DFT (TDDFT) with the B3LYP functional predicts that the characteristic UV-vis absorption maxima are blue-shifted; however, the relative error is almost constant for phthalocyanine and naphthalocyanine compounds. The TDDFT triplet-triplet absorption spectra of Si-phthalocyanine and Si-naphthalocyanine complexes reproduce experimental data well.