Self‐Assembled PAA‐Based Nanoparticles as Potential Gene and Protein Delivery Systems

A series of nanoparticles is prepared via layer‐by‐layer assembly of oppositely charged, synthetic biocompatible polyamidoamine polymers as potential carriers. Particle size, surface charge and internal chain mobility are quantified as a function of the polymer type and number of layers. The effect of addition of surfactant is examined to simulate the effects of nanoparticle dissolution. The cyctotoxicity of these particles (in epithelia and murine cell lines) are orders of magnitude lower than polyethyleneimine controls. Stable nanoparticles may be prepared from mixtures of strongly, oppositely charged polymers, but less successfully from weakly charged polymers, and, given their acceptable toxicity characteristics, such modularly designed constructs show promise for drug and gene delivery.

     

Synthesis of Substituted Trans-1,6-Dimethylbicyclo[4.3.0]-non-2-enes Using A Claisen Rearrangement of α-(Thioalkoxy) Esters

The Claisen rearrangement of α-(thioalkoxy)-esters provided access to substituted trans-1, 6-dimethylbicyclo[4.3.0]non-2-enes characteristic of the CD rings of the cucurbitanes.     

Expanding the Toolbox of Metal–Phenolic Networks via Enzyme‐Mediated Assembly

Functional coatings are of considerable interest because of their fundamental implications for interfacial assembly and promise for numerous applications. Universally adherent materials have recently emerged as versatile functional coatings; however, such coatings are generally limited to catechol, (ortho‐diphenol)‐containing molecules, as building blocks. Here, we report a facile, biofriendly enzyme‐mediated strategy for assembling a wide range of molecules (e.g., 14 representative molecules in this study) that do not natively have catechol moieties, including small molecules, peptides, and proteins, on various surfaces, while preserving the molecule's inherent function, such as catalysis (≈80 % retention of enzymatic activity for trypsin). Assembly is achieved by in situ conversion of monophenols into catechols via tyrosinase, where films form on surfaces via covalent and coordination cross‐linking. The resulting coatings are robust, functional (e.g., in protective coatings, biological imaging, and enzymatic catalysis), and versatile for diverse secondary surface‐confined reactions (e.g., biomineralization, metal ion chelation, and N‐hydroxysuccinimide conjugation).     

Polyphenol‐Mediated Assembly of Proteins for Engineering Functional Materials

Functional materials composed of proteins have attracted much interest owing to the inherent and diverse functionality of proteins. However, establishing general techniques for assembling proteins into nanomaterials is challenging owing to the complex physicochemical nature and potential denaturation of proteins. Here, a simple, versatile strategy is introduced to fabricate functional protein assemblies through the interfacial assembly of proteins and polyphenols (e.g., tannic acid) on various substrates (organic, inorganic, and biological). The dominant interactions (hydrogen‐bonding, hydrophobic, and ionic) between the proteins and tannic acid were elucidated; most proteins undergo multiple noncovalent stabilizing interactions with polyphenols, which can be used to engineer responsiveness into the assemblies. The proteins retain their structure and function within the assemblies, thereby enabling their use in various applications (e.g., catalysis, fluorescence imaging, and cell targeting).     

A Theoretical Study of ãA2 CH2

The potential energy surface and dipole moment surfaces of the ã⁴A₂ electronic state of CH₂⁺ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation-vibration term values for ã-state CH₂⁺, CD⁺₂, and CHD⁺ and to simulate the rotation and rotation-vibration absorption spectrum of CH₂⁺ in the ã⁴A₂ electronic state. Our work is motivated by studies of CH₂⁺ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the X?/Ã ground state pair, it turns out to be relatively high-lying, and we determine that T_e(ã)=30447.5 cm⁻¹. The equilibrium bond angle for ã-state CH₂⁺ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic state.     

Investigation of Brillouin effects in small-core holey optical fiber: lasing and scattering

We demonstrate for what is believed to be the first time a Brillouin laser based on a holey fiber (HF). Using a simple Fabry-Perot resonator scheme containing a 73.5-m-long highly nonlinear HF with an effective area of 2.85 microm(2) , we obtain a threshold of 125 mW and a slope efficiency of ~70% . Stimulated and spontaneous Brillouin scattering effects are investigated in the HF, and we show that the high lasing threshold is due mainly to reduction of the effective gain coefficient caused by structural nonuniformity along the fiber length.     

Greater than 20%-efficient frequency doubling of 1532-nm nanosecond pulses in quasi-phase-matched germanosilicate optical fibers

We fabricated second-order nonlinear gratings in D-shaped germanosilicate fibers, using thermal poling and periodic electrodes defined by standard photolithography. These gratings, which are up to 75 mm long, were used for efficient quasi-phase-matched frequency doubling of 1.532-mum nanosecond pulses from a high-power erbium-doped fiber amplifier. Average second-harmonic powers as high as 6.8 mW and peak powers greater than 1.2 kW at 766 nm were generated, with average and peak conversion efficiencies as high as 21% and 30%, respectively.     

Measurements of the HCN ν3 band broadened by N2

N₂-broadened halfwidths have been measured for 51 absorption lines belonging to the ν₃ fundamental band of hydrogen cyanide (¹H¹²C¹⁴N) near 3311 cm^?1. The data were recorded at room temperature using a Fourier transform spectrometer with a nominal resolution of 0.06 cm^?1. A nonlinear least-squares spectral-fitting procedure was used to obtain both line intensities and collision-broadened halfwidths from scans recorded at several different pressures. The N₂-broadened halfwidths, determined for all lines with J ≤ 25 in both the P and R branches of the band, show the expected distribution with J for broadening by a nonpolar gas. The halfwidth values range from approximately 0.17 cm^?1 atm^?1 near the band center to 0.11 cm^?1 atm^?1 for high-J lines. The band intensity for the ν₃ fundamental derived from these measurements is 236.2 ± 9.5 cm^?2 atm^?1 at 296 K, and empirical coefficients for the vibration-rotation interaction F-factor were also determined.     

The dynamics of ring rotation in ferrocene,nickelocene and ruthenocene by incoherent quadi-elastic neutron scattering

Incoherent quasi-elastic neutron scattering has been used to study the reorientational motions of the cyclopentadienyl rings in ferrocene, nickelocene and ruthenocene. The results for ferrocene show that the activation energy for ring rotation drops above the 164 K phase transition to 4.4 ± 0.5 kJ mol^?1 (which is approximately half its low temperature value) but the rings still appear to jump between only five orientations on the observable time scale. At room temperature, the rings in nickelocene appear to behave the same as in ferrocene but in ruthenocene they reorientate much less frequently and resemble those in ferrocene below 164 K.