Carbohydrate chips for studying high-throughput carbohydrate-protein interactions

Carbohydrate-protein interactions play important biological roles in living organisms. For the most part, biophysical and biochemical methods have been used for studying these biomolecular interactions. Less attention has been given to the development of high-throughput methods to elucidate recognition events between carbohydrates and proteins. In the current effort to develop a novel high-throughput tool for monitoring carbohydrate-protein interactions, we prepared carbohydrate microarrays by immobilizing maleimide-linked carbohydrates on thiol-derivatized glass slides and carried out lectin binding experiments by using these microarrays. The results showed that carbohydrates with different structural features selectively bound to the corresponding lectins with relative binding affinities that correlated with those obtained from solution-based assays. In addition, binding affinities of lectins to carbohydrates were also quantitatively analyzed by determining IC(50) values of soluble carbohydrates with the carbohydrate microarrays. To fabricate carbohydrate chips that contained more diverse carbohydrate probes, solution-phase parallel and enzymatic glycosylations were performed. Three model disaccharides were in parallel synthesized in solution-phase and used as carbohydrate probes for the fabrication of carbohydrate chips. Three enzymatic glycosylations on glass slides were consecutively performed to generate carbohydrate microarrays that contained the complex oligosaccharide, sialyl Le(x). Overall, these works demonstrated that carbohydrate chips could be efficiently prepared by covalent immobilization of maleimide-linked carbohydrates on the thiol-coated glass slides and applied for the high-throughput analyses of carbohydrate-protein interactions.     

Chiral polymer hosts for circularly polarized electroluminescence devices

Polymer electroluminescence devices producing circularly polarized luminescence (CP PLEDs) have valuable photonic applications. The fabrication of a CP PLED requires a polymer host that provides the appropriate chiral environment around the emitting dopant. However, chemical strategies for the design of chiral polymer hosts remain underdeveloped. We have developed new polymer hosts for CP PLED applications. These polymers were prepared through a free-radical polymerization of 3-vinylcarbazole with a chiral N-alkyl unit. This chiral unit forces the carbazole repeat units to form mutually helical half-sandwich conformers with preferred (P)-helical sense along the polymer main chain. Electronic circular dichroism measurements demonstrate the occurrence of chirality transfer from chiral monomers to achiral monomers during chain growth. The (P)-helical-sense-enriched polymer interacts diastereoselectively with an enantiomeric pair of new phosphorescent (R)- and (S)-dopants. The magnitude of the Kuhn dissymmetry factor (g_abs) for the (P)-helically-enriched polymer film doped with the (R)-dopant was found to be one order of magnitude higher than that of the film doped with the (S)-dopant. Photoluminescence dissymmetry factors (g_PL) of the order of 10⁻³ were recorded for the doped films, but the magnitude of diastereomeric enhancement decreased to that of g_abs. The chiral polymer host permits faster energy transfer to the phosphorescent dopants than the achiral polymer host. Our photophysical and morphological investigations indicate that the acceleration in the chiral polymer host is due to its longer Förster radius and improved compatibility with the dopants. Finally, multilayer CP PLEDs were fabricated and evaluated. Devices based on the chiral polymer host with the (R)- and (S)-dopants exhibit electroluminescence dissymmetry factors (g_EL) of 1.09 × 10⁻⁴ and −1.02 × 10⁻⁴ at a wavelength of 540 nm, respectively. Although challenges remain in the development of polymer hosts for CP PLEDs, our research demonstrates that chiroptical performances can be amplified by using chiral polymer hosts.

Polymer electroluminescence devices producing circularly polarized luminescence (CP PLEDs) have valuable photonic applications.     

Multi-stacked organic light-emitting diodes using zinc oxide nanoparticle interfacial layers

Stacked organic light-emitting diodes (SOLEDs) with 30-nm nanoparticle (NP) interfacial layers were investigated. Zinc oxide (ZnO) was used as an interfacial layer between two green polymer (GP) layers. SOLEDs with NP interfacial layers had higher device efficiency than did a single-unit device due to the high probability of exciton recombination that originated from the Auger electron-assisted energy up-conversion process. Although the current density and luminance of SOLEDs with ZnO NP interfacial layers were smaller than those of the reference device, the efficiency was doubled because of the big band alignment difference and the large band gap between GP and ZnO NP interfacial layers, which induced more radiative-exciton recombination.     

Recyclable gold nanoparticle catalyst for the aerobic alcohol oxidation and C-C bond forming reaction between primary alcohols and ketones under ambient conditions

A recyclable gold catalyst is synthesized from readily available reagents by immobilizing gold nanoparticles in aluminum oxyhydroxide support through a simple sol-gel method. The catalyst showed the high activity even at room temperature in the aerobic oxidation of various alcohols and in the coupling reaction between primary alcohols and ketones.     

Protein ubiquitination and formation of polyubiquitin chains without ATP,E1 and E2 enzymes

Studying protein ubiquitination is difficult due to the complexity of the E1–E2–E3 ubiquitination cascade. Here we report the discovery that C-terminal ubiquitin thioesters can undergo direct transthiolation with the catalytic cysteine of the model HECT E3 ubiquitin ligase Rsp5 to form a catalytically active Rsp5∼ubiquitin thioester (Rsp5∼Ub). The resulting Rsp5∼Ub undergoes efficient autoubiquitination, ubiquitinates protein substrates, and synthesizes polyubiquitin chains with native Ub isopeptide linkage specificity. Since the developed chemical system bypasses the need for ATP, E1 and E2 enzymes while maintaining the native HECT E3 mechanism, we named it “Bypassing System” (ByS). Importantly, ByS provides direct evidence that E2 enzymes are dispensable for K63 specific isopeptide bond formation between ubiquitin molecules by Rsp5 in vitro. Additionally, six other E3 enzymes including Nedd4-1, Nedd4-2, Itch, and Wwp1 HECT ligases, along with Parkin and HHARI RBR ligases processed Ub thioesters under ByS reaction conditions. These findings provide general mechanistic insights on protein ubiquitination, and offer new strategies for assay development to discover pharmacological modulators of E3 enzymes.     

Nanoimprinted substrates for high-yield production of topological insulator nanoribbons

We present a growth process mediated by nanoimprinted nanostructures specifically for producing bismuth selenide (Bi₂Se₃) topological insulator nanoribbons with a high yield. In this process, topological insulator nanostructures are grown on nanoimprinted gratings by using a nanoparticle-catalyzed vapor–liquid–solid mechanism. In comparison with the growth processes performed on flat and randomly rough substrates, such a nanograting-mediated growth method produces topological insulator nanoribbons with a higher yield (～15?000 nanoribbons/mm²), a narrower average ribbon width (w _avg<60 nm), and a higher uniformity in ribbon width (σ<30 nm); effectively suppresses the formation of other unwanted morphologies; and also results in the axial growth of nanoribbons along specific in-plane directions relative to pre-structured gratings. Such technical merits of nanograting-mediated growth are attributed to the preferential nucleation of Bi₂Se₃ crystal seeds and the concomitant pinning of catalytic nanoparticles at ordered grating edges. Finally, Aharonov–Bohm interference oscillations in the magnetoresistance were observed and demonstrated the coherent transport of electrons through topological surface states of Bi₂Se₃ nanoribbons. This growth process in combination with large-area nanoimprint lithography could serve as an important foundation for nanomanufacturing topological insulator nanoribbons with controllable feature size, large-area uniformity, and ordering, suitable for applications in future low-dissipation nanoelectronics.     

The average number of divisors of the Euler function

The upper bound and the lower bound of the average number of divisors of Euler Phi function and Carmichael Lambda function were obtained by Luca and Pomerance (see Publ Math Debr 70(1–2):125–148, 2007). We improve the lower bound and provide a heuristic argument which suggests that the upper bound given by Luca and Pomerance (Publ Math Debr 70(1–2):125–148, 2007) is indeed close to the truth.     

Seeded Ising Model and Distributed Biometric Template Storage and Matching

It is known that a variant of Ising model, called Seeded Ising Model, can be used to recover the information content of a biometric template from a fraction of information therein. The method consists in reconstructing the whole template, which is called the intruder template in this paper, using only a small portion of the given template, a partial template. This reconstruction method may pose a security threat to the integrity of a biometric identity management system. In this paper, based on the Seeded Ising Model, we present a systematic analysis of the possible security breach and its probability of accepting the intruder templates as genuine. Detailed statistical experiments on the intruder match rate are also conducted under various scenarios. In particular, we study (1) how best a template is divided into several small pieces called partial templates, each of which is to be stored in a separate silo; (2) how to do the matching by comparing partial templates in the locked-up silos, and letting only the results of these intra-silo comparisons be sent to the central tallying server for final scoring without requiring the whole templates in one location at any time.     

Low-Frequency Relaxation Oscillations in Capacitive Discharge Processes

Low-frequency （2.72-3.70 Hz） relaxation oscillations at 100 mTorr at higher absorbed power were observed from time-varying optical emission of the main discharge chamber and the periphery. We interpret the low frequency oscillations using an electromagnetic model of the slot impedance with parallel connection variational peripheral capacitance, coupled to a circuit analysis of the system including the matching network. The model results are in general agreement with the experimental observations, and indicate a variety of behaviours dependent on the matching conditions.