Intramolecular locking and coumarin insertion: a stepwise approach for TADF design

Three novel TADF (thermally activated delayed fluorescence) emitters based on the well-studied Qx-Ph-DMAC fluorophore are designed and synthesized. The photophysical properties of these materials are studied from a theoretical and experimental point of view, demonstrating the cumulative effects of multiple small modifications that combine to afford significantly improved TADF performance. First, an extra phenyl ring is added to the acceptor part of Qx-Ph-DMAC to increase the conjugation length, resulting in BQx-Ph-DMAC, which acts as an intermediate molecular structure. Next, an electron-deficient coumarin unit is incorporated to fortify the electron accepting ability, affording ChromPy-Ph-DMAC with red-shifted emission. Finally, the conjugated system is further enlarged by ‘locking’ the molecular structure, generating DBChromQx-DMAC with further red-shifted emission. The addition of the coumarin unit significantly impacts the charge-transfer excited state energy levels with little effect on the locally excited states, resulting in a decrease of the singlet–triplet energy gap. As a result, the two coumarin-based emitters show considerably improved TADF performance in 1 w/w% zeonex films when compared to the initial Qx-Ph-DMAC structure. ‘Locking’ the molecular structure further lowers the singlet–triplet energy gap, resulting in more efficient reverse intersystem crossing and increasing the contribution of TADF to the total emission

New Results on the SymSum Distinguisher on Round-Reduced SHA3

In ToSC 2017 Saha et al. demonstrated an interesting property of SHA3 based on higher-order vectorial derivatives which led to self-symmetry based distinguishers referred to as SymSum and bettered the complexity w.r.t the well-studied ZeroSum distinguisher by a factor of 4. This work attempts to take a fresh look at this distinguisher in the light of the linearization technique developed by Guo et al. in Asiacrypt 2016. It is observed that the efficiency of SymSum against ZeroSum drops from 4 to 2 for any number of rounds linearized. This is supported by theoretical proofs. SymSum augmented with linearization can penetrate up to two more rounds as against the classical version. In addition to that, one more round is extended by inversion technique on the final hash values. The combined approach leads to distinguishers up to 9 rounds of SHA3 variants with a complexity of only 264 which is better than the equivalent ZeroSum distinguisher by the factor of 2. To the best of our knowledge this is the best distinguisher available on this many rounds of SHA3

On-demand fuzzy clustering and ant-colony optimisation based mobile data collection in wireless sensor network

In a wireless sensor network (WSN), sensor nodes collect data from the environment and transfer this data to an end user through multi-hop communication. This results in high energy dissipation of the devices. Thus, balancing of energy consumption is a major concern in such kind of network. Appropriate cluster head (CH) selection may provide to be an efficient way to reduce the energy dissipation and prolonging the network lifetime in WSN. This paper has adopted the concept of fuzzy if-then rules to choose the cluster head based on certain fuzzy descriptors. To optimise the fuzzy membership functions, Particle Swarm Optimisation (PSO) has been used to improve their ranges. Moreover, recent study has confirmed that the introduction of a mobile collector in a network which collects data through short-range communications also aids in high energy conservation. In this work, the network is divided into clusters and a mobile collector starts from the static sink or base station and moves through each of these clusters and collect data from the chosen cluster heads in a single-hop fashion. Mobility based on Ant-Colony Optimisation (ACO) has already proven to be an efficient method which is utilised in this work. Additionally, instead of performing clustering in every round, CH is selected on demand. The performance of the proposed algorithm has been compared with some existing clustering algorithms. Simulation results show that the proposed protocol is more energy-efficient and provides better packet delivery ratio as compared to the existing protocols for data collection obtained through Matlab Simulations

Graphene Oxide-Gallic Acid Nanodelivery System for Cancer Therapy

Despite the technological advancement in the biomedical science, cancer remains a life-threatening disease. In this study, we designed an anticancer nanodelivery system using graphene oxide (GO) as nanocarrier for an active anticancer agent gallic acid (GA). The successful formation nanocomposite (GOGA) was characterized using XRD, FTIR, HRTEM, Raman, and UV/Vis spectroscopy. The release study shows that the release of GA from the designed anticancer nanocomposite (GOGA) occurs in a sustained manner in phosphate-buffered saline (PBS) solution at pH 7.4. In in vitro biological studies, normal fibroblast (3T3) and liver cancer cells (HepG2) were treated with different concentrations of GO, GOGA, and GA for 72 h. The GOGA nanocomposite showed the inhibitory effect to cancer cell growth without affecting normal cell growth. The results of this research are highly encouraging to go further for in vivo studies

Mechanical enhancement of UHMWPE fibers by coating with carbon nanoparticles

Fiber-reinforced plastic (FRP) is composed of reinforced fibers and matrix resin, and has high specific strength and low-density materials. Because of the orientation of the fibers within them, FRPs are prone to buckling damage when under compression along the axial direction of the fiber, especially flexible organic ones. The compressive performance of FRP is largely dependent on fiber properties. the buckling load of FRP will increase with the increasing of fiber's. In this study, we developed a way to improve the compressive and bending strength of ultra-high molecular weight polyethylene (UHMWPE) fibers. Carbon nanotubes (CNTs) and vapor-grown carbon fibers (VGCFs) were coated on the surface of UHMWPE fibers by pyrrole vapor deposition. The transverse compressive strength and bending strength of single UHMWPE fibers were determined by microcompression and single fiber bending measurements, respectively. The experiment result showed that coating UHMWPE fibers with CNTs and VGCFs increased both their transverse compressive strength and bending strength. It is excepted that the improved fiber would applied in FRP for better compressive performance.ArticleFIBERS AND POLYMERS. 15(4):723-728 (2014)journal articl

Engineering the Redox Potential over a Wide Range within a New Class of FeS Proteins

Abstract: MitoNEET is a newly discovered mitochondrial protein and a target of the TZD class of antidiabetes drugs. MitoNEET is homodimeric with each protomer binding a [2Fe-2S] center through a rare 3-Cys and 1-His coordination geometry. Both the fold and the coordination of the [2Fe-2S] centers suggest that it could have novel properties compared to other known [2Fe-2S] proteins. We tested the robustness of mitoNEET to mutation and the range over which the redox potential (EM) could be tuned. We found that the protein could tolerate an array of mutations that modified the EM of the [2Fe-2S] center over a range of ∼700 mV, which is the largest EM range engineered in an FeS protein and, importantly, spans the cellular redox range (+200 to-300 mV). These properties make mitoNEET potentially useful for both physiological studies and industrial applications as a stable, water-soluble, redox agent

Reorganization Energy for Internal Electron Transfer in Multicopper Oxidases.

We have calculated the reorganization energy for the intramolecular electron transfer between the reduced type 1 copper site and the peroxy intermediate of the trinuclear cluster in the multicopper oxidase CueO. The calculations are performed at the combined quantum mechanics and molecular mechanics (QM/MM) level, based on molecular dynamics simulations with tailored potentials for the two copper sites. We obtain a reorganization energy of 91-133 kJ/mol, depending on the theoretical treatment. The two Cu sites contribute by 12 and 22 kJ/mol to this energy, whereas the solvent contribution is 34 kJ/mol. The rest comes from the protein, involving small contributions from many residues. We have also estimated the energy difference between the two electron-transfer states and show that the reduction of the peroxy intermediate is exergonic by 43-87 kJ/mol, depending on the theoretical method. Both the solvent and the protein contribute to this energy difference, especially charged residues close to the two Cu sites. We compare these estimates with energies obtained from QM/MM optimizations and QM calculations in a vacuum and discuss differences between the results obtained at various levels of theory

Structural studies of thermally stable, combustion-resistant polymer composites

Composites of the industrially important polymer, poly(methyl methacrylate) (PMMA), were prepared by free-radical polymerization of MMA with varying amounts (1–30 wt. %) of sodium dioctylsulfosuccinate (Aerosol OT or AOT) surfactant added to the reaction mixture. The composites with AOT incorporated show enhanced resistance to thermal degradation compared to pure PMMA homopolymer, and micro-cone combustion calorimetry measurements also show that the composites are combustion-resistant. The physical properties of the polymers, particularly at low concentrations of surfactant, are not significantly modified by the incorporation of AOT, whereas the degradation is modified considerably for even the smallest concentration of AOT (1 wt. %). Structural analyses over very different lengthscales were performed. X-ray scattering was used to determine nm-scale structure, and scanning electron microscopy was used to determine μm-scale structure. Two self-assembled species were observed: large phase-separated regions of AOT using electron microscopy and regions of hexagonally packed rods of AOT using X-ray scattering. Therefore, the combustion resistance is observed whenever AOT self-assembles. These results demonstrate a promising method of physically incorporating a small organic molecule to obtain a highly thermally stable and combustion-resistant material without significantly changing the properties of the polymer