Design,Synthesis, and Self-Assembly Studies of a Suite of Monodisperse,Facially Amphiphilic,Protein–Dendron Conjugates

The custom design of protein–dendron amphiphilic macromolecules is at the forefront of macromolecular engineering. Macromolecules with this architecture are very interesting because of their ability to self-assemble into various biomimetic nanoscopic structures. However, to date, there are no reports on this concept due to technical challenges associated with the chemical synthesis. Towards that end, herein, a new chemical methodology for the modular synthesis of a suite of monodisperse, facially amphiphilic, protein–dendron bioconjugates is reported. Benzyl ether dendrons of different generations (G1–G4) are coupled to monodisperse cetyl ethylene glycol to form macromolecular amphiphilic activity-based probes (AABPs) with a single protein reactive functionality. Micelle-assisted protein labeling technology is utilized for site-specific conjugation of macromolecular AABPs to globular proteins to make monodisperse, facially amphiphilic, protein–dendron bioconjugates. These biohybrid conjugates have the ability to self-assemble into supramolecular protein nanoassemblies. Self-assembly is primarily mediated by strong hydrophobic interactions of the benzyl ether dendron domain. The size, surface charge, and oligomeric state of protein nanoassemblies could be systematically tuned by choosing an appropriate dendron or protein of interest. This chemical method discloses a new way to custom-make monodisperse, facially amphiphilic, protein–dendron bioconjugates.     

Chemical synthesis and compositional analysis of mixed [Mo(S1 − x Se x )2] semiconductor thin films

The synthesis of binary MoS₂, MoSe₂ and mixed [Mo(S_{1 – x} Sex)₂] thin films onto a glass substrates using arrested precipitation technique (APT) is presented in this investigation. Growth kinetics and mechanism of film formation were studied for these films and are explained in brief. The stoichiometry of the film is confirmed by analyzing films using Extractive spectrophotometric (ESP), atomic absorption spectroscopic (AAS) and electron difftraction X-ray microanalysis (EDAX) techniques. The semiconductor solution containing Mo(VI) and Se(IV) is extracted with N-n-octylaniline in xylene and determined by ESP, AAS and EDAX techniques. Further these films are characterized for its semiconducting behavior to test the suitability of molybdenum chalcogenides as a photoelectrode to convert radiant energy into electricity. It is found that stoichiometry of the film formed by our recently developed arrested precipitation technique (APT) has strong influence on photoconduction in molybdenum chalcogenide photoelectrodes.     

An electrochemical impedance spectroscopy and scanning electron microscopy study of the influence of positive plate compression on the electrochemical behaviour of lead-acid batteries

This study has developed an electrochemical impedance spectroscopy (EIS) method for the in situ investigation of the influence of positive plate compression on the electrochemical behaviour of lead-acid batteries during charge/discharge cycling. The EIS data for a fully charged and fully discharged battery are internally consistent with the expected kinetics of a battery in the opposite states of charge, and demonstrate that EIS measurements may be recorded with a high level of reproducibility. Furthermore, this study has necessitated the development of a special cell incorporating horizontally orientated battery plates that can be subjected to elevated pressure through the stacking of lead bricks on top of the cell, as well as a physically robust reference electrode system that can withstand the application of pressure. For this purpose, a platinum-wire pseudo-reference electrode has been developed, and has been shown to exhibit sufficient electrode stability over the period of an EIS recording, enabling the measurement of reproducible and meaningful EIS data. Additionally, the influence of positive plate compression on the behaviour of the lead-acid battery has been investigated by using scanning electron microscopy (SEM). Clearly, the experimental data show that plate compression enhances significantly the kinetics and concomitant performance of the lead-acid battery, and this is related to the enhanced reactivity of the active material, as rationalized by using the agglomeration-of-spheres (AOS) model.     

Rare earth (RE) doped phosphors and their emerging applications: A review

The evolution of luminescent materials has witnessed rapid advancement in research and development. Solid inorganic light-emitting materials or phosphors are the optoelectronic material of the 21st century because of their power-efficient potential over various illumination sources, eco-friendliness and resourceful display perspectives. The inorganic phosphors have been extensively explored to meet the demand of low voltage stimulated lighting sources owing to increased global energy consumption. Due to environmental friendliness, advantages long lifetime, lower energy consumption, reliability and high luminous efficiency, modern white light-emitting diodes (WLEDs) have replaced less effective incandescent and mercury-enclosing conventional fluorescent lighting sources. This review highlights the developments in preparation, luminescence and potential perceptions of rare-earth activated phosphors for solid-state lighting technologies. The role of RE ions as an activator as well as a sensitizer in doped materials and possible transitions within their energy levels are reviewed in detail. The paper reviews the substantial influence of host lattices such as aluminate, oxide, phosphate, silicate, sulfide, etc on the optical transitions of doped RE ions. Studies on the advancement into the design of novel phosphors are very crucial as they will provide an opportunity to boom prospects in the course of promising applications. The sustainable energy facilities include clean technologies providing a cheaper lighting source which can produce significant indirect economic benefits via limiting the deforestation and use of scrubbing technology to mitigate air pollution.     

Efficient Host-Guest Complexation of a Bisporphyrin Host with Electron Deficient Guests: Synthesis,Structure, and Photoinduced Electron Transfer

The encapsulation of 1,8-naphthalic anhydride (NAN), 9-dicyanomethylenefluorene (9-DCF), acenaphthenequinone (ANQ), and 4-chloro-7-nitrobenzofurazan (NBD-Cl) by diethylpyrrole-bridged bisporphyrin (H₄DEP) and its dizinc(II) analogue (Zn₂DEP) are employed to investigate the structural and spectroscopic changes within the bisporphyrin cavity upon substrate binding. Synthesis and X-ray structures of all four encapsulated host-guest complexes (H₄DEP⋅NAN, H₄DEP⋅9-DCF, Zn₂DEP⋅ANQ, and Zn₂DEP⋅NBD-Cl) are reported here. The binding constant calculations show strong 1 : 1 binding between the hosts (H₄DEP and Zn₂DEP) and the guests (NAN/9-DCF/ANQ/NBD-Cl). ¹H-NMR spectra also support the retention of the host-guest assemblies in solution. Negative and positive shifts of the reduction and oxidation potentials, respectively, indicate that it is difficult to reduce/oxidize the encapsulated complexes. The emission intensities of the bisporphyrins (H₄DEP and Zn₂DEP) are substantially quenched in all the complexes, owing to photoinduced electron transfer from the excited state of the bisporphyrins to guest molecules. All the experimental evidence is further substantiated by DFT calculations. Such an efficient electron transfer is only possible when the donor and the acceptor moieties are in close propinquity to each other, which eventually lowers the reorganization energy.     

Investigation of Nd3+ incorporation in Ce-rhabdophane: Insight from structural flexibility and occupation mechanism

LnPO₄ · 0.667H₂O rhabdophane has been considered as a potential material for the precipitation of actinides from radioactive waste liquid, owing to its outstanding characteristics of high actinide bearing and easy synthesis in acid solutions. However, a comprehensive understanding of the actinide occupation and the precipitation response of rhabdophane to remove actinides has yet to be established. In this study, the effect of ions concentration and pH values on the detailed precipitation reaction of Ce_xNd_1-xPO₄ · 0.667H₂O rhabdophane in acid solutions are systematically investigated. Some specific issues such as structural distortion and flexibility, and occupation mechanism are discussed by combining with experiments and density functional theory (DFT) calculation. The results reveal that ions concentration and pH values have a significant impact on the crystallization nucleation step before 12 h. The obtained removal rate of Nd³⁺ is more than 99% in pH 1–5 solutions with the ions concentration of 0.05–0.1 mol/L. Moreover, incorporating Nd in CePO₄ · 0.667H₂O rhabdophane will easily result in the lattice distortion in b-axis. DFT calculation and X-ray photoelectron spectroscopy (XPS) results reveal that Nd is preferentially incorporated in nonhydrated site to form a weaker binding energy of NdO₈ polyhedron.