Interaction between the end groups and the main chain of conjugated polymers by time-resolved EPR and fluorescence spectroscopy

ABSTRACT

Interaction between a zinc porphyrin (ZnPor) as the end-group and poly(9,9-di-n-octylfluorene-2,7-vinylene) (PFV) as the main chain in a porphyrin end-modified fluorescent conjugated polymer, ZnPFV, was studied by time-resolved electron paramagnetic resonance (EPR) and fluorescence spectroscopy. While fluorescence from the PFV part of ZnPFV showed a spectral profile almost identical to that of a PFV oligomer without end-modification, the emission spectrum of the ZnPor part exhibited a much broader profile compared to that of the reference zinc porphyrin monomer. Based on the analysis of lifetimes and quantum yields, it was found that radiative rate constant of the ZnPor part was enhanced by nearly three times. The observed unusual enhancement in the radiative rate constant was rationalised in terms of a partial π-conjugation between the end group and the main chain, as a result of co-planarisation in fluid solution. On the other hand, the time-resolved EPR spectrum of ZnPFV at 100?K basically showed a similar spectral pattern to that of the reference zinc porphyrin, but with significant differences in zero-field spitting parameters and initial population ratios. The π-system of the excited triplet state is deduced to deviate from D_4h symmetry in the end zinc porphyrin groups. The obtained results show that interaction of the porphyrin end group with the main chain of the polymer significantly influences the excited singlet state properties of the porphyrin, while its triplet state properties were affected to a lesser extent.     

Two new aromadendrane sesquiterpenes from Verticillium psalliotae

The chemical constituents of the fungus Verticillium psalliotae were studied. Two new aromadendrane sesquiterpenes inonotin M (1) and inonotin N (2) were isolated from the EtOAc extract of the fungal culture broth. The structures of compounds were elucidated mainly by HRESIMS experiments, and 1D, 2D-NMR spectroscopy analysis.     

DNA interaction,cytotoxicity and molecular structure of cobalt complex of 4‐amino‐N‐(6‐chloropyridazin‐3‐yl)benzene sulfonamide in the presence of secondary ligand pyridine

Novel cobalt complex of 4‐amino‐N‐(6‐chloropyridazin‐3‐yl)benzene sulfonamide (sulfachloropyridazine) has been synthesized and characterized by elemental analysis, FT‐IR spectroscopy and magnetic susceptibility (VSM). Cobalt complex of Sulfachloropyridazine (Co‐SCP) crystallized in monoclinic space group P2₁/n with Z = 4. The structure is solved by direct method and refined to R = 0.099 for 4720 reflections with I ?4σ(I). The results of FT‐IR spectra suggest the binding of cobalt atom to the sulfonamide ligand which is in agreement with the crystal structure determination. In crystal structure, molecule is linked via, C‐H … π, C‐Cl … π and π … π intermolecular interactions. The computational studies like the optimization energy and root means square deviation compare with single crystal structure, frontier molecular orbital (Homo‐Lumo energy) and binding energy of the Co‐SCP has been carried out using DFT/B3LYP level of theory in gaseous phase. Hirshfeld surfaces and the 2D‐fingerprint analysis are performed to study the nature of interactions and their measurable contributions towards crystal packing. The interaction of the complex with DNA is investigated using viscosity measurement and absorption titration studies. The result shows the complex bind to DNA with intercalative mode with high DNA‐binding constant (K_b). Also, in vivo and in vitro cytotoxic studies are performed using S. pombe cells and brine shrimp lethality bioassay. DNA‐cleavage study shows better cleaving ability of the complex.     

Growth and characterization of two-dimensional crystals for communication and energy applications

This review article covers the growth and characterization of two-dimensional (2D) crystals of transition metal chalcogenides, h-BN, graphene, etc. The chemical vapor transport method for bulk single crystal growth is discussed in detail. Top-down methods like mechanical and liquid exfoliation and bottom-up methods like chemical vapor deposition and molecular beam epitaxy for mono/few-layer growth are described. The optimal characterization techniques such as optical, atomic force, scanning electron, and Raman spectroscopy for identification of mono/few-layer(s) of the 2D crystals are discussed. In addition, a survey was done for the application of 2D crystals for both creation and deterministic transfer of single-photon sources and photovoltaic systems. Finally, the application of plasmonic nanoantenna was proposed for enhanced solar-to-electrical energy conversion and faster/brighter quantum communication devices.     

A New Approach for the Synthesis of Miktoarm Star Polymers Through a Combination of Thiol–Epoxy “Click” Chemistry and ATRP/Ring‐Opening Polymerization Techniques

A new approach was developed for synthesis of certain A₃B₃‐type of double hydrophilic or amphiphilic miktoarm star polymers using a combination of “grafting onto” and “grafting from” methods. To achieve the synthesis of desired miktoarm star polymers, acetyl protected poly(ethylene glycol) (PEG) thiols (M_n = 550 and 2000 g mol^?1) were utilized to generate A₃‐type of homoarm star polymers through an in situ protective group removal and a subsequent thiol–epoxy “click” reaction with a tris‐epoxide core viz. 1,1,1‐tris(4‐hydroxyphenyl)ethane triglycidyl ether. The secondary hydroxyl groups generated adjacent to the core upon the thiol–epoxy reaction were esterified with α‐bromoisobutyryl bromide to install atom transfer radical polymerization (ATRP) initiating sites. ATRP of N‐isopropylacrylamide (NIPAM) using the three‐arm star PEG polymer fitted with ATRP initiating sites adjacent to the core afforded A₃B₃‐type of double hydrophilic (PEG)₃[poly(N‐isopropylacrylamide)] (PNIPAM)₃ miktoarm star polymers. Furthermore, the generated hydroxyl groups were directly used as initiator for ring‐opening polymerization of ε‐caprolactone to prepare A₃B₃‐type of amphiphilic (PEG)₃[poly(ε‐caprolactone)]₃ miktoarm star polymers. The double hydrophilic (PEG)₃(PNIPAM)₃ miktoarm star polymers showed lower critical solution temperature around 34 °C. The preliminary transmission electron microscopy analysis indicated formation of self‐assembly of (PEG)₃(PNIPAM)₃ miktoarm star polymer in aqueous solution. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 146–156     

Validation of quartz crystal rheometry in the megahertz frequency regime

The utility of the quartz crystal microbalance (QCM) as a high‐frequency rheometer operating at 15 MHz was demonstrated. High‐frequency data obtained from a series of rubbery materials were compared with results obtained from traditional dynamic mechanical analysis (DMA) at much lower frequencies. The high‐frequency data enable meaningful shift factors to be obtained at temperatures much further above glass‐transition temperature (T _g) than would otherwise be possible, giving a more complete picture of the temperature dependence of the viscoelastic properties. The QCM can also be used to quantify mass uptake and changes in viscoelastic properties during sample oxidation. The viscoelastic response spanning the full range of behaviors from the rubber to glassy regimes was found to fit well with a six‐element model consisting of three power‐law springpot elements. One of these elements is particularly sensitive to the behavior in the transition regime where the phase angle is maximized. The value of this quantity is obtained from the maximum phase angle, which can be obtained from a temperature sweep at fixed frequency, proving a means for more detailed frequency‐dependent rheometric information to be obtained from a fixed‐frequency measurement at a range of temperatures. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1246–1254     

The spectral analysis and exponential stability of a bi‐directional coupled wave‐ODE system

In this paper, an unstable linear time invariant (LTI) ODE system is stabilized exponentially by the PDE compensato—a wave equation with Kelvin‐Voigt (K‐V) damping. Direct feedback connections between the ODE system and wave equation are established: The velocity of the wave equation enters the ODE through the variable v_t(1,t); meanwhile, the output of the ODE is fluxed into the wave equation. It is found that the spectrum of the system operator is composed of two parts: point spectrum and continuous spectrum. The continuous spectrum consists of an isolated point , and there are two branches of asymptotic eigenvalues: the first branch approaches to , and the other branch tends to ?∞. It is shown that there is a sequence of generalized eigenfunctions, which forms a Riesz basis for the Hilbert state space. As a consequence, the spectrum‐determined growth condition and exponential stability of the system are concluded.