Self-assembling dicopper(II) complexes of di-2-pyridyl ketone Schiff base ligands derived from S-alkyldithiocarbazates

Condensation of di-2-pyridyl ketone with S-methyldithiocarbazate or S-benzyldithiocarbazate yields potentially bridging ligands of the form Py₂CNNHC(S)SR; Hdpksme (R = Me; the di-2-pyridyl ketone Schiff base of S-methyldithiocarbazate) and Hdpksbz (R = Bz; the di-2-pyridyl ketone Schiff base of S-benzyldithiocarbazate). Complexation of these ligands with Cu(II) in a 1:1 M ratio leads to the formation of dinuclear complexes of the general formula [Cu(NNNS)X]₂ (X = Cl⁻, NO₃⁻, H₂O). X-ray crystallographic structure determinations show that each ligand provides three donor atoms (NNS) in a meridional configuration to one metal, viz. one of the pyridine nitrogen atoms, the azomethine nitrogen atom and the thiolate sulfur, while the nitrogen atom of the second pyridyl group forms a bridge to another copper(II) ion within the dimer. The coordination geometry around each copper(II) ion is approximately square pyramidal, the basal plane of which is composed of one of the pyridine nitrogen atoms, the azomethine nitrogen atom and a chlorido, nitrato or aqua ligand. The apical position of the square pyramid is always occupied by the pyridine nitrogen atom of the second ligand.     

Hexagonal-to-cubic phase transformation in composite thin films induced by FePt nanoparticles located at PS/PEO interfaces

The organization process of asymmetric poly(styrene-block-ethylene oxide) (PS-b-PEO) copolymer thin films blended with FePt nanoparticles is studied. In a first step, it is shown that FePt nanoparticles stabilized by oleic acid ligands are distributed within the PS matrix phase, whereas the same particles partially covered with short dopamine-terminated-methoxy poly(ethylene oxide) (mPEO-Dopa) are located at PS/PEO interfaces. The swelling of PS domains, induced by FePt_oleic acid nanoparticles during the solvent annealing process, results in formation of a disordered microstructure in comparison to the well-organized hexagonally close-packed (HCP) cylinder phase formed in the neat PS-b-PEO copolymer. The evolution of the microstructure of PS-b-PEO/FePt_mPEO-Dopa composite has been investigated for different solvent annealing treatments. Under high-humidity conditions during the vapor annealing process, the addition of FePt nanoparticles results in formation of spheres in the film split into terraces. The upper and lower terraces are occupied by spheres organized in an unusual square and HCP phases, respectively. Under low-humidity conditions, undulated PEO cylinders oriented parallel to substrate are formed in the presence of FePt nanoparticles. In this case, we observe that most of the nanoparticles accumulate within the core of topological defects, which induces a low nanoparticle concentration at the PS/PEO interfaces and so stabilizes an intermediate undulated cylinder phase.     

Cross Psi(B)-energy operator-based signal detection

In this paper, two methods for signal detection and time-delay estimation based on the cross Psi(B)-energy operator are proposed. These methods are well suited for mono-component AM-FM signals. The Psi(B) energy operator measures how much one signal is present in another one. The peak of the Psi(B) operator corresponds to the maximum of interaction between the two signals. Compared to the cross-correlation function, the Psi(B) operator includes temporal information and relative changes of the signal which are reflected in its first and second derivatives. The discrete version of the continuous-time form of the Psi(B) operator, which is used in its implementation, is presented. The methods are illustrated on synthetic and real signals and the results compared to those of the matched filter and the cross correlation. The real signals correspond to impulse responses of buried objects obtained by active sonar in iso-speed single path environments.     

Measurement of the fundamental thermal noise limit in a cryogenic sapphire frequency standard using bimodal maser oscillations

We report observations of the Schawlow-Townes noise limit in a cryogenic sapphire secondary frequency standard. The effect causes a fundamental limit to the frequency stability, and was measured through the novel excitation of a bimodal maser oscillation of a Whispering Gallery doublet at 12.04 GHz. The beat frequency of 10 kHz between the oscillations enabled a sensitive probe for this measurement of fractional frequency instability of 10(-14) tau(-1/2) with only 0.5 pW of output power.     

Generation of an ultrabroadband supercontinuum in the mid-infrared region using dispersion-engineered GeAsSe photonic crystal fiber

An ultrabroadband mid-infrared (MIR) region supercontinuum (SC) is demonstrated numerically through dispersion-engineered traditional chalcogenide (ChG) photonic crystal fiber (PCF). By varying structural parameters pitch (hole to hole spacing) and air-hole diameter to pitch ratio, a number of 10-mm-long hexagonal PCFs made employing GeAsSe ChG glass as a core and air-holes of hexagonal lattice running through their lengths as a cladding are optimized to predict an efficient mid-infrared region SC spectral emission by pumping them using a tunable pump source between 2.9 and 3.3 µm. Simulations are carried out using an ultrashort pump pulse of 100-fs duration with a low pulse peak powers of between 3 and 4 kW into the optimized designs. It is found through numerical analysis that efficient SC spectral broadening with flattened output can be obtained by increasing the PCF pitch rather than increasing the PCF cladding containing air-hole diameter although a larger nonlinear coefficient could be obtained through increasing air-hole diameter of an optimized design. Simulation results show that the SC spectra can be broadened up to 12.2 µm for a certain design with a peak power of 3 kW. Using a peak power of 4 kW, it is possible to obtain SC spectral broadening beyond 14 µm with an optimized design spanning the wavelength range from 1.8 to 14 µm which covers the electromagnetic spectrum required for MIR molecular fingerprint region applications such as sensing and biological imaging.     

An Investigation into the PVA:MC:NH4Cl-Based Proton-Conducting Polymer-Blend Electrolytes for Electrochemical Double Layer Capacitor (EDLC) Device Application: The FTIR,Circuit Design and Electrochemical Studies

In this report, the preparation of solid polymer electrolytes (SPEs) is performed from polyvinyl alcohol, methyl cellulose (PVA-MC), and ammonium chloride (NH₄Cl) using solution casting methodology for its use in electrical double layer capacitors (EDLCs). The characterizations of the prepared electrolyte are conducted using a variety of techniques, including Fourier transform infrared spectroscopy (FTIR), electrical impedance spectroscopy (EIS), cyclic voltammetry (CV), and linear sweep voltammetry (LSV). The interaction between the polymers and NH₄Cl salt are assured via FTIR. EIS confirms the possibility of obtaining a reasonably high conductance of the electrolyte of 1.99 × 10⁻³ S/cm at room temperature. The dielectric response technique is applied to determine the extent of the ion dissociation of the NH₄Cl in the PVA-MC-NH₄Cl systems. The appearance of a peak in the imaginary part of the modulus study recognizes the contribution of chain dynamics and ion mobility. Transference number measurement (TNM) is specified and is found to be (t_ion) = 0.933 for the uppermost conducting sample. This verifies that ions are the predominant charge carriers. From the LSV study, 1.4 V are recorded for the relatively high-conducting sample. The CV curve response is far from the rectangular shape. The maximum specific capacitance of 20.6 F/g is recorded at 10 mV/s.     

XPS studies of Ni deposition on polymethyl methacrylate and poly(styrene‐co‐acrylonitrile)

Thin Ni layers were deposited onto clean polymethyl methacrylate (PMMA) and poly(styrene‐co‐acrylonitrile) (SAN) surfaces by a high vacuum thermal evaporation process. The resulting interfaces were studied by X‐ray photoelectron spectroscopy. The Ni deposition on PMMA changes the relative intensity of the C1s spectra associated with the O CO and C O carbon species, and modifies the shape of the O1s peak, while the Ni evaporation on SAN alters the C1s band intensity assigned to the CN moiety and gives a second N1s band at low binding energies. These observations suggest the formation of new chemical species at the interface between Ni and the PMMA ester group, and between Ni and the SAN nitrile group, which are the most reactive sites on these two polymers. Copyright © 2000 John Wiley & Sons, Ltd.     

Combinatorial Mapping of Surface Energy Effects on Diblock Copolymer Thin Film Ordering

Combinatorial gradient techniques are used to map the morphology dependence of thin symmetric diblock copolymer films on film thickness and substrate surface energy. An inversion from symmetric to anti‐symmetric lamellar morphology occurs with a progressive change in surface energy. An intermediate neutral region is found between these limiting types of ordering. The width ω of this transitional energy range scales as a power of copolymer mass M, ω ∝ M^1.9.

Optical photograph of a combinatorial map of the thin‐film block‐copolymer morphology on a film thickness and surface energy gradient. Island and holes on the surface scatter light causing the film to appear cloudy (lighter in color) in the areas where they exist. The darker areas do not have surface features and do not scatter light.     

Designing of Zn (II)-based novel coordination polymer (CP): Synthesis,characterization, and heavy metal removal from water

A new coordination polymer, Zn-(OC-AMAM-CO) CP, has been synthesized from Zn (II) as ionic node and 2,2′-((1,2-phenylenebis [azanediyl])bis (carbonyl))dibenzoic acid, (OC-AMAM-CO), as a new linker, where (OC-AMAM-CO) has been synthesized as an amide product through condensation reaction of phthalic acid and o-phenylenediamine. The amide product (OC-AMAM-CO) and Zn-(OC-AMAM-CO) CP were characterized via FTIR and PXRD analyses, and Zn-(OC-AMAM-CO) CP was further characterized via SEM/EDX and XPS analyses. Moreover, DFT study was performed to shed light on the both structures of (OC-AMAM-CO) and Zn-(OC-AMAM-CO). PXRD analysis revealed the successful syntheses of the new linker (OC-AMAM-CO) and Zn-(OC-AMAM-CO) CP where the new CP is crystalline. DFT study revealed that the 3D topological structure assembled through coordination, π–π stacking, and hydrogen bonding. Zn-(OC-AMAM-CO) CP was applied as an adsorbent for the removal of Cu (II) from water as it has abundant chelating groups that serve as adsorptive coordinating sites. Isotherm study revealed the obedience of Cu (II)/Zn-(OC-AMAM-CO) CP adsorption system to Langmuir modeling with adsorption capacity of about 55 mg/g. A kinetic study showed that the rate of adsorption was a pseudo-first-order type. Further, adsorption process was found to be strongly diffusion dependent.