Quick quality assessment of fluid (liquid and gas) is a key requirement for many industries. Acoustic parameters like sound speed in fluid or sound attenuation in fluid can serve as a crucial marker for assessing fluid quality as any deviation of those parameters points to adulteration or degradation of the fluid. Swept Frequency Acoustic Interferometry (SFAI) is a well-known noninvasive technique for taking measurements of fluid's acoustic parameters (e.
View Article and Find Full Text PDFAnnu Int Conf IEEE Eng Med Biol Soc
July 2022
The need for everyday-real-time EEG sensing has resulted in the development of minimalistic and discreet wearable EEG measuring devices. A front runner in this race is in-ear worn device. However, the position of the ear as well as its restricted accessibility poses certain challenges in the design of such devices - from the type of materials used to the placement of electrodes.
View Article and Find Full Text PDFThe mechanism governing the redox-stimulated switching behavior of a tristable [2]rotaxane consisting of a cyclobis(paraquat-p-phenylene) (CBPQT(4+)) ring encircling a dumbbell, containing tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) recognition units which are separated from each other along a polyether chain carrying 2,6-diisopropylphenyl stoppers by a 4,4'-bipyridinium (BIPY(2+)) unit, is described. The BIPY(2+) unit acts to increase the lifetime of the metastable state coconformation (MSCC) significantly by restricting the shuttling motion of the CBPQT(4+) ring to such an extent that the MSCC can be isolated in the solid state and is stable for weeks on end. As controls, the redox-induced mechanism of switching of two bistable [2]rotaxanes and one bistable [2]catenane composed of CBPQT(4+) rings encircling dumbbells or macrocyclic polyethers, respectively, that contain a BIPY(2+) unit with either a TTF or DNP unit, is investigated.
View Article and Find Full Text PDFCharged donor-acceptor [2]catenanes containing cyclobis(paraquat-p-phenylene) as the ring component can be synthesised in yields of up to 88% in under one hour by heating two precursors in the presence of macrocyclic polyether templates in N,N-dimethylformamide at 80 °C.
View Article and Find Full Text PDFThe ability to control the kinetic barriers governing the relative motions of the components in mechanically interlocked molecules is important for future applications of these compounds in molecular electronic devices. In this Full Paper, we demonstrate that bipyridinium (BIPY(2+)) dications fulfill the role as effective electrostatic barriers for controlling the shuttling and threading behavior for rotaxanes and pseudorotaxanes in aqueous environments. A degenerate [2]rotaxane, composed of two 1,5-dioxynaphthalene (DNP) units flanking a central BIPY(2+) unit in the dumbbell component and encircled by the cyclobis(paraquat-p-phenylene) (CBPQT(4+)) tetracationic cyclophane, has been synthesized employing a threading-followed-by-stoppering approach.
View Article and Find Full Text PDFFive donor-acceptor oligorotaxanes made up of dumbbells composed of tetraethylene glycol chains, interspersed with three and five 1,5-dioxynaphthalene units, and terminated by 2,6-diisopropylphenoxy stoppers, have been prepared by the threading of discrete numbers of cyclobis(paraquat-p-phenylene) rings, followed by a kinetically controlled stoppering protocol that relies on click chemistry. The well-known copper(I)-catalyzed alkyne-azide cycloaddition between azide functions placed at the ends of the polyether chains and alkyne-bearing stopper precursors was employed during the final kinetically controlled template-directed synthesis of the five oligorotaxanes, which were characterized subsequently by (1)H NMR spectroscopy at low temperature (233 K) in deuterated acetonitrile. The secondary structures, as well as the conformations, of the five oligorotaxanes were unraveled by spectroscopic comparison with the dumbbell and ring components.
View Article and Find Full Text PDFA subset of mechanically interlocked molecules, namely, donor-acceptor [2]catenanes, have been produced in aqueous solutions in good yields from readily available precursors. The catenations are templated by strong hydrophobic and [π···π] stacking interactions, which serve to assemble the corresponding supramolecular precursors, prior to postassembly covalent modification. Dynamic (1)H NMR spectroscopic investigations performed on one of these [2]catenanes reveal that the pirouetting motion of the butadiyne-triethylene glycol chain occurs with a dramatically lower activation enthalpy, yet with a much higher negative activation entropy in water, compared to organic solvents.
View Article and Find Full Text PDFThe template-directed synthesis of a bistable donor-acceptor [2]catenane wherein both translational isomers--one in which a tetrathiafulvalene unit in a mechanically interlocked crown ether occupies the cavity of a cyclobis(paraquat-p-phenylene) ring and the other in which a 1,5-dioxynaphthalene unit in the crown ether resides inside the cavity of the tetracationic cyclophane--exist in equilibrium in solution, has led to the isolation and separation by hand picking of single crystals colored red and green, respectively. These two crystalline co-conformations have been characterized separately at both the molecular and supramolecular levels, and also by dynamic NMR spectroscopy in solution where there is compelling evidence that the mechanically interlocked molecules are present as a complex mixture of translational, configurational, and conformational isomers wherein the isomerization is best described as being a highly dynamic and adaptable phenomenon.
View Article and Find Full Text PDFA strategy towards increasing the lifetime of the metastable state of a [2]rotaxane incorporating tetrathiafulvalene, 1,5-dioxynaphthalene and bipyridinium (BIPY(2+)) is presented. Incorporation of BIPY(2+) served multiple roles as an electrostatic barrier to relaxation, a supramolecular recognition site for bis-1,5-dioxynaphthalene[38]crown-10 macrocycle, and upon reduction a recognition site for the mechanically bonded cyclobis(paraquat-p-phenylene) ring.
View Article and Find Full Text PDFCyclocondensations of aromatic diamines with 1,1'-bis(2,4-dinitrophenyl)-4,4'-bipyridinium salts afford doubly or quadruply charged, macrocyclic, N,N'-diarylbipyridinium cations. These are tolerant of a wide range of acids, bases, and nucleophiles, although they appear to undergo reversible, one-electron reduction by tertiary amines. Single-crystal X-ray analysis demonstrates the presence of a macrocycle conformation in which the 4,4'-bipyridinium and 4,4'-biphenylenedisulfonyl residues are suitably spaced and aligned for complexation with pi-donor arenes, and NMR studies in solution indeed confirm binding to 1,5-bis[hydroxy(ethoxy)ethoxy]naphthalene.
View Article and Find Full Text PDFAmphiphilic homopolymers containing a hydrophilic and a hydrophobic functionality in each monomer unit have been shown to form polar or apolar containers depending on the solvent environment. When presented with a mixture of solvents, these polymeric containers are capable of releasing certain guest molecules. The fundamental mechanism behind these properties is investigated, and the utility of these assemblies in separations has been demonstrated with an example.
View Article and Find Full Text PDFAmphiphilic dendrimers with a custom-designed biaryl repeat unit have been synthesized. These dendrimers afford hydrophobic nanocontainers in polar solvents and hydrophilic nanocontainers in apolar solvents. These container properties were investigated using dye incorporation studies.
View Article and Find Full Text PDFStimuli-responsive polymers and assemblies are viable candidates for the so-called "smart" materials. In this communication, we report a new class of amphiphilic homopolymers that forms micelle-like structures in polar solvents and inverted micelle-like structures in apolar solvents. We demonstrate that these superstructures are the result of the changes in the molecular-level conformations in the monomer.
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