A bis-propargyl-appended rhodamine B-based receptor BPRB has been synthesised that exhibits pronounced fluorescence enhancement in the presence of Pd2+ ions. The addition of Pd2+ enhanced the fluorescence intensity of BPRB by 113-fold (Φf = 0.37) and BPRB was found to exhibit high selectivity towards Pd2+ compared to a range of other metal ions. The enhancement of fluorescence was triggered by spirolactam ring opening followed by depropargylation of BPRB in the presence of Pd2+, as evidenced by FTIR and NMR analyses. BPRB was able to detect Pd0 without the addition of a reducing agent, and the emission intensity of BPRB–Pd0 was almost identical to that of BPRB–Pd2+; however, a rapid fluorescence response was observed in the presence of PPh3. To explore the efficiency of the rhodamine unit, a bispropargyl derivative of cyclohexane (BPCH) was synthesised and the fluorescence response towards Pd2+ was examined and compared with BPRB, revealing that the rhodamine unit enhanced the fluorescence intensity by 500-fold. The fluorescence images of BPRB and BPRB–Pd2+ samples indicate that BPRB could be useful for imaging Pd2+ in living cells.
New developments in the field of chiral nematic liquid crystals, such as color displays, are now being widely proposed. This article describes the tunable incident reflection band based on composite materials of low-molecular-weight chiroptical dopants and polymeric networks. These materials have advantages including easily manageable color according to a change in the helical pitch of the cholesteric liquid crystal upon exposure to light. A series of novel chiral dopants of isosorbide derivatives containing photochromic groups and three new main-chain liquid crystalline polyesters were synthesized and identified using nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), and elemental analyses. The phase-transition temperatures and the liquid-crystal phase determination of the synthesized polymers were estimated using DSC, WAXD, and POM analyses. The influence of the dopant concentrations and the solubility in a liquid crystalline polymer blend were also studied. The reflection band of the cholesteric liquid crystalline composites could be adjusted and tuned with a wide range of color variation across the entire visible region. A real image recording of the chiral photochromic liquid crystalline polymer blend was achieved by exposing it to UV light through a mask.
A solvent tunable single-layer polymer film with a multipitched photonic structure as a new photonic band gap material has been developed by imprinting the helical structures on polymer matrices through multiple photocrosslinking in an induced chiral nematic mesophase. Here, the polymer matrices themselves served as a chiral template, which exhibited Bragg reflections in the absence of both a chiral dopant and anisotropic materials because of the memory effects of the polymer network. Tuning of colors was achieved by making a refractive index contrast in the two periodic media of imprinted solid helical structure and the isotropic liquids that fill it. On incorporation of various isotropic liquids in the imprinted matrices, a sharp peak in the reflection spectrum shifted drastically, which indicated that the wavelength shifts strongly depended on the sort of liquids that filled the matrices. The effects of temperature on the imprinted polymer template feeding the various liquids were studied through the reflectance spectra. V
Two different series of symmetrical and asymmetrical azobenzenes containing terminal cholesteryl/adamantyl derivatives (SAC/SAA and AAC) with varying spacer lengths (alkyl chains) have been developed. The gelation and aggregation of these derivatives were studied relative to structural motifs, spacer lengths, solvent affinity, temperatures and light conditions. Among these derivatives, the cholesteryl derivatives that have short alkyl chains (<3) act as efficient gelators in a variety of solvents. However, the cholesteryl derivatives with longer alkyl chains (11 spacer) and adamantyl derivatives did not possess this ability. Self-assembled fibrous structures were constructed by gelators with short alkyl chains (<3), while flower-like structures were constructed by gelators with moderately longer alkyl chains (3-6) at their respective critical gelation concentrations (CGCs) according to SEM (Scanning Electron Microscopy) and TEM (Transmission Electron Microscopy) analyses. In some cases, a partial/weak gel was observed in different solvents, which exhibited uniform spherical nanoparticles at CGCs. These nanoparticles were further entangled to form interconnected fibrous structures when the concentration was increased above the CGC (according to the SEM and TEM analyses). Secondary forces (van der Waals/H-bonding) and π-π stacking played important roles in the aggregation of both series in the solvents according to variable temperature (1)H-NMR analysis. The reversibility of sol-gel transitions by light was studied with respect to solvent affinity. This study revealed that reversible transitions were only observed in the non-polar solvents, as supported by the FTIR analysis of the gelators in the various solvents. The thermal and mesomorphic behaviors of the gelators by DSC (Differential Scanning Calorimetry) and POM (Polarized Optical Microscopy) analyses revealed that the chiral nematic (N*) and cholesteric mesophase (Ch*) were exhibited by only the short and longer alkyl chain cholesteryl derivatives, respectively. However, the cholesteryl derivative without a spacer (AAC0) did not exhibit any liquid crystalline phase but acted as an efficient gelator relative to the other gelators in this study.
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