Dharmendar Kumar Sharma

1-, 3-, 6-, and 8-Tetrasubstituted Asymmetric Pyrene Derivatives with Electron Donors and Acceptors: High Photostability and Regioisomer-Specific Photophysical Properties

The systematic synthesis of five 1-, 3-, 6-, and 8-tetrasubstituted asymmetric pyrenes with electron donor and acceptor moieties is presented, together with an examination of their photophysical properties. Pyrene derivative PA1, containing one formyl and three piperidyl groups, showed bright solvatochromic fluorescence from green (λem = 557 nm, ΦFL = 0.94 in hexane) to red (λem = 648 nm, ΦFL = 0.50 in methanol), suggesting potential applications for PA1 as an environmentally responsive probe. Although the synthesis of simple 1- and 3-disubstituted pyrene derivatives is considered difficult, PA13, with two formyl groups at the 1- and 3-positions and two piperidyl groups at the 6- and 8-positions, could be synthesized successfully. PA13 exhibited less pronounced solvatochromism, but displayed a narrow fluorescent band with high ΦFL in all solvents (ΦFL > 0.75). Moreover, its absorption band displayed an exceptional bathochromic shift compared to the other derivatives (e.g., λabs = 480 and 522 nm in ethanol for PA1 and PA13, respectively), suggesting that such modifications of pyrene may be quite important for the modulation of its energy gap. Additionally, all compounds exhibited exceptionally high photostability, which highlights the advantage of these new dyes and provides new insights on the design of photostable fluorophores.

Narrow band-edge photoluminescence from AgInS 2 semiconductor nanoparticles by the formation of amorphous III–VI semiconductor shells

Nanoparticles of I–III–VI semiconductors are promising candidates for novel non-toxic fluorescent materials. However, removal of defect levels responsible for their broad-band emission has not been successful to date. The present study demonstrates, for the first time, the coating of core AgInS2 nanoparticles—one of the I–III–VI group semiconductors with a bandgap in the visible region—with III–VI group semiconductors. The AgInS2/InSx and AgInS2/GaSx (x = 0.8–1.5) core/shell structures generate intense narrow-band photoluminescence originating from a band-edge transition at a wavelength shorter than that of the original defect emission. Microscopic analyses reveal that the GaSx shell has an amorphous nature, which is unexpected for typical shell materials such as crystalline lattice-matching ZnS. Single-particle spectroscopy shows that the average linewidth of the band-edge photoluminescence is as small as 80.0 meV (or 24 nm), which is comparable with that of industry-standard II–VI semiconductor quantum dots. In terms of photoluminescence quantum yield, a value of 56% with nearly single-band emission has been achieved as a result of several modifications to the reaction conditions and post-treatment to the core/shell nanoparticles. This work indicates the increasing potential of AgInS2 nanoparticles for use as practical cadmium-free quantum dots.Nanoparticles: A coating for sharper luminescenceA method for controlling the optical properties of tiny semiconductor particles and making them useful for medical, optical, and display application has been demonstrated by scientists in Japan. Crystals of semiconducting material with nanometer-scale dimensions absorb and emit light across a very narrow range of wavelengths. This makes them potentially useful for bioimaging and other optical applications. Nanoparticles of silver indium sulfide (AgInS2) is one such non-toxic fluorescent material, but their intrinsic spectral responses are broadened. Taro Uematsu, Osaka University, and colleagues show that much narrower optical emission can be achieved by coating AgInS2 nanoparticles with gallium sulfide or indium sulfide. The sharpness of the the resulting spectal response was comparable to that of commercially available cadmium selenide or cadmium telluride nanoparticles, but had the advantage of avoiding the use of toxic cadmium.Silver indium sulfide (AgInS2) semiconductor nanoparticles are cadmium-free quantum dots emitting in visible to near infrared regions. The present study demonstrates the narrowing of their broad defect emission by coating AgInS2 core nanoparticles with amorphous indium sulfide or gallium sulfide shells. The new emission from the core/shell nanoparticles originating from the band-edge transition is substantially narrower (FWHM of 28.6 nm) than the defect emission of core nanoparticles (FWHM of 220 nm). The photoluminescence quantum yield is increased to 56% after giving several modifications to the synthetic procedures so that we can see the vibrant yellow emission under room light.

Glycopolypeptide-Grafted Bioactive Polyionic Complex Vesicles (PICsomes) and Their Specific Polyvalent Interactions

Glycopolypeptide-based self-assembled nano-/microstructures with surface-tethered carbohydrates are excellent mimics of glycoproteins on the cell surface. To expand the broad repertoire of glycopolypeptide-based supramolecular soft structures such as polymersomes formed via self-assembly of amphiphilic polymers, we have developed a new class of polyionic complex vesicles (PICsomes) with glycopolypeptides grafted on the external surface. Oppositely charged hydrophilic block copolymers of glycopolypeptide20-b-poly-l-lysine100 and PEG2k-b-poly-l-glutamate100 [PEG = poly(ethylene glycol)] were synthesized using a combination of ring-opening polymerization of N-carboxyanhydrides and “click” chemistry. Under physiological conditions, the catiomer and aniomer self-assemble to form glycopolypeptide-conjugated PICsomes (GP-PICsomes) of micrometer dimensions. Electron and atomic force microscopy suggests a hollow morphology of the PICsomes, with inner aqueous pool (core) and peripheral PIC (shell) regions. Owing to their relatively large (∼micrometers) size, the hollowness of the supramolecular structure could be established via fluorescence microscopy of single GP-PICsomes, both in solution and under dry conditions, using spatially distributed fluorescent probes. Furthermore, the dynamics of single PICsomes in solution could be imaged in real time, which also allowed us to test for multivalent interactions between PICsomes mediated by a carbohydrate (mannose)-binding protein (lectin, Con-A). The immediate association of several GP-PICsomes in the presence of Con-A and their eventual aggregation to form large insoluble aggregate clusters reveal that upon self-assembly carbohydrate moieties protrude on the outer surface which retains their biochemical activity. Challenge experiments with excess mannose reveal fast deaggregation of GP-PICsomes as opposed to that in the presence of excess galactose, which further establishes the specificity of lectin-mediated polyvalent interactions of the GP-PICsomes.