Fluorescent Molecular Logic Gates and Pourbaix Sensors in Polyacrylamide Hydrogels.

Polyacrylamide hydrogels formed by free radical polymerisation were formed by entrapping anthracene and 4-amino-1,8-naphthalimide fluorescent logic gates based on photoinduced electron transfer (PET) and/or internal charge transfer (ICT). The non-covalent immobilisation of the molecules in the hydrogels resulted in semi-solid YES, NOT, and AND logic gates. Two molecular AND gates, examples of Pourbaix sensors, were tested in acidic aqueous methanol with ammonium persulfate, a strong oxidant, and displayed greater fluorescence quantum yields than previously reported. The logic hydrogels were exposed to aqueous solutions with chemical inputs, and the fluorescence output response was viewed under 365 nm UV light. All of the molecular logic gates diffuse out of the hydrogels to some extent when placed in solution, particularly those with secondary basic amines. The study exemplifies an effort of taking molecular logic gates from homogeneous solutions into the realm of solid-solution environments. We demonstrate the use of Pourbaix sensors as pE-pH indicators for monitoring oxidative and acidic conditions, notably for excess ammonium persulfate, a reagent used in the polymerisation of SDS-polyacrylamide gels.

Aminonaphthalimide hybrids of mitoxantrone and amonafide as anticancer and fluorescent cellular imaging agents.

Novel water-soluble 4-aminonaphthalimides were synthesised and their cellular fluorescent imaging, cytotoxicity and ability to induced apoptosis evaluated. The lead compound 1 was designed from the cross-fertilisation of the basic hydrophilic amino pharmacophore of mitoxantrone, and an aminonaphthalimide scaffold of the drug candidate, amonafide. The compounds are also fluorescent pH probes based on photoinduced electron transfer (PET) and internal charge transfer (ICT). The compounds are sensitive to solvent polarity with large Stoke shifts (>90 nm) and provide emissive-coloured solutions (blue to yellow). Excited state pKas of 9.0-9.3 and fluorescence quantum yields of 0.47-0.58 were determined in water. The cytotoxicity and cellular fluorescent imaging properties of the compounds were tested on human cancer cell lines K562 and MCF-7 by the MTT assay, phase contrast and fluorescence microscopy. Compounds 1 and 3 with flexible aminoalkyl chains exhibited GI50 comparable to amonafide, while 2 and 4 with a rigid piperazine moiety and butyl chain are less cytotoxic. Fluorescence microscopy with 1 allowed for the visualization of the intracellular microenvironment exemplifying the potential utility of such hybrid molecules as anticancer and fluorescent cellular imaging agents.

Giant Enhancement of Defect-Bound Exciton Luminescence and Suppression of Band-Edge Luminescence in Monolayer WSe2-Ag Plasmonic Hybrid Structures.

We have investigated how the photoluminescence (PL) of WSe2 is modified when coupled to Ag plasmonic structures at low temperature. Chemical vapor deposition (CVD) grown monolayer WSe2 flakes were transferred onto a Ag film and a Ag nanotriangle array that had a 1.5 nm Al2O3 capping layer. Using low-temperature (7.5 K) micro-PL mapping, we simultaneously observed enhancement of the defect-bound exciton emission and quenching of the band edge exciton emission when the WSe2 was on a plasmonic structure. The enhancement of the defect-bound exciton emission was significant with enhancement factors of up to ∼200 for WSe2 on the nanotriangle array when compared to WSe2 on a 1.5 nm Al2O3 capped Si substrate with a 300 nm SiO2 layer. The giant enhancement of the luminescence from the defect-bound excitons is understood in terms of the Purcell effect and increased light absorption. In contrast, the surprising result of luminescence quenching of the bright exciton state on the same plasmonic nanostructure is due to a rather unique electronic structure of WSe2: the existence of a dark state below the bright exciton state.

Redox-Enabled, pH-Disabled Pyrazoline-Ferrocene INHIBIT Logic Gates.

Pyrazoline-ferrocene conjugates with an "electron-donor-spacer-fluorophore-receptor" format are demonstrated as redox-fluorescent two-input INHIBIT logic gates.

Fluorescent Photoinduced Electron Transfer (PET) Logic Gates for Acidity (pH) and Redox Potential (pE).

This mini-review highlights the photophysical properties of fluorescent molecular logic gates responsive to acids and oxidants, particularly those developed in our laboratory the past few years. The review pays tribute to earlier developments that lay the foundation for this emerging class of molecules. The logic gates incorporate design concepts based on photoinduced electron transfer from the cross-fertilization of the fluorophore-spacer-receptor and fluorophore-spacer-electron-donor formats. The molecular logic gates explored in detail consist of anthracene and/or naphthalimide fluorophores, while the receptor and electron-donor are typically alkyl amines and ferrocene, respectively. This emerging class of molecule has numerous probable uses, most notably, in corrosion science, geochemistry, molecular cell biology and biomedical diagnostics.

4-Amino-1,8-naphthalimide-ferrocene conjugates as potential multi-targeted anticancer and fluorescent cellular imaging agents.

Herein we present eight ferrocenyl 4-amino-1,8-naphthalimides. Designed as fluorescent logic gates for acidity and oxidisability, the molecules have been repurposed as anti-proliferation and cellular imaging agents. The compounds were studied in vitro against MCF-7 and K562 cancer cell lines by the MTT method. Compounds with protonable secondary amines tended to exhibit greater cytotoxicity than those with tertiary amines. Compounds with no measurable GI50 values within a 24 hour time window, as well as at shorter exposure times, may be suitable as fluorescent cellular imaging probes.

Photophysics of Thermally-Assisted Photobleaching in "Giant" Quantum Dots Revealed in Single Nanocrystals.

Quantum dots (QDs) are steadily being implemented as down-conversion phosphors in market-ready display products to enhance color rendering, brightness, and energy efficiency. However, for adequate longevity, QDs must be encased in a protective barrier that separates them from ambient oxygen and humidity, and device architectures are designed to avoid significant heating of the QDs as well as direct contact between the QDs and the excitation source. In order to increase the utility of QDs in display technologies and to extend their usefulness to more demanding applications as, for example, alternative phosphors for solid-state lighting (SSL), QDs must retain their photoluminescence emission properties over extended periods of time under conditions of high temperature and high light flux. Doing so would simplify the fabrication costs for QD display technologies and enable QDs to be used as down-conversion materials in light-emitting diodes for SSL, where direct-on-chip configurations expose the emitters to temperatures approaching 100 °C and to photon fluxes from 0.1 W/mm2 to potentially 10 W/mm2. Here, we investigate the photobleaching processes of single QDs exposed to controlled temperature and photon flux. In particular, we investigate two types of room-temperature-stable core/thick-shell QDs, known as "giant" QDs for which shell growth is conducted using either a standard layer-by-layer technique or by a continuous injection method. We determine the mechanistic pathways responsible for thermally-assisted photodegradation, distinguishing effects of hot-carrier trapping and QD charging. The findings presented here will assist in the further development of advanced QD heterostructures for maximum device lifetime stability.