Ionic Covalent Organic Framework as a Dual Functional Sensor for Temperature and Humidity.

Visual sensing of humidity and temperature by solids plays an important role in the everyday life and in industrial processes. Due to their hydrophobic nature, most covalent organic framework (COF) sensors often exhibit poor optical response when exposed to moisture. To overcome this challenge, the optical response is set out to improve, to moisture by incorporating H-bonding ionic functionalities into the COF network. A highly sensitive COF, consisting of guanidinium and diformylpyridine linkers (TG-DFP), capable of detecting changes in temperature and moisture content is fabricated. The hydrophilic nature of the framework enables enhanced water uptake, allowing the trapped water molecules to form a large number of hydrogen bonds. Despite the presence of non-emissive building blocks, the H-bonds restrict internal bond rotation within the COF, leading to reversible fluorescence and solid-state optical hydrochromism in response to relative humidity and temperature.

Long-Lived Polypyridyl Based Mononuclear Ruthenium Complexes: Synthesis, Structure, and Azo Dye Decomposition.

Two mononuclear ruthenium complexes [(bpy)2RuIIL1/L2](ClO4)2 ([1]2+/[2]2+) (bpy-2,2' bipyridine, L1 = 2,3-di(pyridin-2-yl)pyrazino[2,3-f][1,10]phenanthroline) and L2 = 2,3-di(thiophen-2-yl)pyrazino[2,3-f][1,10]phenanthroline have been synthesized. The complexes have been characterized using various analytical techniques. The complex [1]2+ has further been characterized by its single crystal X-ray structure suggesting ruthenium is coordinating through the N donors of phenanthroline end. Theoretical investigation suggests that the HOMOs of both complexes are composed of pyridine and pyrazine unit of ligands L1 and L2 whereas the LUMOs are formed by the contribution of bipyridine units. The low energy bands at ∼480 nm of the complexes can be assigned as MLCT with partial contribution from ligand transitions, whereas the rest are ligand centered. The complexes have shown RuII/RuIII oxidation couples at E1/2 at 1.26 (70 mV) V and 1.28 (62 mV) V for [1]2+ and [2]2+ vs Ag/AgCl, respectively, suggesting no significant role of distal thiophene or pyridine units of the ligands. The complexes are emissive and display solvent dependent emission properties. Both complexes have shown highest emission quantum yield and lifetime in DMSO (ϕ = 0.05 and τavg = 460 ns and λmaxem at 620 nm for [1]2+; ϕ = 0.043 and τavg = 425 ns and λmaxem at 635 nm for [2]2+). Further, the long luminescent lifetime of these complexes has been utilized to generate reactive oxygen species for efficient azo dye decomposition.

Spectroscopic investigation of bio-mimetic solvolysis of 6-(N,N-dimethylamino)-2,3-naphthalic anhydride in confined nanocavities.

Enzymes are biological catalysts that can vastly accelerate the reaction rate of a substrate by accommodating it within the active site. The local environment provided by the active site of a natural catalyst causes a significant rate-enhancement of the reaction as compared to that without catalyst. The solvolysis reaction of a 6-(N,N-dimethylamino)-2,3-naphthalic anhydride probe is investigated using UV-Vis and fluorescence spectroscopy in pure alcohols and in bio-mimetic nano-sized environments like surfactants, macrocyclic hosts and protein nanocavities. The solvolysis rate in alcohols is found to be regulated directly by the alkyl chain length and follows Arrhenius dependence. The hydrolysis rate of the probe in water under physiological conditions (pH 7.4, at 25 °C) is very slow. However, under identical conditions, the rate can be accelerated significantly by protein and supramolecular nanocavities. Therefore, such fundamental kinetic analysis of the understanding of this bio-mimetic solvolysis will allow us to design a novel probe-drug conjugate with efficient controlled-release and function.

A ratiometric fluorescent probe for detection of biogenic primary amines with nanomolar sensitivity.

An ultrasensitive ratiometric fluorescent sensor made of an N,N-dimethylaminonaphthalene anhydride moiety for detection of aliphatic primary amines is reported. Biogenic amines at nanomolar concentration is detected with the additional ability to discriminate between primary, secondary and tertiary amines by using both UV-Visible and fluorescence spectroscopy.

Investigation of the effect of cucurbit[7]uril complexation on the photophysical and acid-base properties of the antimalarial drug quinine.

Host-guest complexation of mono and dicationic quinine with cucurbit[7]uril (CB7), a water-soluble macrocyclic host molecule, has been investigated. Job's plot, time-resolved anisotropy as well as concentration dependent NMR titration confirm the binding of two CB7 macrocycles with one quinine molecule. The binding affinity of dicationic quinine with CB7 is one order of magnitude higher than the binding constant of mono-cationic quinine. Such preferential binding results in one unit pKa shift in the ground-state of the quinoline ring. However, using fluorescence spectroscopy we have obtained two acid-dissociation constants, one for quinoline ring nitrogen and the other for the nitrogen of the quinuclidine moiety. In the excited state, CB7 complexation causes one unit pKa shift for the quinoline ring and 1.9 unit shift for the quinuclidine moiety. Interestingly, a large enhancement of fluorescence lifetime and anisotropy of quinine at pH 2.7 and pH 9.0 upon CB7 complexation was observed due to the restriction of conformational flexibility. Moreover, at pH 3.0, a large fluorescence enhancement of quinine due to CB7 complexation was observed and it was quite significant as compared to that of quinine in 0.1 (M) HCl without CB7. We believe that this study of quinine complexation with CB7 will reduce phototoxicity, increase bioavailability and offer an alternative standard for quantum yield measurements in an amiable condition.

Separation of mercuric ions using 2-thienylbenzimidazole/cucurbit[7]uril/iron-oxide nanoparticles by pH control.

2-Thienylbenzimidazole (TBI)/cucurbit[7]uril (CB7) host-guest complex was used as a motif to significantly improve the turnover of γ-Fe3O4 magnetic nanoparticles for potential application in the separation of toxic mercuric ions in polluted water samples. The mechanism of restoring the original solid materials is based on applying the pH-controlled preferential binding of the CB7 host to the TBI guest. The analytical application of this concept has not been realized in the literature. The pH-controlled stimuli-responsive abilities were confirmed in aqueous solution by the three-order of magnitudes higher stability constant of the protonated TBIH+/CB7 complex (e.g., K = 4.8 × 108 M-1) when compared to neutral TBI/CB7 complex (e.g., K = 2.4 × 105 M-1), also manifested in an increase in pKa values by ~ 3.3 units in the ground state. The supramolecular interaction and adsorption on iron oxide nanoparticles (NPs) were also spectroscopically confirmed in the solid state. The excited-state lifetime values of TBI/CB7NPs increased upon lowering the pH values (e.g., from 0.6 to 1.3 ns) with a concomitant blue shift of ~ 25 nm because of polarity effects. The time-resolved photoluminescent behaviors of the final solids in the presence of CB7 ensured pH-driven reusable systems for capturing toxic mercuric ions. The study offers a unique approach for the controllable separation of mercury ions using an external magnet and in response to pH through preferential binding of the host to guest molecules on the top of magnetic surfaces.

Light-driven self-assembly of spiropyran-functionalized covalent organic framework.

Controlling the number of molecular switches and their relative positioning within porous materials is critical to their functionality and properties. The proximity of many molecular switches to one another can hinder or completely suppress their response. Herein, a synthetic strategy involving mixed linkers is used to control the distribution of spiropyran-functionalized linkers in a covalent organic framework (COF). The COF contains a spiropyran in each pore which exhibits excellent reversible photoswitching behavior to its merocyanine form in the solid state in response to UV/Vis light. The spiro-COF possesses an urchin-shaped morphology and exhibits a morphological transition to 2D nanosheets and vesicles in solution upon UV light irradiation. The merocyanine-equipped COFs are extremely stable and possess a more ordered structure with enhanced photoluminescence. This approach to modulating structural isomerization in the solid state is used to develop inkless printing media, while the photomediated polarity change is used for water harvesting applications.

Dyeing Non-Recyclable Polyethylene Plastic with Photoacid Phycocyanobilin from Spirulina Algae: Ultrafast Photoluminescence Studies.

Despite the enormous environmental damage caused by plastic waste, it makes up over one-third of globally produced plastics. Polyethylene (PE) wastes have low recycling but high production rates. Towards the construction of ionic solar cells from PE, the present work describes the loading of a bioactive photoacid phycocyanobilin (PCB) dye from the pigment of Spirulina blue-green algae (as a natural resource) on low-density polyethylene (LDPE) plastic film. Dyeing was confirmed by X-ray photoelectron spectroscopy (XPS). Upon excitation of the Soret-band (400 nm), the photoluminescence (PL) spectra of PCB in neat solvents revealed two prominent emission peaks at 450-550 and 600-700 nm. The first band assigned to bilirubin-like (PCBBR) species predominated the spectral profile in the highly rigid solvent glycerol and upon loading 0.45 % (w/w) of the dye on plastic. The photoluminescence excitation (PLE) spectra of PCB for the second region (Q-band) at 672 nm in the same solvents confirmed the ground state heterogenicity previously associated with the presence of PCBA (neutral), PCBB (cationic), and PCBC (anionic) conformers. Time-resolved photoluminescence (TRPL) measurements induced via excitation of all PCB species at 510 nm in methanol revealed three-lifetime components with τ1 = ~0.1 ns and τ2 = ~2 ns associated with PCBBR species and τ3 = ~5 ns pertinent to the long-living photoproduct X*. Decay-associated spectra (DAS) analysis of the photoluminescence transient spectra of the final dyed films in the solid-state confirmed the improved generation of the long-living photoproduct as manifested in a significant increase in the PL intensity (~100-fold) and lifetime value (~90 ns) in the Q-region upon loading 6.92 % (w/w) of the dye on plastic. The photoproduct species were presumably assigned to the deprotonated PCB species, suggesting improved ionic mobility. The potential implementation of the PCB-sensitized PE solid wastes for the fabrication of ionic solar cells is discussed.

Temperature Control of Yellow Photoluminescence from SiO2-Coated ZnO Nanocrystals.

In this study, we aimed to elucidate the effects of temperature on the photoluminescence from ZnO-SiO2 nanocomposite and to describe the preparation of SiO2-coated ZnO nanocrystals using a chemical precipitation method, as confirmed by Fourier transform infrared (FTIR) and powder X-ray diffraction analysis (XRD) techniques. Analyses using high-resolution transmission microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), and electrophoretic light scattering (ELS) techniques showed that the new nanocomposite has an average size of 70 nm and 90% silica. Diffuse reflectance spectroscopy (DRS), photoluminescence (PL), and photoluminescence-excitation (PLE) measurements at different temperatures revealed two emission bands at 385 and 590 nm when the nanomaterials were excited at 325 nm. The UV and yellow emission bands were attributed to the radiative recombination and surface defects. The variable-temperature, time-resolved photoluminescence (VT-TRPL) measurements in the presence of SiO2 revealed the increase in the exciton lifetime values and the interplay of the thermally induced nonradiative recombination transfer of the excited-state population of the yellow emission via deep centers (DC). The results pave the way for more applications in photocatalysis and biomedical technology.

Supramolecular Encapsulation of a Neurotransmitter Serotonin by Cucurbit[7]uril.

pH-dependent host-guest complexation of a monoamine neurotransmitter, Serotonin, with cucurbit[7]uril has been thoroughly investigated. The binding phenomena were explored using steady-state and time-resolved fluorescence spectroscopy at different pH values. At lower pH, i.e., protonated Serotonin, the binding affinity with cucurbit[7]uril was significantly higher compared to higher pH. Furthermore, detailed NMR titration experiments depicted the solution structure of the host-guest complex through the complexation induced chemical shift values. A competitive binding assay with cesium ions at pD 2.8 was subsequently performed for the further manifestation of the binding. Finally, the molecular docking studies provided well-documented proof of the 1:1 inclusion complex and the geometry of the complex. We believe that understanding from such studies can be important for pH-controlled delivery of serotonin for biological applications.

Encapsulation and modulation of protolytic equilibrium of ß-carboline-based norharmane drug by cucurbit[7]uril and micellar environments for enhanced cellular uptake.

The effect of supramolecular nanocavity on photophysical and acid-dissociation properties of Norharmane (NHM), a physiologically important, anxiety control and memory-enhancing ß-carboline-based drug, has been investigated using steady-state absorption and fluorescence spectroscopy. Self-assembled organization derived from surfactants and rigid water-soluble macrocyclic host Cucurbit[7]uril (CB7) have been selected for this investigation. The confined-space offered by the supramolecular assemblies modulates the pKa value of NHM (up to 3 units) as it can exist in two protolytic forms at near neutral pH. Therefore, the pH-dependent binding properties, modulation of pKa value and its consequences on the photophysical, chemical and solubility properties are investigated in detail. This investigation shows a large shift in the protolytic equilibrium which in turn causes ca. 15 times solubility-enhancement at near neutral pH. Moreover, the effect of enhanced solubility has been further investigated by the augmentation in the cellular uptake of NHM entrapped inside CB7. Thus, the modulation of the acid-base properties and solubility of ß-carboline-based drugs will have immense potential for their formulation, cellular uptake and bioavailability.

A rapid, naked-eye detection of hypochlorite and bisulfite using a robust and highly-photostable indicator dye Quinaldine Red in aqueous medium.

A "naked-eye" detection of health hazardous bisulfite (HSO3-) and hypochlorite (ClO-) using an indicator dye (Quinaldine Red, QR) in a wide range of pH is demonstrated. The molecule contains a quinoline moiety linked to an N,N-dimethylaniline moiety with a conjugated double bond. Treatment of QR with HSO3- and ClO-, in aqueous solution at near-neutral pH, resulted in a colorless product with high selectivity and sensitivity. The detection limit was 47.8µM and 0.2µM for HSO3- and ClO- respectively. However, ClO- was 50 times more sensitive and with 2 times faster response compared to HSO3-. The detail characterization and related analysis demonstrate the potential of QR for a rapid, robust and highly efficient colorimetric sensor for the practical applications to detect hypochlorite in water samples.

Alkyl chain-modified cyclometalated iridium complexes as tunable anticancer and imaging agents.

Five mononuclear cyclometalated iridium complexes [1](PF6)-[5](PF6) were prepared using imidazole-based ligands of varying alkyl chain length. The complexes were characterised by various analytical techniques. The single crystal X-ray structures of [2](PF6), [3](PF6) and [4](PF6) revealed the expected distorted Oh structures around the metal centre; however, the chain length was found to play a crucial role in deciding the overall geometry. Theoretical investigations demonstrated that the HOMOs were mainly contributed by iridium and cyclometalated ligands, whereas the LUMOs were constituted from bpy/phen units. The complexes were found to be luminescent with a moderate emission quantum yield and lifetime in CH3CN. The in vitro growth inhibition assay of the complexes with a shorter alkyl chain ([4]+ and [5]+) displayed higher anticancer activity (IC50 < 0.5 µM) compared to the complexes with a longer alkyl chain ([1]+-[3]+) (IC50 < 30 µM) against human breast cancer (MCF-7) cells. The complexes [4]+ and [5]+ also displayed moderate cancer cell selectivity (∼3 times) over normal breast (MCF-10) cells. The flow cytometry assay and fluorescence microscopy analysis suggested that cellular accumulation was primarily responsible for the variation in anticancer activity. Interestingly, without possessing any anticancer activity or toxicity ((IC50 > 50 µM), the complex [1]+ mainly accumulated near the cell membrane outside the cell and displayed a clear image of the cell membrane. The light microscopy images and western blot analysis reveal that complex [4]+ induced combined apoptosis and paraptosis. Thus, tuning the anticancer activity and cellular imaging property mediated by the alkyl chain would be of great importance and would be useful in anticancer research.

Supramolecular guest relay using host-protein nanocavities: an application of host-induced guest protonation.

Small drug molecules and other important metabolites are delivered via a suitable carrier protein-mediated transport through a specific receptor. The process is highly coordinated and associated with complexation induced properties of deliverable molecules. To get a molecular insight, in this report, we tried to mimic the delivery process to know how the carrier protein relocates the drug molecule from the macrocyclic host cavity to its binding pocket and how the electronic and the chemical properties of the guest get altered. Bovine and human serum albumin (BSA and HSA) were used as the model carrier proteins which can snatch out 6-propanoyl-2-(N,N-dimethylamino)naphthalene (PRO), dye used as a drug model (known to bind at the drug-binding pocket of the carrier protein), from the cucurbit[7]uril (CB7) cavity, a potential drug delivery carrier. Prior to performing the fluorescence-based bio-supramolecular relocation assay using BSA and HSA, CB7 and PRO, we have investigated the effect of CB7 encapsulation and protonation on the fluorescence properties of PRO. A significant shift in the pKa value from 3.4 to 6.6 (ca. 3.2 logarithmic units) of PRO was observed upon encapsulation with CB7, which causes a huge fluorescence quenching even at neutral pH. The binding affinity of protonated and neutral PRO for CB7 also confirms a 3.2 unit shift in the acid-dissociation constant. A displacement assay using a strong CB7 binder, viz., 1,6-diaminohexane, confirms encapsulation of PRO in the CB7 cavity. Encapsulation of neutral PRO by CB7 shows a significant fluorescence enhancement accompanied by a ∼35 nm blue shift in the emission maxima.

Iridium Complexes as a Roadblock for DNA Polymerase during Amplification.

Iridium-based metal complexes containing polypyridyl-pyrazine ligands show properties of DNA intercalation. They serve as roadblocks to DNA polymerase activity, thereby inhibiting the polymerization process. Upon the addition of increasing concentrations of these iridium complexes, a rapid polymerase chain reaction (PCR)-based assay reveals the selective inhibition of the DNA polymerization process. This label-free approach to study the inhibition of fundamental cellular processes via physical roadblock can offer an alternative route toward cancer therapy.