Dual Applications of Cobalt-Oxide-Grafted Carbon Quantum Dot Nanocomposite for Two Electrode Asymmetric Supercapacitors and Photocatalytic Behavior.

Carbon materials, such as graphene, carbon nanotubes, and quantum-dot-doped metal oxides, are highly attractive for energy storage and environmental applications. This is due to their large surface area and efficient optical and electrochemical activity. In this particular study, a composite material of cobalt oxide and carbon quantum dots (Co3O4-CQD) was prepared using cobalt nitrate and ascorbic acid (carbon source) through a simple one-pot hydrothermal method. The properties of the composite material, including the functional groups, composition, surface area, and surface morphology, were evaluated by using various methods such as ultraviolet, Fourier transform infrared, X-ray diffraction, Raman, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller, scanning electron microscopy, and transmission electron microscopy analysis. The electrochemical performance of the Co3O4-CQD composite has been studied using a three-electrode system. The results show that at 1 A g-1, the composite delivers a higher capacitance of 1209 F g-1. The asymmetric supercapacitor (Co3O4-CQD//AC) provided 13.88 W h kg-1 energy and 684.65 W kg-1 power density with a 96% capacitance retention. The Co3O4-CQD composite also demonstrated excellent photocatalytic activity (90% in 60 min) for the degradation of methylene blue dye under UV irradiation, which is higher than that of pristine Co3O4 and CQD. This demonstrates that the Co3O4-CQD composite is a promising material for commercial energy storage and environmental applications.

Phytochemical analysis and biological investigation of Cheilanthes tenuifolia (Burm.f.) Swartz.

Introduction: Cheilanthes tenuifolia is an evergreen ornamental small fern, belonging to the family Pteridaceae, that grows in warm and rocky regions worldwide. Many species of Cheilanthes genus are evidently endowed with important phytochemicals and bioactivities. This study aimed to perform a preliminary phytochemical analysis of Cheilanthes tenuifolia leaves alongside an evaluation of free radical scavenging, anti-inflammatory, antimicrobial, and clot lysis activities of extract fractions. Materials and methods: A preliminary phytochemical analysis was done after fractionation of ethanolic extract (ECT) with n-hexane (HCT) and chloroform (CCT). Then, 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging, egg albumin and RBC membrane stabilization tests, disc diffusion, and human blood clot lysis assays were performed. Results: Phytochemical investigations suggested that the plant is rich in alkaloids, glycosides, tannins, and flavonoids. All obtained fractions exhibited concentration-dependent radical scavenging, inhibition of egg protein denaturation and RBC membrane lysis capacities. Except for antifungal tests, ECT exhibited better DPPH radical scavenging, anti-inflammatory, antibacterial, and clot lysis capacities than HCT and CCT fractions. However, all fractions exhibited a mild anti-inflammatory activity. Conclusion: C. tenuifolia might be a good source of antioxidant, anti-microbial, and anti-atherothrombotic agents. Further studies are required to isolate and characterize the active principles liable for each bioactivity, along with possible molecular interactions.

Design and Exploration by Quantum Chemical Analysis of Photosensitizers Having [D-π-π-A]- and [D-D-triad-A]-Type Molecular Structure Models for DSSC.

Density functional theory (DFT) calculations are performed on the newly developed and designed photosensitizers having [D-D-triad-A]- and [D-π-π-A]-type structural models for near-infrared absorption dye-sensitized solar cells (DSSCs). For this purpose, three novel molecules are designed, which are named as follows: [naphthalene-anthracene-thiophene-furan-benzonitrile] as dye S1, [coronene-anthracene-thiophene-furan-benzonitrile] as dye S2, and [fluorene-thiophene-furan-benzonitrile] as dye S3. In all three systems, benzonitrile is the acceptor moiety, while thiophene and furan are bridging moieties. Naphthalene and anthracene are donor moieties in S1, whereas coronene and anthracene are donor moieties in S2, and fluorene is the only single donor moiety used for designing the dye complex S3. All three dye complexes are optimized under the DFT framework by using the B3LYP hybrid functional with 6-31G(d,p) basis set on Gaussian 16W software. The absorption spectra are calculated utilizing time-dependent density functional theory (TD-DFT) with the CAM-B3LYP/6-31G(d,p) basis set. The calculated absorption maxima of S1 and S2 are 749.45 and 750.04 nm, respectively, while for S3, it is reported to be at 337.35 nm, which suggests that the designed molecular structure having a double-donor moiety is suitable for high absorption wavelength. Further, the analysis of frontier molecular orbital energy gap suggests that the molecular systems S1, S2, and S3 have values 2.17, 2.13, and 3.618 eV, respectively, which lie in the semiconducting region. The other parameters calculated for the photovoltaic performance are exciton binding energy, change in free energy of charge regeneration, change in free energy of charge injection, oscillator strength, light harvesting efficiency, and open-circuit voltage.

Construction of a binder-free PANI-CQD-Cu electrode via an electrochemical method for flexible supercapacitor applications.

In recent years, flexible hybrid supercapacitors (FSCs) have played a significant role in energy storage applications owing to their superior flexibility and electrochemical properties. In this study, carbon quantum dots (CQDs) were prepared from ascorbic acid via a hydrothermal method and physical and chemical characterizations were performed. Then, the carbon quantum dots (CQDs) were doped with polyaniline (PANI) and copper (Cu) to form a PANI-CQD-Cu composite coated on carbon cloth (CC) using an electropolymerization method. In the polymerization process, CQDs bind with the PANI chain and form a PANI-CQD-Cu composite. The prepared electrode's functional group and surface morphology were characterized through XRD, Raman, BET, XPS and SEM with EDAX studies. The electrochemical properties of the PANI-CQD-Cu electrode were investigated using cyclic voltammetry, impedance spectroscopy and galvanostatic charge-discharge study. The capacitance value of PANI-CQD-Cu was 1070 mF cm-2 at 5 mA cm-2 (1070 F g-1 at 1 A g-1), which was higher than that of PANI (775 mF cm-2). Moreover, a flexible asymmetric supercapacitor (FASC) based on an activated carbon/PVA-H2SO4/PANI-CQD-Cu device was fabricated, which exhibited outstanding energy and power densities of 23.10 µW h cm-2 and 0.978 mW cm-2, respectively. The capacitance value remained at 92% after 3000 cycles. The outcome results indicated that the PANI-CQD-Cu-coated CC electrode material can be a promising electrode material for practical energy storage applications.

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.

Evaluation of the Immunosafety of Cucurbit[n]uril In Vivo.

Cucurbiturils are a family of macrocyclic oligomers capable of forming host-guest complexes with various molecules. Due to noncovalent binding to drug molecules and low toxicity, cucurbiturils has been extensively investigated as potential carriers for drug delivery. However, the immune system's interactions with different drug carriers, including cucurbiturils, are still under investigation. In this study, we focused on cucurbiturils' immunosafety and immunomodulation properties in vivo. We measured blood counts and lymphocyte subpopulations in blood, spleen, and bone marrow, and assessed the in vivo toxicity to spleen and bone marrow cells after intraperitoneal administration to BALB/c mice. When assessing the effect of cucurbit[6]uril on blood parameters after three intraperitoneal injections within a week in laboratory animals, a decrease in white blood cells was found in mice after injections of cucurbit[6]util, but the observed decrease in the number of white blood cells was within the normal range. At the same time, cucurbit[7]uril and cucurbit[8]uril did not affect the leukocyte counts of mice after three injections. Changes in the number of platelets, erythrocytes, and monocytes, as well as in several other indicators, such as hematocrit or erythrocyte volumetric dispersion, were not detected. We show that cucurbiturils do not have immunotoxicity in vivo, with the exception of a cytotoxic effect on spleen cells after сucurbit[7]uril administration at a high dosage. We also evaluated the effect of cucurbiturils on cellular and humoral immune responses. We founded that cucurbiturils in high concentrations affect the immune system in vivo, and the action of various cucurbiturils differs in different homologues, which is apparently associated with different interactions in the internal environment of the body.

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.

Cucurbituril-assisted sensitive fluorescence detection and quantitation of naproxen drug in wastewater samples: Guest-host characterization and HPLC investigation.

Sensitive spectrofluorometric and liquid chromatography with fluorescence detection methods have been developed for detection and determination of naproxen drug in the presence of cucurbit7uril (CB7). Fluorescence signals have been improved with the addition of CB7 to the drug aqueous solution. Fluorescence spectroscopy, mass spectrometry, 1H-NMR, and liquid chromatography with fluorescence detection were used to investigate the guest-host interaction of naproxen drug and cucurbiturils. Naproxen was found to form a supramolecular complex with CB7 that had a high formation constant. The optimal conditions for the interaction were discovered using spectroflurometry to be 0.2 mg/ml of CB7, 2.4 µg/ml of naproxen drug, and pH10. A 1:1 complex between naproxen and CB7 is revealed by proton NMR and tandem mass spectrometry. Using the standard addition calibration method, an HPLC with a fluorescence detector was used to detect naproxen in influent and effluent wastewater samples. Finally, it was discovered that the measured concentrations of naproxen in the influent and the effluent wastewater were 1.87 × 10-4 ppb and 2.1 × 10-5 ppb, respectively. This was done by sample enrichment, which reduced the 1000 mL into 1 ml.

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.

A new mode of luminescence in lanthanide oxalates metal-organic frameworks.

Two lanthanide metal-organic frameworks [Ln-MOFs, Ln = Eu(III), Tb(III)] composed of oxalic acid and Ln building units were hydrothermally synthesized and fully characterized by powder X-ray diffraction, Fourier-transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscope, and energy-dispersive X-ray spectroscopy. Furthermore, their magnetic susceptibility measurements were obtained using SQUID based vibrating sample magnetometer (MPMS 3, Quantum Design). Both Ln-MOFs exhibited highly efficient luminescent property. Solid-state photoluminescence (PL) measurements revealed phosphorescence emission bands of Eu-MOF and Tb-MOF centered at 618 nm (red emission) and 550 nm (green emission) upon excitation at 396 nm and 285 nm, respectively. Eu-MOF and Tb-MOF displayed a phosphorescence quantum yield of 53% and 40%, respectively. Time-resolved PL analyses showed very long lifetime values, at 600 and 1065 ± 1 µs for Eu-MOF and Tb-MOF, respectively. Calculations performed by density functional theory indicated a charge transfer form metal centres to the ligand which was in good agreement with the experimental studies. Therefore, this new mode of highly photoluminescent MOF materials is studied for the first time which paves the way for better understanding of these systems for potential applications.

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.

Fluorescence turn on amine detection in a cationic covalent organic framework.

Ionic covalent organic frameworks (iCOFs) are new examples of porous materials and have shown great potential for various applications. When functionalized with suitable emission sites, guest uptake via the ionic moieties of iCOFs can cause a significant change in luminescence, making them excellent candidates for chemosensors. In here, we present a luminescence sensor in the form of an ionic covalent organic framework (TGH+•PD) composed of guanidinium and phenanthroline moieties for the detection of ammonia and primary aliphatic amines. TGH+•PD exhibits strong emission enhancement in the presence of selective primary amines due to the suppression of intramolecular charge transfer (ICT) with an ultra-low detection limit of 1.2 × 10‒7 M for ammonia. The presence of ionic moieties makes TGH+•PD highly dispersible in water, while deprotonation of the guanidinium moiety by amines restricts its ICT process and signals their presence by enhanced fluorescence emission. The presence of ordered pore walls introduces size selectivity among analyte molecules, and the iCOF has been successfully used to monitor meat products that release biogenic amine vapors upon decomposition due to improper storage.

Benzimidazole-Piperazine-Coumarin/Cucurbit[7]uril Supramolecular Photoinduced Electron Transfer Fluorochromes for Detection of Carnosol by Stimuli-Responsive Dye Displacement and pK a Tuning.

A new fluorescent dye (4PBZC) comprising coumarin (C), piperazine (P), and benzimidazole (BZ) was designed, prepared, and complexed to cucurbit[7]uril (CB7) to detect carnosol (CAR), an anti-breast cancer drug, in sub-nanomolar concentrations utilizing the supramolecular indicator displacement assay strategy, the CB7-assisted pK a shift, and the CB7-retarded photoinduced electron transfer process. The host-guest complexation was confirmed by UV-visible absorption, fluorescence, and 1H NMR spectroscopy, which established the binding of 4PBZC to CB7. CB7 preferentially binds the indicator dye (4PBZC) via the protonated BZ residue compared to the neutral BZ one, demonstrated by a higher binding constant of the complex in its di-protonated form, which led to an increase in the pK a of the BZ moiety by ca. 3.0 units after the addition of CB7. In aqueous solution (pH 6), switching the emission signals between 4PBZH+C/CB7 (ON state) and 4PBZC (OFF state) was achieved by displacement of the protonated dye from the cavity of CB7 by the CAR analyte. An efficient sensor was obtained for the sensitive detection of CAR in aqueous solution with a low detection limit of 0.148 ng/mL (0.45 nM) and a linear range from 20 to 627 ng/mL.

Discovery of Natural Product Inspired 3-Phenyl-1H-isochromen-1-ones as Highly Potent Antioxidant and Antiplatelet Agents: Design, Synthesis, Biological Evaluation, SAR and In Silico Studies.

BACKGROUND: Several natural/synthetic molecules having a structure similar to 1H-isochromen- 1-ones have been reported to display promising antioxidants and platelet aggregation inhibitory activity. Isocoumarin (1H-2-benzopyran-1-one) skeleton, either whole or as a part of the molecular framework, has been explored for its antioxidant or antiplatelet activities. INTRODUCTION: Based on the literature, a new prototype, i.e., 3-phenyl-1H-isochromen-1-ones based compounds, has been rationalized to possess both antioxidant as well as antiplatelet activities. Consequently, no reports are available regarding its inhibition either by cyclooxygenase-1 (COX-1) enzyme or by arachidonic acid (AA)-induced platelet aggregation. This prompted us to investigate 3-phenyl-1H-isochromen-1-ones towards antioxidant and antiplatelet agents. METHODS: The goal of this work was to identify new 3-phenyl-1H-isochromen-1-ones based compounds via synthesis of a series of analogues, followed by performing in vitro antioxidant as well as AA-induced antiplatelet activities. Then, identification of potent compounds by SAR and molecular docking studies was carried out. RESULTS: Out of all synthesized 3-phenyl-1H-isochromen-1-ones analogues, five compounds showed 7-fold to 16-fold more highly potent antioxidant activities than ascorbic acid. Altogether, ten 3-phenyl-1H-isochromen- 1-one analogues displayed antioxidant activities in 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. Almost all the 3-phenyl-1H-isochromen-1-one analogues exhibited potent AA-induced antiplatelet activity; few of them displayed 7-folds more activity as compared to aspirin. Further, in silico analysis validated the wet results. CONCLUSION: We disclose the first detailed study for the identification of 3-phenyl-1H-isochromen-1-one analogues as highly potent antioxidant as well as antiplatelet agents. The article describes the scaffold designing, synthesis, bioevaluation, structure-activity relationship, and in silico studies of a pharmaceutically privileged bioactive 3-phenyl-1H-isochromen-1-one class of heterocycles.

Photoinduced Electron Transfer in Encapsulated Heterocycles by Cavitands.

Host-guest complexation of small heterocyclic (guest) and macrocyclic cavitands (hosts) organic molecules is still to date a very popular, inexpensive approach that bypasses the burdens of conventional covalent synthesis. Understanding the selection criteria of these chemicals is crucial to the design and potential applications of their supramolecular assemblies. This review surveys examples within the last 15 years (2005-2020) of supramolecular complexes in which the interacting photoinduced electron transfer (PET)-based chromophore and quencher fragments are commonly used in the market with reported CAS numbers. It appears from this survey that the supramolecular effects can be directed to specifically disrupt PET when the nonemissive macrocycles separately encapsulate the fluorescent acceptor or donor molecules, among other specific factors, such as when inducing conformational changes or pKa shift of the donor. On the contrary, synergetic encapsulation of both donor and acceptor molecules, formation of ternary self-assembly at the rim or encapsulation of one component while grafting the other onto the macrocycle, among other specific factors such as the modulation of the excited-state structure of donor, will lead to the enhancement of PET process. In the event the donor or acceptor molecules have multitopic structures, the PET process can repeatedly be switched on and off. It is generally concluded that understanding the criteria for the combination of these available products for the purpose of manipulating their PET efficiency should pave the way for the facile alternative generation of new noncovalently bonded host-guest supramolecular assemblies with a more specific design tailored for more advanced, diverse and economic applications such as chemical sensing, molecular gates, drug delivery and biolabeling.

Cucurbituril Ameliorates Liver Damage Induced by Microcystis aeruginosa in a Mouse Model.

Microcystis aeruginosa is a cyanobacterium that produces a variety of cyclic heptapeptide toxins in freshwater. The protective effects of the macromolecular container cucurbit[7]uril (CB7) were evaluated using mouse models of cyanotoxin-induced liver damage. Biochemical analysis of liver function was performed to gauge the extent of liver damage after exposure to cyanobacterial crude extract [CCE; LD50 = 35 mg/kg body weight; intraperitoneal (i.p.)] in the absence or presence of CB7 (35 mg/kg body weight, i.p.). CCE injection resulted in liver enlargement, potentiated the activities of alanine aminotransferase (ALT) and glutathione S-transferase (GST), increased lipid peroxidation (LPO), and reduced protein phosphatase 1 (PP1) activity. CCE-induced liver enlargement, ALT and GST activities, and LPO were significantly reduced when CB7 was coadministered. Moreover, the CCE-induced decline of PP1 activity was also ameliorated in the presence of CB7. Treatment with CB7 alone did not affect liver function, which exhibited a dose tolerance of 100 mg/kg body wt. Overall, our results illustrated that the addition of CB7 significantly reduced CCE-induced hepatotoxicity (P < 0.05).

Encapsulation of Cinnamic Acid by Cucurbit[7]uril for Enhancing Photoisomerization.

Cis- or Z-configuration is required for the plant growth-promoting activity of cinnamic acid (CA), whereas the E-form is inactive. Herein, we describe the encapsulation of E-CA by cucurbit[7]uril (CB7) and show that photoisomerization reactions can be more efficiently controlled in aqueous solutions by utilizing this supramolecular approach. Measurements of UV-visible absorption and proton NMR spectra at different pH values confirm that E-CA and its methyl ester, methyl-E-cinnamate (MC), form stronger 1:1 host-guest complexes with CB7 compared to cucurbit[8]uril (CB8) or three cyclodextrins (α-, ß-, and γ-CD). Irradiation of (300 nm) UV light to an aqueous solution of the CB7-bound E isomers induces E to Z photoisomerization and the dissociation of the complex. When the same solution is irradiated by (254 nm) UV light, Z to E conformational changes of the unbound Z isomers are observed and are accompanied by restoring the host-guest complex formation.

pH-controlled preferential binding of cucurbit[7]uril-coated iron-oxide nanoparticles to 6-mercaptonicotinic acid for fluorescent detection of cadmium ions in the solid state.

A host-guest complex of 6-mercaptonicotinic acid (MNA) and cucurbit[7]uril (CB7) was prepared and conjugated to γ-Fe3O4 nanoparticles (NPs) to detect toxic cadmium ions in water as a solid-state sensor. The formation of an inclusion host-guest complex with CB7 was confirmed by UV-vis absorption and proton NMR spectroscopy. CB7 preferentially binds the protonated MNA form compared to the neutral form, demonstrated by a binding constant for the protonated form that is four orders of magnitude higher than that of the neutral form. An increase in the pKa of MNA by 1.2 units was demonstrated after the addition of CB7, which further supports preferential binding between MNA and CB7. The NMR results confirm binding to cadmium via the carboxylic acid moiety. Stationary and time-resolved fluorescence results, in solution and in the solid state, indicate that cadmium and CB7 cause a blue shift in the MNA emission bands and extend its excited-state lifetime due to dissociation of the MNA dimer. In the solid state, switching the emission signals between Cd2+-MNA/CB7NPs (ON state) and MNAH+/CB7NPs (OFF state) was achieved by controlling the pH. An efficient, regenerable, and stable sensor device was fabricated for sensitive and selective detection of Cd2+ in contaminated water samples. Graphical abstract Regeneration of MNA/CB7 nanoparticles for the detection of cadmium ions in the solid state by a visible blue emission signal upon suppression of photoinduced electron transfer (PET).

Enhanced Energy Conversion of Z907-Based Solar Cells by Cucurbit[7]uril Macrocycles.

A dye-sensitized solar cell was constructed on the basis of encapsulating the ruthenium polypyridyl photosensitizer Z907 in the macrocycle cucurbit[7]uril (CB7). The work focuses on the photophysical properties of the new host-guest complexes in acetonitrile and water (volume ratio 1:9) and on the top of nanocrystalline titanium dioxide (TiO2) electrode prior to the addition of poly(3-hexylthiophene) polymer and gold electrode. Complexation to CB7 in aqueous solutions has decreased the emission intensity and excited-state lifetime for metal-to-ligand charge transfer (MLCT) state at 650 nm by twofold because of collisional quenching, which opens a non-radiative deactivation channel. Similarly, a twofold decrease in the emission intensity and excited-state lifetime of MLCT at 750 nm on the top of TiO2 electrodes was observed with the addition of CB7. Encapsulation of Z907 dye to CB7 host has, also, led to fourfold enhancement in the short circuit current and power conversion efficiency of the final solar cell. The results support the premise that host-guest complexation of CB7 facilitates faster electron injection from Z907 dye into the conduction band of TiO2 electrodes.