BODIPY-fused uracil: synthesis, photophysical properties, and applications.

Fluorescent nucleobase and nucleic acid analogs are important tools in chemical and molecular biology as fluorescent labelling of nucleobases has applications in cellular imaging and anti-tumor activity. Boron-dipyrromethene (BODIPY) dyes exhibiting high brightness and good photostability are extensively used as fluorescent labelling agents and as type II photosensitizers for photodynamic therapy. Thus, the combination of nucleobases and BODIPY to obtain new compounds with both anti-tumor activity and fluorescent imaging functions is the focus of our research. We synthesized two new nucleobase analogs 1 and 2 by fusing the BODIPY core directly with uracil which resulted in favorable photophysical properties and high emission quantum efficiencies particularly in organic solvents. Further, we explored the newly synthesized derivatives, which possessed good singlet oxygen generation efficiencies and bio-compatibility, as potential PDT agents and our results show that they exhibit in vitro anti-tumor activities.

Exceptionally Plastic/Elastic Organic Crystals of a Naphthalidenimine-Boron Complex Show Flexible Optical Waveguide Properties.

The design of molecular compounds that exhibit flexibility is an emerging area of research. Although a fair amount of success has been achieved in the design of plastic or elastic crystals, realizing multidimensional plastic and elastic bending remains challenging. We report herein a naphthalidenimine-boron complex that showed size-dependent dual mechanical bending behavior whereas its parent Schiff base was brittle. Detailed crystallographic and spectroscopic analysis revealed the importance of boron in imparting the interesting mechanical properties. Furthermore, the luminescence of the molecule was turned-on subsequent to boron complexation, thereby allowing it to be explored for multimode optical waveguide applications. Our in-depth study of the size-dependent plastic and elastic bending of the crystals thus provides important insights in molecular engineering and could act as a platform for the development of future smart flexible materials for optoelectronic applications.

Nanomolar detection of biothiols via turn-ON fluorescent indicator displacement.

The thiol group is known to have a high affinity for gold nanoparticles and is capable of displacing other capping agents. We report a fluorescent indicator displacement technique for the detection of biothiols based on this principle. The displacement of BODIPY from the surface of gold nanoparticles served as a sensitive method for the detection of cysteine, homocysteine, and glutathione under a variety of conditions. It is noteworthy that the turn-ON fluorescence mechanism enabled the differentiation of normal cells from cancer cells because of the inherently higher concentrations of biothiols in the latter.

Iodo-Functionalized Salicylideneimine-Boron Complexes: Synthesis and Photosensitized Degradation of Organic Water Pollutants.

Boron-containing organic compounds are reported to have excellent luminescent properties, however, their ability to photosensitize singlet oxygen generation remains unexplored. The synthesis of several Schiff-base based boranils is reported, starting from commercially available salicylaldehydes and anilines. The iodo-functionalized derivatives were observed to aid in the photosensitized generation of singlet oxygen. Poly(methylmethacrylate) films incorporating these molecules were prepared and were demonstrated to be capable of serving as a reusable heterogeneous medium for the photosensitized degradation of organic water pollutants.

Simultaneous binding of a cyclophane and classical intercalators to DNA: observation of FRET-mediated white light emission.

DNA-assisted Förster resonance energy transfer (FRET) between an anthracene-based cyclophane (CP) and mono- and bis-intercalators such as propidium iodide (PI) and ethidium homodimer-1 (EHD), respectively, has been studied using various photophysical and biophysical techniques. The cyclophane and PI exhibited simultaneous binding to DNA at all concentrations studied and showed DNA-assisted FRET from the excimer of cyclophane with a FRET efficiency of ca. 71%. On the other hand, the bis-intercalator EHD, only at lower concentrations (<3 µM), can act as an acceptor for the energy transfer process with a lower efficiency of ca. 44%. At higher concentrations (>15 µM), EHD, on account of its higher binding affinity, displaces cyclophane from the DNA scaffold. Employing the ternary system comprising of the cyclophane, DNA and PI and fine-tuning the concentrations of the components in a molar ratio of 1 : 0.75 : 0.05 (CP : DNA : PI) we have demonstrated white light emission with CIE coordinates (0.35, 0.37).

An Autocatalytic System of Photooxidation-Driven Substitution Reactions on a Fe(II)4L6 Cage Framework.

The functions of life are accomplished by systems exhibiting nonlinear kinetics: autocatalysis, in particular, is integral to the signal amplification that allows for biological information processing. Novel synthetic autocatalytic systems provide a foundation for the design of artificial chemical networks capable of carrying out complex functions. Here we report a set of Fe(II)4L6 cages containing BODIPY chromophores having tuneable photosensitizing properties. Electron-rich anilines were observed to displace electron-deficient anilines at the dynamic-covalent imine bonds of these cages. When iodoaniline residues were incorporated, heavy-atom effects led to enhanced (1)O2 production. The incorporation of (methylthio)aniline residues into a cage allowed for the design of an autocatalytic system: oxidation of the methylthio groups into sulfoxides make them electron-deficient and allows their displacement by iodoanilines, generating a better photocatalyst and accelerating the reaction.

BODIPY directed one-dimensional self-assembly of gold nanorods.

The assembly of anisotropic nanomaterials into ordered structures is challenging. Nevertheless, such self-assembled systems are known to have novel physicochemical properties and the presence of a chromophore within the nanoparticle ensemble can enhance the optical properties through plasmon-molecule electronic coupling. Here, we report the end-to-end assembly of gold nanorods into micrometer-long chains using a linear diamino BODIPY derivative. The preferential binding affinity of the amino group and the steric bulkiness of BODIPY directed the longitudinal assembly of gold nanorods. As a result of the linear assembly, the BODIPY chromophores positioned themselves in the plasmonic hotspots, which resulted in efficient plasmon-molecule coupling, thereby imparting photothermal properties to the assembled nanorods. This work thus demonstrates a new approach for the linear assembly of gold nanorods resulting in a plasmon-molecule coupled system, and the synergy between self-assembly and electronic coupling resulted in an efficient system having potential biomedical applications.

Surface coating induced room-temperature phosphorescence in flexible organic single crystals.

Materials exhibiting room temperature phosphorescence (RTP) are in high demand for signage, information encryption, sensing, and biological imaging. Due to weak spin-orbit coupling and other non-radiative processes that effectively quench the triplet excited states, RTP is sparsely observed in organic materials. Although the incorporation of a heavy atom through covalent or non-covalent modification circumvents these drawbacks, heavy-atom-containing materials are undesirable because of their deleterious side effects. Here, we designed and synthesized a new naphthalidenimine-boron complex as a coating material for the single crystals of 4,4'-dimethoxybenzophenone. The coated surface was observed to exhibit yellowish-green phosphorescence with ms lifetimes at ambient conditions through Förster resonance energy transfer (FRET). Importantly, the mechanical flexibility of the single crystals was observed to be retained after coating. The fluorescence-phosphorescence dual emission was utilised for colour-tunable optical waveguiding and anti-counterfeiting applications. As organic single crystals that can sustain mechanical deformations are emerging as the next-generation materials for electronic device fabrication, the flexible RTP organic crystals showing colour-tuneable optical waveguiding could be omnipotent in electronics.

Multifunctional BODIPY embedded non-woven fabric for CO release and singlet oxygen generation.

Materials that can simultaneously release CO and generate singlet oxygen upon visible light irradiation under ambient conditions are highly desirable for therapeutic applications. Furthermore, materials that can sequester the undesirable side products into the matrix without affecting the release of CO and singlet oxygen generation would allow them to be used for practical applications. Focussing on these aspects, we prepared two dipicolylamine appended BODIPY­manganese(I) tricarbonyl complexes wherein the metal core was systematically tethered at 5- and 8- positions of the BODIPY core. The complexes were embedded into a polymer matrix via electrospinning and the resulting non-woven fabrics showed CO release as well as singlet oxygen generation upon irradiation. While the hybrid materials were non-toxic in dark, they were strongly photocytotoxic to c6 cancer cells when exposed to light. Rapid CO release alongside significant singlet oxygen generation, indefinite dark stability, good biocompatibility and negligible dark toxicity makes these fabrics a potent candidate for phototherapeutic applications.

Luminescent hexagonal microtubes prepared through water-induced self-assembly of a polymorphic organoboron compound: formation mechanism and waveguide behaviour.

Tetra-coordinated organoboron (TCOB) compounds are promising candidates for developing high-performance optical devices due to their excellent optoelectronic performance. Fabricating TCOB-based nanomaterials of controlled and defined morphology through rapid and easy-to-execute protocols can significantly accelerate their practical utility in the aforesaid applications. Herein, we report water-induced self-assembly (WISA) to convert a polymorphic TCOB complex (HNBI-B, derived from a 2-(2'-hydroxy-naphthyl)-benzimidazole precursor) into two unique nanomorphologies viz. nanodiscoids (NDs) and fluorescent microtubes with hexagonal cross-sections (HMTs). Detailed electron microscopic investigations revealed that oriented assembly and fusion of the initially formed NDs yield the blue emissive HMTs (SSQY = 26.7%) that exhibited highly promising photophysical behaviour. For example, the HMTs outperformed all the crystal polymorphs of HNBI-B obtained from CHCl3, EtOAc and MeOH in emissivity and also exhibited superior waveguide behaviour, with a much lower optical loss coefficient α' = 1.692 dB mm-1 compared to the rod-shaped microcrystals of HNBI-B obtained from MeOH (α' = 1.853 dB mm-1). Thus, this work reports rapid access to high performance optical nanomaterials through WISA, opening new avenues for creating useful nanomaterial morphologies with superior optical performance.

Facially-selective thymine-thymine photodimerization in TTT triads.

Irradiation of alkane-linked DNA hairpins possessing TTT steps with flanking purine bases yields products identified as the cis-syn (2 + 2) dimers formed between the central thymine and its 3'- and 5'-neighbors. Selective formation of the 3'-dimer is attributed to ground state conformational effects and electron transfer quenching by purine bases.

Isomer Selective Thermosalience and Luminescence Switching in Organic Crystals.

Organic crystals that respond to external stimuli are interesting for the design of smart materials. Here, we show that molecular engineering can transform simple naphthalidenimine-boron complexes─known for their exciting photophysical properties─into functional materials that exhibit thermosalience and thermal-luminescence switching. Detailed crystallographic and spectroscopic investigations revealed the role of subtle molecular parameters in deciphering charge-transfer interactions, which in turn imparted dynamic properties to the crystals. The simultaneous observation of thermally induced jumping and luminescence switching makes these crystals ideal for optoelectronic applications.

Aggregation-Induced Emission, Mechanofluorochromism, and Selective Fluoride Detection by a Tripodal Salicylaldimine.

Fluoride ions are indispensable in biology and environmental science and hence the selective and sensitive detection of fluoride is important. This work reports the design and synthesis of a tripodal Schiff's base 1 through a simple condensation reaction between a commercially available aldehyde and an amine. Single crystal X-ray crystallography revealed that compound 1 is a planar entity with the three salicylidene derivatives on the three arms of the central phenyl moiety linked by imine groups. Compound 1 forms a molecular dimer that resembles a six-petal flower and is stabilized through multiple intermolecular interactions such as C-H.π and π.π interactions. Compound 1 exhibited moderately good emission in the solid state with aggregation induced emission and reversible mechanofluorochromic properties. Moreover, 1 was observed to selectively detect fluoride among various anions with a limit of detection of ∼9 ppm. Compound 1 was also capable of detecting fluoride under a variety of conditions such as in thin films and under cellular conditions.

A visible-light activated ROS generator multilayer film for antibacterial coatings.

The current scenario of antibiotic-resistant bacteria and pandemics caused by viruses makes research in the area of antibacterial and antiviral materials and surfaces more urgent than ever. In this regard, salicylideneimine based tetracoordinate boron-containing organic compounds are emerging as a new class of photosensitizers for singlet oxygen generation. However, the inherent inability of small organic molecules to be processed limits their potential use in functional coatings. Here we show the synthesis of a novel polymer functionalized with diiodosalicylideneimine-boron difluoride (PEI-BF2) and its utility for surface coating inside glass vials via layer-by-layer (LbL) assembly. The multilayer thin films are characterized using AFM and UV-Vis spectroscopy and the resultant coatings display excellent stability. The multilayer coating could be activated using visible light, and owing to the photocatalytic activity of the incorporated PEI-BF2, the surface coating is able to generate singlet oxygen efficiently upon light irradiation. Further, the multilayer coated surfaces exhibit remarkable antimicrobial activity towards both Gram-positive and Gram-negative bacteria under a variety of conditions. Thus, owing to the simple synthesis and the convenient methodology adopted for the preparation of multilayer coatings, the material reported here could pave the way for the development of sunlight activated large area self-sterile surfaces.

Study of cavity size and nature of bridging units on recognition of nucleotides by cyclophanes.

We synthesized a few novel cyclophanes CP-1 to CP-4 containing anthracene units linked together through different bridging and spacer groups and have investigated their interactions with various nucleosides and nucleotides. Of these systems, CP-1 and CP-3 showed selectivity for 5'-GTP and 5'-ATP as compared to other nucleotides and nucleosides, whereas negligible selectivity was observed with CP-2 and CP-4. Interestingly, CP-1, CP-2 and CP-3 exhibited significant binding interactions with the fluorescent indicator, 8-hydroxy-1,3,6-pyrene trisulfonate (HPTS), resulting in the formation of non-fluorescent complexes. Titration of these complexes with nucleosides and nucleotides resulted in the displacement of HPTS, leading to the revival of its fluorescence intensity. It was observed that 5'-GTP induced the maximum displacement of HPTS from the complex [CP-1·HPTS] with an overall fluorescence enhancement of ca. 150-fold, while 5'-ATP induced ca. 45-fold. Although the displacement of HPTS from the complexes [CP-2·HPTS] and [CP-3·HPTS] was found to be similar to that of [CP-1·HPTS], these complexes showed lesser selectivity and sensitivity. In contrast, negligible displacement of HPTS was observed from the complex [CP-4·HPTS] under similar conditions. These results indicate that CP-1, having a well-defined cavity and good electron acceptor (viologen), is capable of forming selective and stable complexes. Though CP-2 and CP-3 retain the good electron acceptor (viologen), their reduced aromatic surface and larger cavity, respectively, resulted in lesser sensitivity. In contrast, CP-4 having a large cavity and a poor acceptor (1,2-bis(pyridin-4-yl)ethene) showed negligible selectivity, thereby indicating the importance of cavity size, bridging unit and aromatic surface on biomolecular recognition properties of cyclophanes.

Functional cyclophanes: promising hosts for optical biomolecular recognition.

Cyclophanes possess a defined cavity size and are efficient in encapsulating and stabilising guest molecules inside the cavity through various non-covalent interactions. This unique property of the cyclophanes has been widely exploited for the development of selective probes for a variety of guest molecules. The present tutorial review highlights the use of various interesting functionalised cyclophane architectures for the sensitive and selective optical recognition of important biomolecules.

Fine-Tuning Plasmon-Molecule Interactions in Gold-BODIPY Nanocomposites: The Role of Chemical Structure and Noncovalent Interactions.

Strong coupling between localized surface plasmons and molecular absorptions leads to remarkable changes in the photophysical properties of dye-loaded metal nanoparticles. Here, we report supramolecular nanocomposites consisting of BODIPY, tryptophan, and gold nanoparticles, and investigate the effect of structural variations on their photophysical properties. Our results indicate that the photostability and photosensitization properties of the nanocomposites depend on the chemical composition of the BODIPY molecules. The singlet oxygen quantum yield of the nanocomposites NC1 (BODIPY, B1 bearing a single methyl group) and NC3 (BODIPY, B3 with 5 methyl and 2 iodo groups) were 0.46 and 0.42, respectively, which were significantly higher compared to their individual components. Ultrafast spectroscopy studies revealed that the migration of photoexcited BODIPY electrons to the plasmonic photoexcitation allowed electron transfer into the singlet oxygen states, thereby leading to efficient generation of singlet oxygen.

Hydrophobic self-assembly of a perylenediimide-linked DNA dumbbell into supramolecular polymers.

The self-assembly of DNA dumbbell conjugates possessing hydrophobic perylenediimide (PDI) linkers separated by an eight-base pair A-tract has been investigated. Cryo-TEM images obtained from dilute solutions of the dumbbell in aqueous buffer containing 100 mM NaCl show the presence of structures corresponding to linear end-to-end assemblies of 10-30 dumbbell monomers. The formation of assemblies of this size is consistent with analysis of the UV-vis and fluorescence spectra of these solutions for the content of PDI monomer and dimer chromophores. Assembly size is dependent upon the concentration of dumbbell and salt as well as the temperature. Kinetic analysis of the assembly process by means of salt-jump stopped-flow measurements shows that it occurs by a salt-triggered isodesmic mechanism in which the rate constants for association and dissociation in 100 mM NaCl are 3.2 × 10(7) M(-1)s(-1) and 1.0 s(-1), respectively, faster than the typical rate constants for DNA hybridization. TEM and AFM images of samples deposited from solutions having higher concentrations of dumbbell and NaCl display branched assemblies with linear regions >1 µm in length and diameters indicative of the formation of small bundles of dumbbell end-to-end assemblies. These observations provide the first example of the use of hydrophobic association for the assembly of small DNA duplex conjugates into supramolecular polymers and larger branched aggregates.

A three-component supramolecular nanocomposite as a heavy-atom-free photosensitizer.

Design of photosensitizers capable of generating singlet oxygen is crucial for the success of photodynamic therapy, and biocompatible supramolecular systems are emerging in this area. We report a supramolecular nanocomposite consisting of BODIPY, tryptophan and gold nanoparticles. While the individual components in isolation were inactive, the nanocomposite was found to be photostable and exhibited efficient photosensitization properties.