Dynamics of Anthracene Excimer Formation within a Water-Soluble Nanocavity at Room Temperature.

Excited anthracene is well-known to photodimerize and not to exhibit excimer emission in isotropic organic solvents. Anthracene (AN) forms two types of supramolecular host-guest complexes (2:1 and 2:2, H:G) with the synthetic host octa acid in aqueous medium. Excitation of the 2:2 complex results in intense excimer emission, as reported previously, while the 2:1 complex, as expected, yields only monomer emission. This study includes confirming of host-guest complexation by NMR, probing the host-guest structure by molecular dynamics simulation, following the dynamics AN molecules in the excited state by ultrafast time-resolved experiments, and mapping of the excited surface through quantum chemical calculations (QM/MM-TDDFT method). Importantly, time-resolved emission experiments revealed the excimer emission maximum to be time dependent. This observation is unique and is not in line with the textbook examples of time-independent monomer-excimer emission maxima of aromatics in solution. The presence of at least one intermediate between the monomer and the excimer is inferred from time-resolved area normalized emission spectra. Potential energy curves calculated for the ground and excited states of two adjacent anthracene molecules via the QM/MM-TDDFT method support the model proposed on the basis of time-resolved experiments. The results presented here on the excited-state behavior of a well-investigated aromatic molecule, namely the parent anthracene, establish that the behavior of a molecule drastically changes under confinement. The results presented here have implications on the behavior of molecules in biological systems.

Remote electron and energy transfer sensitized photoisomerization of encapsulated stilbenes.

Excited state chemistry and physics of molecules, in addition to their inherent electronic and steric features, depend on their immediate microenvironments. This study explores the influence of an organic capsule, slightly larger than the reactant molecule itself, on the excited state chemistry of the encapsulated molecule. Results presented here show that the confined molecule, in fact, is not isolated and can be manipulated from outside even without direct physical interaction. Examples where communication between a confined molecule and a free molecule present outside is brought about through electronic and energy transfer processes are presented. Geometric isomerization of octa acid encapsulated stilbenes induced by energy and electron transfer by cationic sensitizers that attach themselves to the anionic capsule is examined. The fact that isomerization occurs when the sensitizer present outside is excited illustrates that the reactant and sensitizer are communicating across the molecular wall of the capsule. Ability to remotely activate a confined molecule opens up new opportunities to bring about reactions of confined radical ions and triplet excited molecules generated via long distance energy and electron transfer processes.

Competing pathways for photoremovable protecting groups: the effects of solvent, oxygen and encapsulation.

Extending the applications of Photoremovable Protecting Groups (PPGs) to "cage" phenols has generally met with unusually complex PPG byproducts. In this study, we demonstrate that the p-hydroxyphenacyl (pHP) cage for both simple and complex phenolics, including tyrosine, dispenses free phenols. With the simpler unsubstituted phenols, the reaction is governed by their Brønsted Leaving Group ability. On the other hand, the byproducts of the cage vary with these phenols. For the more acidic phenols the cage byproduct follows the Favorskii rearrangement to form p-hydroxyphenylacetic acid whereas for the weaker phenols other reactions such as reduction and hydrolysis begin to emerge. When the photolysis is conducted in octa acid (OA) containers, non-Favorskii, unrearranged fragments of the cage and other byproducts arise.

Marcus Relationship Maintained During Ultrafast Electron Transfer Across a Supramolecular Capsular Wall.

Photoinduced electron transfer across an organic capsular wall between excited donors and ground-state acceptors is established to occur with rate constants varying in the range 0.32-4.0 × 1011 s-1 in aqueous buffer solution. The donor is encapsulated within an anionic supramolecular capsular host, and the cationic acceptor remains closer to the donor separated by the organic frame through Coulombic attraction. Such an arrangement results in electron transfer proceeding without diffusion. Free energy of the reaction (ΔG°) and the rate of electron transfer show Marcus relation with inversion. From the plot, λ and Vel were estimated to be 1.918 and 0.0058 eV, respectively. Given that the donor remains within the nonpolar solvent-free confined space, and there is not much change in the environment around the acceptor, the observed λ is believed to be because of "internal" reorganization rather than "solvent" reorganization. A similarity exists between the capsular assembly investigated here and glass and crystals at low temperature where the medium is rigid. The estimated electronic coupling (Vel) implies the existence of interaction between the donor and the acceptor through the capsular wall. Existence of such an interaction is also suggested by 1H NMR spectra. Results of this study suggest that molecules present within a confined space could be activated from outside. This provides an opportunity to probe the reactivity and dynamics of radical ions within an organic capsule.

Supramolecular photochemistry of encapsulated caged ortho-nitrobenzyl triggers.

ortho-Nitrobenzyl (oNB) triggers have been extensively used to release various molecules of interest. However, the toxicity and reactivity of the spent chromophore, o-nitrosobenzaldehyde, remains an unaddressed difficulty. In this study we have applied the well-established supramolecular photochemical concepts to retain the spent trigger o-nitrosobenzaldehyde within the organic capsule after release of water-soluble acids and alcohols. The sequestering power of organic capsules for spent chromophores during photorelease from ortho-nitrobenzyl esters, ethers and alcohols is demonstrated with several examples.

Room-Temperature Phosphorescence from Encapsulated Pyrene Induced by Xenon.

Phosphorescence from pyrene especially at room temperature is uncommon. This emission was recorded utilizing a supramolecular organic host and the effect due to the heavy atom. Poor intersystem crossing from S1 to T1, small radiative rate constant from T1, and large rate constant for oxygen quenching hinder the phosphorescence of aromatic molecules at room temperature in solution. In this study, these limitations are overcome by encapsulating a pyrene molecule within a water-soluble capsule (octa acid, OA) and purging with xenon. While OA suppressed oxygen quenching, xenon enabled the intersystem crossing from S1 to T1 and radiative process from T1 to S0 through the well-known heavy atom effect. The close interaction facilitated between the pyrene and the heavy atom perturber xenon in the three-component supramolecular assembly (OA, pyrene, and xenon) resulted in phosphorescence from pyrene. Computational modeling and NMR studies supported the postulate that pyrene and more than one molecule of xenon are present within a confined space of the OA capsule.

Implication of the Whitefly, Bemisia tabaci, Collagen Protein in Begomoviruses Acquisition and Transmission.

Begomoviruses are the largest group of plant viruses transmitted exclusively by the whitefly, Bemisia tabaci (Gennadius), in a persistent, circulative, and nonpropagative manner. Begomoviruses in association with B. tabaci cause enormous loss to world agricultural crops. Transmission, retention, and circulation of begomovirus in B. tabaci are facilitated by its interaction with several proteins of the insect and its endosymbionts. However, very few such proteins have been identified from B. tabaci that are involved in this specific interaction. Here, we have performed yeast two-hybrid assay between B. tabaci complementary DNA expression library and the coat protein (CP) of tomato leaf curl New Delhi virus (ToLCNDV) and cotton leaf curl Rajasthan virus (CLCuV). Collagen was the common protein found to be interacting with both of the viruses. The collagen protein was found to be localized in gut layers of B. tabaci. Additionally, pull-down and dot-blot assays confirmed the association of endogenous collagen with ToLCNDV CP. Immunolocalization analysis also showed colocalization of ToLCNDV particles and collagen within insect gut. Finally, B. tabaci fed on anticollagen antibody and exhibited ∼46% reduction in ToLCNDV transmission, suggesting a supportive role for collagen in virus transmission.

A Bemisia tabaci midgut protein interacts with begomoviruses and plays a role in virus transmission.

Begomoviruses are a major group of plant viruses, transmitted exclusively by Bemisia tabaci (Gennadius) in a persistent circulative non-propagative manner. The information regarding molecular and cellular basis underlying Begomovirus - whitefly interaction is very scarce. Evidences have suggested that the insect gut possesses some crucial protein receptors that allow specific entry of virus into the insect haemolymph. We have performed yeast two hybrid gut cDNA expression library screening against coat protein of Tomato leaf curl New Delhi virus (ToLCV) and Cotton leaf curl Rajasthan virus (CLCuV) as bait. Midgut protein (MGP) was the common protein found interacting with both ToLCV and CLCuV. MGP was localized in whole mount B. tabaci as well as in dissected guts through confocal microscopy. Pull down and dot blot assays confirmed in vitro interaction between ToLCV/CLCuV coat protein and MGP. Immunolocalization analysis also showed colocalization of ToLCV/CLCuV particles and MGP within insect's gut. Finally, anti-MGP antibody fed B. tabaci, exhibited 70% reduction in ToLCV transmission, suggesting a supportive role for MGP in virus transmission.

Correction: Photoinduced electron transfer across an organic molecular wall: octa acid encapsulated ESIPT dyes as electron donors.

Correction for 'Photoinduced electron transfer across an organic molecular wall: octa acid encapsulated ESIPT dyes as electron donors' by Fabiano S. Santos et al., Photochem. Photobiol. Sci., 2017, 16, 840-844.

Photoinduced electron transfer across an organic molecular wall: octa acid encapsulated ESIPT dyes as electron donors.

Efficient photoinduced electron transfer from proton transfer dyes encapsulated within water soluble supramolecular host octa acid to electron acceptors present outside the capsule was observed in aqueous solution. 4,4'-Dimethylviologen dichloride was found to be the best acceptor compared to N-methylpyridinium iodide, most likely due to its better binding with the exterior of the host octa acid walls [corrected].

Adenylate cyclase in Arthrospira platensis responds to light through transcription.

Cyclic 3',5' adenosine monophosphate (cAMP) is a ubiquitous signaling molecule, but its role in higher plants was in doubt due to its very low concentration. In this study we wanted to look at the flux of cAMP in response to light in algae, considered to be the more primitive form of photosynthetic organisms. While it did not fluctuate very much in the tested green algae, in the cyanobacterium Arthrospira platensis its level was closely linked to exposure to light. The expression from cyaC, the major isoform of adenylate cyclase was strongly influenced by exposure of the cells to light. There was about 300 fold enhancement of cyaC transcripts in cells exposed to light compared to the transcripts in cells in the dark. Although post-translational regulation of adenylate cyclase activity has been widely known, our studies suggest that transcriptional control could also be an important aspect of its regulation in A. platensis.

Supramolecular Surface Photochemistry: Cascade Energy Transfer between Encapsulated Dyes Aligned on a Clay Nanosheet Surface.

Three coumarin derivatives (7-propoxy coumarin, coumarin-480, and coumarin-540a, 2, 3, and 4, respectively) having different absorption and emission spectra were encapsulated within a water-soluble organic capsule formed by the two positively charged ammonium-functionalized cavitand octaamine (OAm, 1). Guests 2, 3, and 4 absorb in ultraviolet, violet, and blue regions and emit in violet, blue, and green regions, respectively. Energy transfer between the above three coumarin@(OAm)2 complexes assembled on the surface of a saponite clay nanosheet was investigated by steady-state and time-resolved emission techniques. Judging from their emission and excitation spectra, we concluded that the singlet-singlet energy transfer proceeded from 2 to 3, from 2 to 4, and from 3 to 4 when OAm-encapsulated 2, 3, and 4 were aligned on a clay surface as two-component systems. Under such conditions, the energy transfer efficiencies for the paths 2* to 3, 2* to 4, and 3* to 4 were calculated to be 33, 36, and 50% in two-component systems. When all three coumarins were assembled on the surface and 2 was excited, the energy transfer efficiencies for the paths 2* to 3, 2* to 4, and 3* to 4 were estimated to be 32, 34, and 33%. A comparison of energy transfer efficiencies of the two-component and three-component systems revealed that excitation of 2 leads to emission from 4. Successful merging of supramolecular chemistry and surface chemistry by demonstrating novel multi-step energy transfer in a three-component dye encapsulated system on a clay surface opens up newer opportunities for exploring such systems in an artificial light-harvesting phenomenon.

Supramolecular photochemistry: from molecular crystals to water-soluble capsules.

Photochemical and photophysical behavior of molecules in supramolecular assemblies are different and more selective than in gas and isotropic solution phases. Knowledge of the inherent electronic and steric properties of the reactant is insufficient to predict the excited state behavior of molecules confined in such assemblies. Weak interactions between the medium and the reactant as well as the free space in a reaction cavity would play a significant role in modulating the excited state properties of molecules when they are included within confined spaces. The concepts of 'Molecular Photochemistry' should be modified while applying them to 'Supramolecular Photochemistry'. In this review we show that the topochemical rules established to understand reactions in crystals could be extended to supramolecular assemblies in general. To make the best use of the medium one needs to understand the features of the medium, the nature of interaction between the medium and the molecule and the rules that govern the behavior of a molecule in that medium. This tutorial provides introduction to these aspects of 'Supramolecular Photochemistry'.

Supramolecular Photochemistry in Solution and on Surfaces: Encapsulation and Dynamics of Guest Molecules and Communication between Encapsulated and Free Molecules.

Supramolecular assemblies that help to preorganize reactant molecules have played an important role in the development of concepts related to the control of excited-state processes. This has led to a persistent search for newer supramolecular systems (hosts), and this review briefly presents our work with octa acid (OA) to a host to control excited-state processes of organic molecules. Octa acid, a water-soluble host, forms 1:1, 2:1, and 2:2 (host-guest) complexes with various organic molecules. A majority of the guest molecules are enclosed within a capsule made up of two molecules of OA whereas OA by itself remains as a monomer or aggregates. Luminescence and (1)H NMR spectroscopy help to characterize the structure and dynamics of these host-guest complexes. The guest molecule as well as the host-guest complex as a whole undergoes various types of motion, suggesting that the guests possess freedom inside the confined space of the octa acid capsule. In addition, the confined guests are not isolated but are able to communicate (energy, electron, and spin) with molecules present closer to the capsule. The host-guest complexes are stable even on solid surfaces such as silica, clay, α-Zr phosphate, TiO2, and gold nanoparticles. This opens up new opportunities to explore the interaction between confined guests and active surfaces of TiO2 and gold nanoparticles. In addition, this allows the possibility of performing energy and electron transfer between organic molecules that do not adsorb on inert surfaces of silica, clay, or α-Zr phosphate. The results summarized here, in addition to providing a fundamental understanding of the behavior of molecules in a confined space provided by the host OA, are likely to have a long-range effect on the capture and release of solar energy.

Taxonomy of Fulgoraecia melanoleuca (Fletcher, 1939), (Lepidoptera: Epipyropidae) in India, a biological control agent of Pyrilla perpusilla (Walker) (Hemiptera: Lophopidae).

The parasitic lepidopteran insect, Fulgoraecia melanoleuca (Fletcher) has been reported as an ectoparasitoid of Pyrilla perpusilla (Walker) from the Indian subcontinent. For the first time, the complete morphology, field biology, egg laying behavior, larval pupal, and adult morphology, including male and female gentialic features, are described and illustrated.

Photophysical studies of an encapsulated neutral guest intercalated into the 2-dimensional space of α-Zr(IV) phosphate.

Our long-range objective of developing surface anchored supramolecular assemblies as artificial light harvesting systems led us to explore the intercalation of guest molecules confined within octaamine hydrochloride (OAm·HCl) in the 2-dimensional galleries of layered inorganic material α-Zr(IV)phosphate (α-ZrP). Photophysical properties of 4,4'-dimethylbenzil, camphorthione, 4,4'-dimethylstilbene, pyrene and coumarin-1 were used to probe the intercalation behavior of OAm capsules within the galleries of α-ZrP. (1)H NMR and emission spectral investigations suggested the inclusion of guests within OAm and also confirmed the stability of host-guest complexes under acidic conditions in water. Stirring guest encapsulated OAm capsule with exfoliated α-ZrP nanosheets resulted in intercalation of the host-guest assembly as a whole in the case of 4,4'-dimethylbenzil, camphorthione, and 4,4'-dimethylstilbene as guests. According to powder X-ray diffraction and emission data these capsules are stable in the galleries of α-ZrP. The fact that the capsules are stable and can be included in α-ZrP nanosheets opens up further opportunities to explore inclusion of two different capsules, one with a donor and the other with an acceptor, and study the energy and electron transfer phenomenon between neutral molecules in α-ZrP galleries.

Role of hydrogen bonds in molecular packing of photoreactive crystals: templating photodimerization of protonated stilbazoles in crystalline state with a combination of water molecules and chloride ions.

A difference in photobehavior and molecular packing between hydrated and anhydrous crystals of protonated trans-stilbazoles has been identified. While stilbazoles are not photoreactive in the crystalline state, upon protonation with HCl in the solid state they dimerized to a single dimer (anti-head-tail) when exposed to UV light. In these photoreactive crystals the protonated stilbazole molecules are arranged in a ladder-like format with the rungs made up of water molecules and chloride ions. A combination of water and chloride ion holds the protonated trans-stilbazoles through either N-HO or N-HCl(-) interactions. Anhydrous protonated stilbazole crystals prepared by heating the 'wet' crystals under reduced pressure were inert upon exposure to UV light. As per X-ray crystal structure analyses these light stable crystals did not contain water molecules in their lattice. The current investigation has established that water molecules are essential for photodimerization of crystalline protonated trans-stilbazoles. To compare the reactivity of protonated trans-stilbazoles with that of protonated cis-stilbazoles, photoreactivity and packing arrangement of cis-4-iodo stilbazole·HCl salt was examined. This molecule in the crystalline state only isomerized to the trans isomer and did not dimerize. Thus, while the trans isomer dimerized and did not isomerize, the cis isomer only isomerized and did not dimerize in the crystalline state. To probe the role of cationπ interaction in the packing of protonated trans-stilbazoles, energies of various types of packing in the gas phase were estimated by MP-2 calculations and cationπ interaction was found to be unimportant in the packing of protonated trans-stilbazole crystals investigated here.

Excited state chemistry of flavone derivatives in a confined medium: ESIPT emission in aqueous media.

The excited state behavior of two flavone derivatives 3-hydroxyflavone and 4'-N,N-diethylaminoflavonol in a confined medium indicates that supramolecular effects could alter the nature of the fluorescence emission. Within the octa acid host the neutral unionized species of these two dyes are present showing large Stokes shifted emission due to intramolecular proton transfer, a pattern different from that in aqueous medium.

Photoisomerization and photooxygenation of 1,4-diaryl-1,3-dienes in a confined space.

Geometric isomerization of light-activated olefins plays a significant role in biological events as well as in modern materials science applications. In these systems, the isomerization occurs in highly confined spaces, and concepts derived from solution investigations are only partially applicable. This study makes contributions in understanding the excited-state behavior of olefins in confined spaces by investigating the excited-state behavior of 1,4-diphneyl-13-butadiene (DPB) and 1,4-ditolyl-1,3-butadiene (DTB) encapsulated in a well-defined organic capsule made up of the octa acid (OA) host. Both of these dienes that exist in three isomeric forms (trans,trans; trans,cis; and cis,cis) formed 1:2 guest-host complexes with OA in aqueous borate buffer. Competition experiments monitored by (1)H NMR signals revealed that among the three isomers the cis,cis isomer of DPB and DTB formed the most stable complex with OA. Molecular modeling studies suggested that all six isomers of DPB and DTB preferred the cisoid conformation within the OA capsule. Irradiation (>280 nm) of the diene-OA complex (diene@OA2) resulted in geometric isomerization, and the photostationary state consisted of cis,trans isomer as major and cis,cis as minor products. The photostationary state could be enriched with the cis,cis isomer in yields close to 70% with proper cutoff filters because the cis,cis isomer absorbs at shorter wavelength than the other two isomers. Consistent with the MD simulation prediction that trans,trans-DPB and trans,trans-DTB existed in cisoid conformation within OA capsule, the generation of singlet oxygen in the presence of OA encapsulated DPB or DTB resulted in facile [4 + 2] addition between the diene and the singlet oxygen.

Flea weevils of the genus Megorchestes Kojima (Coleoptera, Curculionidae, Curculioninae, Rhamphini), with description of a second species from India.

A second species of Megorchestes Kojima, M. deccanensis sp. nov., is described from India and a key to the two species is provided.