Discovery of new mutually orthogonal bioorthogonal cycloaddition pairs through computational screening

Density functional theory (DFT) calculations and experiments in tandem led to discoveries of new reactivities and selectivities involving bioorthogonal sydnone cycloadditions. Dibenzocyclooctyne derivatives (DIBAC and BARAC) were identified to be especially reactive dipolarophiles, which undergo the (3 + 2) cycloadditions with N-phenyl sydnone with the rate constant of up to 1.46 M^–1 s^–1. Most significantly, the sydnone-dibenzocyclooctyne and norbornene-tetrazine cycloadditions were predicted to be mutually orthogonal. This was validated experimentally and used for highly selective fluorescence labeling of two proteins simultaneously.     

Regioselective E(trans)-Z(cis) photoisomerization in naphthyldiene derivatives

Naphthyldiene derivatives,1-4, carrying electron-donating groups at one end and electron-withdrawing groups at the other, were synthesized to study the photoisomerization process. All the compounds showed efficient photoisomerization upon direct excitation leading to the formation of 4-Z isomer with high selectivity. Triplet sensitization studies indicated inefficientE-Z isomerization process. Room temperature fluorescence of1 and2 displayed fine structure in hexane solvent and the same was replaced by broad or structureless fluorescence in acetonitrile and methanol solvents. A mechanism involving a polarized or charge transfer singlet excited state is proposed for the observed photoisomerization in these naphthyldiene derivatives.     

Redox‐Active Peptide‐Functionalized Quinquethiophene‐Based Electrochromic π‐Gel

An electrochromic system based on a self‐assembled dipeptide‐appended redox‐active quinquethiophene π‐gel is reported. The designed peptide‐quinquethiophene consists of a symmetric bolaamphiphile that has two segments: a redox‐active π‐conjugated quinquethiophene core for electrochromism, and peptide motif for the involvement of molecular self‐assembly. Investigations reveal that self‐assembly and electrochromic properties of the π‐gel are strongly dependent on the relative orientation of peptidic and quinquethiophene scaffolds in the self‐assembly system. The colors of the π‐gel film are very stable with fast and controlled switching speed at room temperature.     

FLUORESCENCE AND CIRCULAR DICHROISM STUDIES ON THE PHYCOERYTHROCYANINS FROM THE CYANOBACTERIUM

Two phycoerythrocyanin (PEC) fractions have been obtained from the phycobilisomes of the cyanobac-terium Westiellopsis prolifica ARM 365. They have been characterized by absorption, fluorescence and circular dichroism spectroscopy. One of them is spectroscopically similar to a PEC trimer known from other organisms. Whereas efficient energy transfer from its violin (α-84) to the cyanin (β-84, 155) chromophores is efficient in the trimer (αβ it is impeded after dissociation to the monomer (α,β). A second fraction of PEC which we earlier termed PEC(X) (Maruthi Sai et al., Photochem. Photobiol. 55 ,119–124, 1992), exhibited the spectral properties similar to that of the α-subunit of PEC from Mastigocladus laminosus. With this highly photoactive fraction, the circular dichroism spectra of the violobilin chromophore in both photoreversible states were obtained.     

Solvatochromic study of three indoloquinoline derivatives: Effect of chloro group/s on the photophysics of thecompounds

Photophysical modulations of three indoloquinoline derivatives, viz., 5-Methyl-5H-indolo[3,2-c]quinoline (MIQ), 8-Chloro-5-methyl-5H-indolo[3,2-c]quinoline (CMIQ), and 2,8-Dichloro-5-methyl-5H-indolo[3,2-c]quinoline (DCMIQ) have been studied. These compounds belong to the cryptosanguinolentine family and are known to have potential anti-cancer abilities. In the present work we studied the effect of solvent polarity on introduction of one or two chloro (-Cl) group/s at chosen sites on the parent cryptosanguinolentine. The compounds exist mainly in two forms, neutral and zwitterionic, in equilibrium at ground state. Interestingly, all the three compounds exhibit hypsochromic shift in their absorption and fluorescence spectra with increase in relative permittivity of solvents in most of the cases. Blue-shift in fluoroscence might be due to lesser dipole moment of the species in the excited state. Time-resolved fluorescence spectroscopy clearly indicates the presence of two species in all the solvents in the excited state (except MIQ in water). The shift in the molecular polarity with chloro substitution/s seems to be responsible for the contributions of the two species in the excited state. The relative contributions are found to alter remarkably in a regular manner when MIQ is compared with CMIQ and DCMIQ. This behavior is supposed to be mainly due to dipole-dipole interaction between the solvent molecules and the fluorophores.     

Enantioselective Synthesis of Herbarumin III by Using a Chelation‐Controlled Reduction

The total synthesis of herbarumin III ( 1 ) was achieved via an alkynide ion addition onto a chiral aldehyde and LiAlH₄/LiI reduction as key steps (Scheme 2).     

Molecular mean field theory for liquid water

Attractive bonding interactions between molecules typically have inherent conservation laws which influence the statistical properties of such systems in terms of corresponding sum rules. We have considered lattice water as an example, and we have enunciated the consequences of the sum rule through a general computational procedure called molecular mean field theory. Fluctuations about the mean field are computed and many of the liquid properties have been deduced and compared with Monte Carlo simulation, molecular dynamics, and experimental results. Large correlation lengths are seen to be a consequence of the sum rule in the liquid phase. Long-range Coulomb interactions are shown to have minor effects on our results.     

Spectral anomalies due to temporal correlation in a white-light interferometer

We present what we believe to be the first experimental demonstration of anomalous spectral behavior such as spectral shifts and spectral switches due to temporal correlation around the intensity minima in a white-light interferometer. Unusual behavior in the number of spectral fringes, measured within the source bandwidth, as a function of path delay between the interfering beams is also reported. Experimental observations match well with the spectra calculated by using the interference law in the spectral domain.     

PHYCOERYTHROCYANINS FROM Westiellopsis prolifica AND Nostoc rivulare: CHARACTERIZATION OF THE PHYCOVIOLOBILIN CHROMOPHORE IN BOTH STATES*

Abstract— Phycoerythrocyanin or fractions enriched in it have been isolated from the filamentous cyanobacteria, Westiellopsis prolifica ARM 365 and Nostoc rivulare ARM 212. Both show the photoreversible photochromism (difference maxima at 503 and 570 nm) characteristic of this pigment, which is related to the phycoviolobilin chromophore on the α-subunit. Native phycoerythrocyanin and its β-subunit show little if any reversible photochemistry in the 600–620 nm region, where the phycocyanobilin chromophores absorb maximally. Instead the phycocyanobilin chromophores are bleached irreversibly. At the same time, the data show that reversible photochemistry is a useful analytical tool to detect phycoerythrocyanin in cyanobacterial extracts. Fluorescence measurements indicate that: (i) the 510 nm absorbing isomer of the violobilin chromophore has only little fluorescence; and (ii) the energy transfer from the violobilin chromophores to the cyanin chromophores is efficient only in the 570 nm form.     

Hydrophobic force,a Casimir-like effect due to hydrogen-bond fluctuations

Hydrophobic force, interfacial tension, and transverse density profile in a confined water system are addressed from first principles of statistical mechanics in a lattice model for water. Using the molecular mean field theory technique we deduce explicit expressions for each of the above mentioned phenomena and show that hydrophobic force is a manifestation of a Casimir-like effect due to hydrogen-bond fluctuations in confined water. It is largely influenced by the long range correlations of orientational fluctuations. Furthermore, the temperature dependence of hydrophobic force between large non-polar surfaces is suggested to be different from that between small solutes. The mechanisms contributing to characteristic behavior in each case are identified. In the case of large surfaces, the prevalence of discrete fluctuation modes in the confinement direction and their entropic contribution to the overall free energy dominate the temperature dependence. Mode discretization is also implicated in the variation of interfacial tension with separation distance between confining surfaces and characteristic density profile of the confined fluid. All the computations are parameter free and compare favorably with results of molecular dynamics simulations and experiments.