3 + 2]-cycloaddition of nonstabilized azomethine ylides. 10. An efficient strategy for the construction of x-Azatricyclo[m.n.0. 0

Various new structural entities related to x-azatricyclo[m.n.0. 0(a)()(,)(b)()]alkanes are constructed by the intramolecular [3 + 2] dipolar cycloaddition of nonstabilized cyclic azomethine ylides. The ylide is generated by the sequential double desilylation of N-alkyl alpha,alpha'-bis(trimethylsilyl)cyclic amines using Ag(I)F as a one-electron oxidant.     

Conformational effects on vibronic spectra and excited state dynamics of 3-fluorobenzoic acid dimer

Two conformational isomers of 3-fluorobenzoic acid dimer (3-FBA(2)) have been identified in a supersonic jet expansion by use of laser-induced fluorescence excitation (FE), UV-UV hole-burning, and dispersed fluorescence (DF) spectroscopic methods. In the FE spectrum, the S(1) origins of the two isomeric species appear at a frequency gap of only 24 cm(-1), and the vibronic intensities of the redshifted dimer (dimer I) are about two times weaker than those of dimer II. However, ab initio quantum chemistry calculations at the MP2/6-31G(**) level of theory predict that all the isomeric species of 3-FBA(2) have almost the same binding energy (approximately 17 kcal/mol) in the ground state. Furthermore, unlike benzoic acid dimer, the present system shows intense activity for a low-frequency mode in both the FE and DF spectra. With the aid of DFT (B3LYP/6-311G(**)) predicted normal mode frequencies, we have assigned the mode to the in-plane gear (cogwheel) vibration of the cyclic hydrogen-bonded frame of the dimer. The Franck-Condon profiles for vibronic excitation of the mode indicate that the distortion of the cyclic hydrogen bond frame as a result of S(1)<--S(0) excitation is larger for dimer I than dimer II. Moreover, the fluorescence lifetime at the S(1) zero-point level of the former is also significantly smaller than the latter. Using the predictions of configuration interaction singles calculations, we have proposed that the spectral and dynamical differences between the two isomeric species observed in this study are manifestations of the different characteristics of their S(1) surfaces. By measuring FE, DF, and hole-burning spectra of a mixed dimer between 3-fluobenzoic acid and benzoic acid we have shown that the isomeric features in the homodimer spectra are due to two locally excited rotamers of the 3-fluorobenzoic acid moiety.     

New phenylethanoid glycosides from Bacopa monniera

Three new phenylethanoid glycosides, viz. monnierasides I-III (1-3) along with the known analogue plantainoside B were isolated from the glycosidic fraction of Bacopa monniera. Their structures were elucidated mainly on the basis of two dimensional (2D) NMR spectral analyses.     

Multifunctional magnetic calcium phosphate nanoparticles for targeted platin delivery

Magnetic mesoporous amorphous calcium phosphate nanoparticles with a size of 62 nm and abundant -COOH groups on the surface have been prepared by a simple method. The particles show excellent aqueous dispersion stability in physiological pH without any deterioration in hydrodynamic size and zetapotential. By virtue of the carboxylate groups on the surface, the platinum pharmacophore cis-diaquadiamine platinum(ii), folic acid and rhodamine isothiocyanate were conjugated on these magnetic calcium phosphate nanoparticles. The cytotoxicity and internalization efficiency of these nanocarriers have been evaluated on folate receptor overexpressed HeLa cells. These drug loaded nanoagents exhibit elevated cytotoxicity and induce apoptosis in HeLa cells.     

Full spin and spatial symmetry adapted technique for correlated electronic hamiltonians: Application to an icosahedral cluster

One of the long standing problems in quantum chemistry had been the inability to exploit full spatial and spin symmetry of an electronic Hamiltonian belonging to a non‐Abelian point group. Here, we present a general technique which can utilize all the symmetries of an electronic (magnetic) Hamiltonian to obtain its full eigenvalue spectrum. This is a hybrid method based on Valence Bond basis and the basis of constant z‐component of the total spin. This technique is applicable to systems with any point group symmetry and is easy to implement on a computer. We illustrate the power of the method by applying it to a model icosahedral half‐filled electronic system. This model spans a huge Hilbert space (dimension 1,778,966) and in the largest non‐Abelian point group. The C₆₀ molecule has this symmetry and hence our calculation throw light on the higher energy excited states of the bucky ball. This method can also be utilized to study finite temperature properties of strongly correlated systems within an exact diagonalization approach. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Peptide‐poly(ε‐caprolactone) biohybrids by grafting‐from ring‐opening polymerization: Synthesis,aggregation, and crystalline properties

Well‐defined peptide‐poly(ε‐caprolactone) (Pep‐PCL) biohybrids were successfully synthesized by grafting‐from ring‐opening polymerization (ROP) of ε‐caprolactone (CL) using designed amine‐terminated sequence‐defined peptides as macroinitiators. MALDI‐TOF‐MS and ¹H NMR analyses confirmed the successful attachment of peptide to the PCL chain. The gel permeation chromatography (GPC) measurement showed that the Pep‐PCL biohybrids with controllable molecular weights and low polydispersities (PDI <1.5) were obtained by this approach. The aggregation of Pep‐PCL hybrid molecules in THF solution resulted in the formation of micro/nanospheres as confirmed through FESEM, TEM, and DLS analyses. The circular dichroism study revealed that the secondary structure of peptide moiety was changed in the peptide‐PCL biohybrids. The crystallization and melting behavior of Pep‐PCL hybrids were somewhat changed compared with that of neat PCL of comparable molecular weight as revealed by DSC and XRD measurements. In Pep‐PCL biohybrids, extinction rings were observed in the PCL spherulites, in contrast with the normal spherulite morphology of the neat PCL. There was a substantial decrease (4–5 folds) in the spherulitic growth rate after the incorporation of peptide moiety at the end of PCL chain as measured by polarizing optical microscopy. Pseudomonas lipase catalyzed enzymatic degradation was studied for Pep‐PCL hybrids and neat PCL. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Vitamin B6 cofactor derived chemosensor for the selective colorimetric detection of acetate anions

A novel vitamin B₆ cofactor derived anion sensor L for the selective colorimetric detection of acetate has been developed by the condensation of pyridoxal and 2-aminothiophenol. The sensor L showed a noteworthy change in the visible region of the spectrum and was detected by the ‘naked-eye’ for both acetate and fluoride anions in DMSO but selectively for acetate in DMSO/H₂O (88:12, v/v). The anion recognition ability of L was investigated by spectroscopic (UV–vis and ¹H NMR) and DFT methods.     

Sensing of Phosphates by Using Luminescent EuIII and TbIII Complexes: Application to the Microalgal Cell Chlorella vulgaris

Phenanthroline‐based chiral ligands L¹ and L² as well as the corresponding Eu^III and Tb^III complexes were synthesized and characterized. The coordination compounds show red and green emission, which was explored for the sensing of a series of anions such as F^?, Cl^?, Br^?, I^?, NO₃^?, NO₂^?, HPO₄^2?, HSO₄^?, CH₃COO^?, and HCO₃^?. Among the anions, HPO₄^2? exhibited a strong response in the emission property of both europium(III) and terbium(III) complexes. The complexes showed interactions with the nucleoside phosphates adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP). Owing to this recognition, these complexes have been applied as staining agents in the microalgal cell Chlorella vulgaris. The stained microalgal cells were monitored through fluorescence microscopy and scanning electron microscopy. Initially, the complexes bind to the outer cell wall and then enter the cell wall through holes in which they probably bind to phospholipids. This leads to a quenching of the luminescence properties.     

Amine‐Responsive Adaptable Nanospaces: Fluorescent Porous Coordination Polymer for Molecular Recognition

Flexible and dynamic porous coordination polymers (PCPs) with well‐defined nanospaces composed of chromophoric organic linkers provide a scaffold for encapsulation of versatile guest molecules through noncovalent interactions. PCPs thus provide a potential platform for molecular recognition. Herein, we report a flexible 3D supramolecular framework {[Zn(ndc)(o‐phen)]?DMF}_n (o‐phen=1,10‐phenanthroline, ndc=2,6‐napthalenedicarboxylate) with confined nanospaces that can accommodate different electron‐donating aromatic amine guests with selective turn‐on emission signaling. This system serves as a molecular recognition platform through an emission‐readout process. Such unprecedented tunable emission with different amines is attributed to its emissive charge‐transfer (CT) complexation with o‐phen linkers. In certain cases this CT emission is further amplified by energy transfer from the chromophoric linker unit ndc, as evidenced by single‐crystal X‐ray structural characterization.