A p‐Hydroxyphenacyl–Benzothiazole–Chlorambucil Conjugate as a Real‐Time‐Monitoring Drug‐Delivery System Assisted by Excited‐State Intramolecular Proton Transfer

Among the well‐known phototriggers, the p‐hydroxyphenacyl (pHP) group has consistently enabled the very fast, efficient, and high‐conversion release of active molecules. Despite this unique behavior, the pHP group has been ignored as a delivery agent, particularly in the area of theranostics, because of two major limitations: Its excitation wavelength is below 400 nm, and it is nonfluorescent. We have overcome these limitations by incorporating a 2‐(2′‐hydroxyphenyl)benzothiazole (HBT) appendage capable of rapid excited‐state intramolecular proton transfer (ESIPT). The ESIPT effect also provided two unique advantages: It assisted the deprotonation of the pHP group for faster release, and it was accompanied by a distinct fluorescence color change upon photorelease. In vitro studies showed that the p‐hydroxyphenacyl–benzothiazole–chlorambucil conjugate presents excellent properties, such as real‐time monitoring, photoregulated drug delivery, and biocompatibility.     

Pyridine based thorium(IV) phosphate hybrid fibrous ion exchanger

Pyridine based thorium(IV) phosphate (PyThP) has been synthesized by drop-wise addition of the thorium(IV) nitrate with constant stirring into a mixture of pyridine and phosphoric acid. This material has been characterized using X-ray, IR spectra, TG, DTG and SEM studies in addition to its ion exchange capacity, elution and pH titrations. The material has been found amorphous and fibrous in nature on the basis of X-ray diffraction and SEM studies. TG has revealed the changes incurred in the material on thermal treatment and IR spectral studies have shown the presence of various groups in its structure.     

Interaction of azide ion with hemin and cytochrome c immobilized on Au and Ag nanoparticles

This paper presents a set of investigations on the binding of a metabolic inhibitor, azide with prosthetic heme group of biomolecules, hemin chloride (Hem) and cytochrome c (Cyt c) immobilized on Au and Ag nanoparticles. A variety of spectroscopic tools have been used to understand the chemistry occurring on the nanoparticle surface. While the nature of binding of the model system, hemin has been investigated by UV-visible, fluorescence, FTIR, and Raman spectroscopies, the azide binding has been studied in detail by MALDI-TOF MS. Hemin binding on the nanoparticle surface occurs through the carboxylic acid groups. The hemin-N(3) adduct on the nanoparticle surface has been detected by mass spectrometry and its fragments have been studied by post source decay analysis. The chemistry of hemin on the nanoparticle surface has been compared with that of the protein, Cyt c. Azide binding of Cyt c requires thermal activation due to reduced accessibility of the heme center, unlike in the case of hemin. The binding chemistry is similar for free Cyt c and Cyt c bound to the nanoparticles.     

Formation of bifunctional cross-linked products due to reaction of NAMI-A with DNA bases – a DFT study

Structural Chemistry - It is reported that NAMI-A and other Ru-anticancer complexes preferably bind with the N7 site of guanine and can also form DNA inter-strand cross-links. Therefore, in order...     

Kinetics of ion-exchange of transition metals on tin(IV) arseno-silicate cation exchanger

Exchange kinetics of some transition metal ions on tin(IV) arsenosilicate has been studied at various temperatures under particle diffusion controlled conditions. Various useful kinetic parameters such as self-diffusion coefficient (D_o), energy of activation (E_a) and entropy of activation (S^*) have been calculated and compared with other similar materials.

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(IV) . , (D_O), (E_a) (S^*), .

     

Effect of beta-cyclodextrin nanocavity confinement on the photophysics of robinetin

We have studied the confinement of robinetin, a therapeutically active plant flavonol, in cyclodextrin (CDx) nanocavities, using steady state and time resolved fluorescence spectroscopy. Enhanced tautomer emission (arising from excited state intramolecular proton transfer (ESIPT)) as well as dramatically blue shifted (approximately 10 nm in beta-CDx and approximately 33 nm in SHP beta-CDx) normal fluorescence observed upon addition of the beta-CDxs indicate that robinetin readily enters the doughnut-shaped hydrophobic cavity of beta-CDx where the chromone moiety is well shielded from external hydrogen bonding perturbations. Detailed analyses of the fluorescence data (emission profile, anisotropy, decay times) indicate that robinetin forms 1:1 inclusion complexes with both natural and chemically modified beta-cyclodextrins (beta-CDx and SHP beta-CDx) with affinity constant values K=195+/-17 M(-1) and 1055+/-48 M(-1) respectively, indicating the prospective utility of SHP beta-CDx in particular as an effective drug carrier. Unlike beta-CDxs, alpha-CDxs do not form inclusion complexes with robinetin. To further characterize the robinetin/beta-CDxs complexes, circular dichroism (CD) spectroscopic studies have been performed, which reveal that incorporation of robinetin molecules in the chiral environment of the beta-CDxs strongly affects the electronic transitions of robinetin leading to the occurrence of positive induced circular dichroism (ICD) bands in the near ultra-violet (UV) region. Molecular mechanics calculations show that the inclusion complex with the chromone ring inserted into the beta-CDx cavity is most favorable, in agreement with our spectroscopic data.     

Mixed chelates of some trivalent lanthanide ions containing (trans-1,2-cyclhexylenedinitrilo)tetraacetate and norleucinate

Summary Formation constants of mixed chelates with (trans-1,2-cyclohexylenedinitrilo)tetra-acetate (DCTA) as primary ligand and norleucinate (nle) as secondary ligand with metal ions La(III), Ce(III), Pr(III), Sm(III), Gd(III), Tb(III), Dy(III), Er(III), and Yb(III) have been determined by the modified potentiometricpH titration method of Irving-Rossotti in aqueous medium at (295±1) K and fixed ionic strength of =0.1M (NaClO₄). Formation constants of binary complexes of the metal ions with the secondary ligand have also been determined under identical conditions. The mixed chelates were found to be more stable than the binary ones. The order of stabilities in terms of metal ions is La(III)Gd(III)

Gemischte Chelate einiger dreiwertiger Lanthanidenionen mit (trans-1,2-Cyclohexylendinitril)tetraacetat und Norleucinat

Zusammenfassung Es wurden die Komplexbildungskonstanten gemischter Chelate mit (trans-1,2-Cyclohexylendinitril)tetraacetat als Primärkomponente und Norleucinat als Sekundärkomponente mit den Metallionen La(III), Ce(III), Pr(III), Sm(III), Gd(III), Tb(III), Dy(III), Er(III) und Yb(III) mittels einer modifizierten potentiometrischen Titrationsmethode nach Irving-Rossotti in wäßrigem Medium bei (295±1) K und einer konstanten Ionenstärke von =0.1M (NaClO₄) bestimmt. Die Bildungskonstanten der binären Komplexe der Metallionen mit dem Sekundärliganden wurden ebenfalls unter identen Bedingungen bestimmt. Es wurde festgestellt, daß die gemischten Chelate stabiler sind als die binären. Die Stabilitätsreihenfolge bezüglich der Metallionen ist La(III)Gd(III)     

Synthetic Heparanase Inhibitors Can Prevent Herpes Simplex Viral Spread

Herpes simplex virus (HSV-1) employs heparan sulfate (HS) as receptor for cell attachment and entry. During late-stage infection, the virus induces the upregulation of human heparanase (Hpse) to remove cell surface HS allowing viral spread. We hypothesized that inhibition of Hpse will prevent viral release thereby representing a new therapeutic strategy for HSV-1. A range of HS-oligosaccharides was prepared to examine the importance of chain length and 2-O-sulfation of iduronic moieties for Hpse inhibition. It was found that hexa- and octasaccharides potently inhibited the enzyme and that 2-O-sulfation of iduronic acid is tolerated. Computational studies provided a rationale for the observed structure–activity relationship. Treatment of human corneal epithelial cells (HCEs) infected with HSV-1 with the hexa- and octasaccharide blocked viral induced shedding of HS which significantly reduced spread of virions. The compounds also inhibited migration and proliferation of immortalized HCEs thereby providing additional therapeutic properties.     

Synthesis and structural characterisation of a novel tris-methylene bridged compound (NO) 4Fe2 Se(μ-CH2)3

The tris-methylene bridged compound (NO)₄Fe₂Se(μ-CH₂)₃ has been isolated. It has been characterised by IR and ¹H, ¹³C, and ⁷⁷Se NMR spectroscopy. Its structure has been determined by single-crystal X-ray diffraction methods. The structure consists of a heavy atom triangle consisting of one Se and two Fe atoms. The Fe-Fe and the two Fe-Se edges are bridged by methylene groups.