Water-soluble green perylenediimide (PDI) dyes as potential sensitizers for photodynamic therapy

[reaction: see text] A series of water-soluble green perylenediimide (PDI) dyes have been synthesized. On red light excitation, these dyes were shown to be efficient generators of singlet oxygen, and in cell culture media, they were shown to display significant light-induced cytotoxic effects on the human erythroleukemia cell line (K-562). It appears that highly versatile PDI dyes are likely to find new applications in photodynamic therapy.     

Thermodynamics of folding, stabilization, and binding in an engineered protein--protein complex

We analyzed the thermodynamics of a complex protein-protein binding interaction using the (engineered) Z(SPA)(-)(1) affibody and it's Z domain binding partner as a model. Free Z(SPA)(-)(1) exists in an equilibrium between a molten-globule-like (MG) state and a completely unfolded state, wheras a well-ordered structure is observed in the Z:Z(SPA)(-)(1) complex. The thermodynamics of the MG state unfolding equilibrium can be separated from the thermodynamics of binding and stabilization by combined analysis of isothermal titration calorimetry data and a separate van't Hoff analysis of thermal unfolding. We find that (i) the unfolding equilibrium of free Z(SPA)(-)(1) has only a small influence on effective binding affinity, that (ii) the Z:Z(SPA)(-)(1) interface is inconspicuous and structure-based energetics calculations suggest that it should be capable of supporting strong binding, but that (iii) the conformational stabilization of the MG state to a well-ordered structure in the Z:Z(SPA)(-)(1) complex is associated with a large change in conformational entropy that opposes binding.     

Minute amounts of organically modified montmorillonite improve the properties of polyisobutylene‐based polyurethanes

We discovered that polyisobutylene (PIB)‐based polyurethanes (PIB‐PUs) containing minute amounts (0.5%) of chemically bound organically modified montmorillonite (OmMMT) surprisingly produce films exhibiting improved properties. The OmMMT was prepared by reacting sodium montmorillonite (Na⁺MMT^?) with quaternary ammonium salts of a tertiary amine carrying a ? NH₂ functionality. The positively charged quaternary amine group becomes electrostatically attached to negatively charged MMT layers and defoliates it, whereas the free ? NH₂ group reacts with diisocyanates and acts as an additional chain extender. Thus, when OmMMT is added to a mixture of ingredients assembled for the synthesis of PIB‐PUs, this modified clay becomes an integral part of the PU. Specifically, we found that the integration of 0.5% OmMMT to PIB‐based PUs produces films with significantly enhanced tensile strength, elongation, toughness, creep, and stress relaxation relative to that of PIB‐PUs. The findings were discussed and explained in terms of a proposed morphology for the nanocomposite. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4076–4087     

Solvent‐Catalyzed Ring–Chain–Ring Tautomerization in Axially Chiral Compounds

The mechanism of ring–chain–ring tautomerization and the prominent effect of the solvent environment have been computationally investigated in an effort to explain the enantiomeric interconversion observed in 2‐oxazolidinone derivatives, heterocyclic analogues of biphenyl atropisomers, which were isolated as single stable enantiomers and have the potential to be used as axially chiral catalysts. This study has shed light on the identity of the intermediate species involved in the ring–chain–ring tautomerization process as well as the catalytic effect of polar protic solvents. These mechanistic details will prove very useful in predicting and understanding ring–chain tautomeric equilibria in similar heterocyclic systems and will further enable experimentalists to devise appropriate experimental conditions in which axially chiral catalysts remain stable as single enantiomers.     

Identifying the Geometric Site Dependence of Spinel Oxides for the Electrooxidation of 5-Hydroxymethylfurfural

Co-based spinel oxides, which are of mixing valences with the presence of both Co²⁺ and Co³⁺ at different atom locations, are considered as promising catalysts for the electrochemical oxidation of 5-hydroxymethylfurfural (HMF). Identifying the role of each atom site in the electroxidation of HMF is critical to design the advanced electrocatalysts. In this work, we found that Co²⁺_Td in Co₃O₄ is capable of chemical adsorption for acidic organic molecules, and Co³⁺_Oh play a decisive role in HMF oxidation. Thereafter, the Cu²⁺ was introduced in spinel oxides to enhance the exposure degree of Co³⁺ and to boost acidic adsorption and thus to enhance the electrocatalytic activity for HMF electrooxidation significantly.     

Asymmetric synthesis and molecular docking study of enantiomerically pure pyrrolidine derivatives with potential antithrombin activity

The (2R,4R,5S)- and (2S,4S,5R)-enantiomers of 4-(tert-butyl) 2-methyl 5-(4-bromophenyl)-pyrrolidine-2,4-dicarboxylate 3 were synthesized efficiently with an ee of >90% on a gram scale using a FAM-catalytic methodology. Subsequent modification afforded enantiopure N-((4-chlorophenyl)thio)acetyl pyrrolidine derivatives 4, which are potential thrombin inhibitors according to comprehensive molecular docking studies.     

Why do some Fischer indolizations fail?

The mechanisms of the Fischer indole synthesis and competing cleavage pathways were explored with SCS-MP2/6-31G(d) and aqueous solvation calculations. Electron-donating substituents divert the reaction pathway to heterolytic N-N bond cleavage and preclude the acid-promoted [3,3]-sigmatropic rearrangement.     

exo-Selective inverse-electron-demand hetero Diels–Alder reactions of norbornene with 5-benzylidine-2-arylimino-3-aryl-thiazolidine-4-thiones at room temperature

2-Arylimino-3-aryl-thiazolidine-4-thiones were synthesized from the corresponding thiazolidine-4-ones using Lawesson's reagent (LR) and converted into 5-benzylidine-2-arylimino-3-aryl-thiazolidine-4-thiones by reaction with benzaldehyde, which were then used as heterodienes in the inverse-electron-demand hetero Diels–Alder cycloadditions with norbornene as a dienophile at 25 ^°C. The reactions with norbornene were found to proceed with 100% exo-selectivity as determined by NMR experiments. The hetero Diels–Alder reactions with axially chiral heterodienes with ΔG^#>116 kJ/mol showed kinetic atroposelectivities up to 11:1. However, the products were found to equilibrate, as revealed by the 97.1 kJ/mol barrier to hindered rotation of the most sterically hindered product, to produce 2:1 diastereoselectivities after the 24 h reaction time.     

Electrochemical Investigations of the Anticancer Drug Idarubicin Using Multiwalled Carbon Nanotubes Modified Glassy Carbon and Pyrolytic Graphite Electrodes

The effect of surface modifications on the electrochemical behavior of the anticancer drug idarubicin was studied at multiwalled carbon nanotubes modified glassy carbon and edge plane pyrolytic graphite electrodes. The surface morphology of the modified electrodes was characterized by scanning electron microscopy. The modified electrodes were constructed for the determination of idarubicin using adsorptive stripping differential pulse voltammetry. The experimental parameters such as supporting electrolyte, pH, accumulation time and potential, amount of carbon nanotubes for the sensitive assay of idarubicin were studied as details. Under the optimized conditions, idarubicin gave a linear response in the range 9.36×10^?8–1.87×10^?6 M for modified glassy carbon and 9.36×10^?8–9.36×10^?7 M for modified edge plane pyrolytic graphite electrodes. The detection limits were found as 1.87×10^?8 M and 3.75×10^?8 M based on modified glassy carbon and edge plane pyrolytic graphite electrodes, respectively. Interfering species such as ascorbic acid, dopamine, and aspirin showed no interference with the selective determination of idarubicin. The analyzing method was fully validated and successfully applied for the determination of idarubicin in its pharmaceutical dosage form. The possible oxidation mechanism of idarubicin was also discussed. The results revealed that the modified electrodes showed an obvious electrocatalytic activity toward the oxidation of idarubicin by a remarkable enhancement in the current response compared with bare electrodes.