Albumin–Folate Conjugates for Drug‐targeting in Photodynamic Therapy

Photodynamic therapy (PDT) is based on the cytotoxicity of photosensitizers in the presence of light. Increased selectivity and effectivity of the treatment is expected if a specific uptake of the photosensitizers into the target cells, often tumor cells, can be achieved. An attractive transporter for that purpose is the folic acid receptor α (FRα), which is overexpressed on the surface of many tumor cells and mediates an endocytotic uptake. Here, we describe the synthesis and photobiological characterization of polar β‐carboline derivatives as photosensitizers covalently linked to folate‐tagged albumin as the carrier system. The particles were taken up by KB (human carcinoma) cells within <90 min and then co‐localized with a lysosomal marker. FRα antibodies prevented the uptake and also the corresponding conjugate without folate was not taken up. Accordingly, a folate‐albumin‐β‐carbolinium conjugate proved to be phototoxic, while the corresponding albumin–β‐carbolinium conjugates without FA were nontoxic, both with and without irradiation. An excess of free folate as competitor for the FRα‐mediated uptake completely inhibited the photocytotoxicity. Interestingly, the albumin conjugates are devoid of photodynamic activity under cell‐free conditions, as shown for DNA as a target. Thus, phototoxicity requires cellular uptake and lysosomal degradation of the conjugates. In conclusion, albumin–folate conjugates appear to be promising vehicles for a tumor cell targeted PDT.     

Organocatalytic Asymmetric Addition of Naphthols and Electron‐Rich Phenols to Isatin‐Derived Ketimines: Highly Enantioselective Construction of Tetrasubstituted Stereocenters

A quinine‐derived thiourea organocatalyst promoted the highly enantioselective addition of naphthols and activated phenols to ketimines derived from isatins. The reaction afforded chiral 3‐amino‐2‐oxindoles with a quaternary stereocenter in high yields (up to 99 %) with excellent enantioselectivity (up to 99 % ee). To the best of our knowledge, this transformation is the first highly enantioselective addition of naphthols to ketimines.     

Transition metal complexes with thiosemicarbazide-based ligand – Part LV: Synthesis and X-ray structural study of novel Ni(II) complexes with pyridoxal semicarbazone and pyridoxal thiosemicarbazone

Reaction of aqueous solutions of Ni(NO₃)₂ and pyridoxal semicarbazone (PLSC) in the presence of NaN₃ afforded two complexes, viz. green, paramagnetic binuclear octahedral [Ni₂(PLSC)₂(μ_1,1-N₃)₂(N₃)₂] · 2H₂O (1) and, as admixture, red, octahedral [Ni(PLSC–H)₂] · 2H₂O (2) complex. Under the same reaction conditions, pyridoxal thiosemicarbazone (PLTSC) gave only one diamagnetic square-planar, red complex [Ni(PLTSC–H)N₃] · H₂O (3). In the absence of NaN₃, the reaction of PLTSC and Ni(NO₃)₂ yielded brown paramagnetic octahedral complex [Ni(PLTSC)₂](NO₃)₂ · H₂O (4).     

From chain collapse to new structures: spectroscopic properties of poly(3-thiophene acetic acid) upon binding by alkyl trimethylammonium bromide surfactants

The binding of cationic surfactants with varying alkyl chain length to a regiorandom conjugated polyanion, poly(3-thiophene acetic acid) (PTAA), is studied in an aqueous buffer by using absorption and emission spectroscopies, photon correlation spectroscopy, isothermal titration calorimetry, and cryogenic transmission electron microscopy. We study the mixed solutions as a function of composition ratio R of surfactant molecules to monomer units molar concentrations, at low polymer concentration and in a very wide composition range (10(-6) < R < 10(2)) below the critical micellar concentration. Upon surfactant binding, the molecularly dispersed chains first collapse progressively and then form new structures as the mixed aggregates get enriched in surfactant. The collapse leads to a strong decrease of the conjugation length and to a blue shift of the absorption spectra by 30 to 50 nm. The new structures are responsible for a new intense emission band at about 600 nm, red-shifted by nearly 130 nm from the initial emission maximum of the polymer (~472 nm). As the surfactant tail becomes shorter, the blue shift of the absorption spectra and the intensity raise of the new emission are delayed to larger composition ratios while their variations become smoother functions of the surfactant concentration. These particular spectroscopic properties of PTAA seem related to its unique combination of a strongly hydrophobic backbone, a large ratio of contour length to persistence length, and an overall good aqueous solubility. Our results show that such features are well suited to design a colorimetric biosensor at small composition ratio, and a fluorescent biomarker at large composition ratio.     

Studies on Reactivity of Pyridinium Chlorochromate — Iodine System: An Efficient Method for Converting Enol Silyl Ethers into α-Iodo Ketones

A new synthesis of α-iodo carbonyl derivatives is described. They are obtained, in very high yields, through an original and efficient procedure, by reaction of enol silyl ethers with I₂-PCC system.     

Determination of Vanadium by Solid-Phase Spectrophotometry in a Continuous Flow System

Abstract

A flow analysis method based on direct absorptiometric measurement in solid phase of the violet complex formed between V(V) and 5-Bromosalicylhydroxamic acid has been developed. The measurement is continuously performed at 555 nm, while the coloured species is being concentrated on-line on the beads of an anion exchanger packed into a flow-through cell. The sensing solid phase is regenerated after each measurement achieving a sampling frequency ranged between 10 to 15 h^?1 depending on the working conditions. The sensitivity of the method depended on the sample volume injected, being the detection limit 0.024 and 0.014 μg mL^?1 for 2 and 5 mL, respectively. The method shows a good selectivity and has been applied to determination of V(V) in many different sample matrices namely mussel, oyster and toadstool tissues, petroleum crudes and water samples.     

Low Pressure Hydrogenation of Unsaturated Sulphides with Homogeneous and Heterogeneous Ruthenium Catalysts

Ru₂O-nH₂O and [Ru₃O(AcO)₆(H₂O)3j⁺AcO-were examined for catalytic activity in the hydrogenation of a series of unsaturated sulphides under heterogeneous and homogeneous conditions, respectively. By the appropriate combination of these two methodologies, a number of saturated sulphides could be synthesized in satisfactory to good yields, thus minimizing side reactions.     

Bile enterogastric reflux sensor using plastic optical fibers

Abstract

A portable optical-fiber sensor for ambulatory assessment of the enterogastric reflux, based on the optical properties of the bile, was developed. It makes use of two light-emitting diodes and of an appropriate electronic circuit that processes the signals and provides the readout on a display. A suitable probe for in vivo measurements was designed. Plastic fiber bundles are used in order to obtain probe flexibility and low price. In vivo measurements performed on different patients show the superiority of this technique over existing methods.