Synthesis and photochemistry of beta,beta'-di(2-furyl)-substituted o-divinylbenzenes: intra- and/or intermolecular cycloaddition as an effect of annelation

New heteroaryl-substituted o-divinylbenzenes, 2,2'-(1,2-phenylenedivinylene)difuran (9), 2,2'-(1,2-phenylenedivinylene)bisbenzo[b]furan (10), and 2,2'-(1,2-phenylenedivinylene)bisnaphtho[2,1-b]furan (11), were prepared and irradiated at various concentrations; intramolecular photocycloaddition and intermolecular [2+2] twofold photoaddition reactions took place to give bicyclo[3.2.1]octadiene derivatives 12-14 and cyclophane derivatives 15-17, respectively. Compound 11 was the most selective of these o-divinylbenzenes, which, owing to pi-pi intra- or intermolecular complexation, gave only the exo-bicyclo[3.2.1]octadiene derivative 14 at low concentrations, and only the cyclophane derivative 17 at high concentrations.     

Thermally induced sign change of Soret coefficient for dilute and semidilute solutions of poly(N-isopropylacrylamide) in ethanol

We studied the thermal diffusion behavior of poly(N-isopropylacrylamide) (PNiPAM) in ethanol in a temperature range from T = 14.0 degrees C to T = 40.0 degrees C by means of thermal diffusion forced Rayleigh scattering. The obtained Soret coefficient S(T) of PNiPAM was positive for lower temperatures (T < 34 degrees C), while S(T) showed a negative value for higher temperatures (T > 34 degrees C). This means PNiPAM molecules move to the cold side for temperatures T < 34 degrees C, whereas they move to the warm side for T > 34 degrees C. This is the first nonaqueous polymeric system for which a sign change with temperature has been observed. We performed static and dynamic light scattering experiments in the same temperature range. The second virial coefficient determined from dilute solutions by static light scattering (SLS) was positive in the comparable temperature range. The results of SLS for the semidilute solution showed a strong repulsion among PNiPAM chains which was enhanced by increasing temperature. These results imply that the observed thermally induced sign change of S(T) does not depend on the intermolecular interactions among PNiPAM chains.     

Kinetics and mechanism of one dipicolinato ligand substitution in the chromium(III)–bis(dipicolinato) complex: an unusual rate dependence on acid concentration

The Na[Cr(PDA)₂] · 2H₂O complex (PDA¹ = dipicolinic acid anion) and its aquation product, [Cr(PDA)(H₂O)₃]⁺, were prepared and characterized. The electronic spectra demonstrate that the bis(dipicolinato) complex undergoes very fast partial dechelation during dissolution. In acidic media, pH controlled, rapid protolytic and ring opening processes lead to coexistence of complexes with one tridentate (PDA) and the other bi- or mono-dentate (PDA). The kinetics of PDA ligand liberation were followed spectrophotometrically within the 0.1–2.0 M HClO₄ range at I = 2.0 M. The observed first-order rate constant depends on [H⁺] according to the equation: k _obs = A[H⁺]/(1 + B[H⁺] + C[H⁺]²). A reaction course via the uncharged [Cr(PDA)(HPDA)(H₂O)₂]⁰ complex is proposed. The observed rate increase, followed by rate retardation with [H⁺] increase, is attributed to the unreactive [Cr(PDA)(H₂PDA)(H₂O)₂]⁺ complex. In terms of the proposed mechanism, A, B, C parameters have been defined as: A = k ₁ Q ₁, B = Q ₁, C = Q ₁ Q ₂ where k ₁ is the rate constant of the Cr^III-carboxylato oxygen bond-breaking in the monodentate HPDA ligand, Q ₁ is a composite value describing protolytic and dechelation processes and Q ₂ is the protonation constant of the uncharged [Cr(PDA)(HPDA)(H₂O)₂]⁰ complex.     

Collective dynamics of sub- and supercritical methanol by inelastic X-ray scattering

Inelastic X-ray scattering experiments have been performed on methanol as a function of density from ambient to the supercritical state. Positive dispersion of the sound velocity, as compared to the hydrodynamic values, is 50% in the ambient condition and decreases to zero at 0.50 g cm⁻³ over the momentum transfer Q = 1–10 nm⁻¹ with lowering density; however, it increases again with a further decrease in density down to 0.20 g cm⁻³in the supercritical state only in the Q-range above 5 nm⁻¹. These results have been interpreted as the formation of small oligomers in the low-density supercritical methanol.     

Manipulating the Through‐Space Spin–Spin Interaction of Organic Radicals in the Confined Cavity of a Self‐Assembled Cage

We show a new approach to manipulating the through‐space spin–spin interaction by utilizing the confined cavity of a self‐assembled M₆L₄ coordination cage. The coordination cage readily encapsulates stable organic radicals in solution, which brings the spin centers of the radicals closer to each other. In sharp contrast to the fact that the radical in solution in the absence of the cage is in a doublet state, in the presence of the cage through‐space spin–spin interaction is induced through cage‐encapsulation effects in solution as well as in the solid state, resulting in the triplet state of the complex. These results were confirmed by ESR spectroscopy and X‐ray crystallography. The quantity of triplet species generated by encapsulation in the cage increases with increasing affinity of the radicals to the cage. We estimated the affinity between several types of guests and the cage in solution by cyclic voltammetry. We also demonstrate that the through‐space interaction of organic radicals within the self‐assembled coordination cage can be controlled by external stimuli such as heat or pH.     

ZINC TETRAPHENYLPORPHYRIN-SENSITIZED PHOTOREDUCTION OF ANTHRAQUINONESULFONATE IN AQUEOUS MICELLAR SOLUTIONS*

Abstract— Zn-tetraphenylporphyrin (ZnTPP), solubilized in non-ionic surfactant micelles, was found to sensitize photoreductions of some sodium anthraquinonesulfonatesz in the presence of ascorbic acid under anaerobic conditions. The reaction rate was increased by the addition of an anionic surfactant, while retardation was observed with a cationic surfactant. The pH-reaction rate profiles showed maxima located in the order corresponding to pK_a-values for the semiquinone of each anthraquinone-sulfonate. A reaction scheme involving the formation of ZnTPP⁺ at the primary step, followed by back-reduction with ascorbic acid, is proposed. The reaction scheme is in good agreement with the results of flash photolysis. The surfactant micelles are suggested to aid the charge-separation between the ionic species just after the redox reaction involving the photoexcited ZnTPP and anthraquinonesulfonates.     

A novel and efficient oxidative biaryl coupling reaction of phenol ether derivatives using a combination of hypervalent iodine(III) reagent and heteropoly acid

A novel and efficient oxidative biaryl coupling reaction of phenol ether derivatives using a combination of hypervalent iodine(III) reagent, phenyliodine(III) bis(trifluoroacetate) (PIFA), and heteropoly acid has been developed.     

Chiral Recognition of Phenylacetic Acid Derivatives by Aminated Cyclodextrins

Chiral recognition of mandelic acid ( 1), acetylmandelic acid ( 2), 1-methoxyphenylacetic acid ( 3), phenylsuccinic acid ( 4), 2-phenylpropanoic acid ( 5) and ibuprofen ( 6) in their anionic forms by protonated 6A-amino-6A-deoxy--cyclodextrin (mono-NH3+--CD) and 6A,6D-diamino-6A,6D-dideo xy--cyclodextrin (di-NH3+--CD) has been studied by means of capillary zone electrophoresis (CZE) and 1H NMR spectroscopy. Both methods show the preferable guests for mono-NH3+--CD to be the (R)-enantiomers of 1, 3 and 5 and the (S)-enantiomers of 2, 4 and 6. Cooperative work of Coulomb interactions and inclusion is essential for chiral recognition of these anionic guests.     

A straightforward approach to antibodies recognising cancer specific glycopeptidic neoepitopes

Aberrantly truncated immature O-glycosylation in proteins occurs in essentially all types of epithelial cancer cells, which was demonstrated to be a common feature of most adenocarcinomas and strongly associated with cancer proliferation and metastasis. Although extensive efforts have been made toward the development of anticancer antibodies targeting MUC1, one of the most studied mucins having cancer-relevant immature O-glycans, no anti-MUC1 antibody recognises carbohydrates and the proximal MUC1 peptide region, concurrently. Here we present a general strategy that allows for the creation of antibodies interacting specifically with glycopeptidic neoepitopes by using homogeneous synthetic MUC1 glycopeptides designed for the streamlined process of immunization, antibody screening, three-dimensional structure analysis, epitope mapping and biochemical analysis. The X-ray crystal structure of the anti-MUC1 monoclonal antibody SN-101 complexed with the antigenic glycopeptide provides for the first time evidence that SN-101 recognises specifically the essential epitope by forming multiple hydrogen bonds both with the proximal peptide and GalNAc linked to the threonine residue, concurrently. Remarkably, the structure of the MUC1 glycopeptide in complex with SN-101 is identical to its solution NMR structure, an extended conformation induced by site-specific glycosylation. We demonstrate that this method accelerates dramatically the development of a new class of designated antibodies targeting a variety of “dynamic neoepitopes” elaborated by disease-specific O-glycosylation in the immunodominant mucin domains and mucin-like sequences found in intrinsically disordered regions of many proteins.

We developed new class of designated antibodies targeting of “dynamic neoepitopes” elaborated by disease-specific O-glycosylation at the immunodominant mucin domains.