Design and development of a fiber-optic immunosensor utilizing near-infrared fluorophores

The design and application of a fluorescent fiber-optic immunosensor (FFOI) are reported. The FFOI is utilized for the detection of antibody/antigen binding within the near-infrared (NIR) spectral region. The technique is developed through the combined use of fiber-optic, semiconductor laser-excitation, fluorescence detection, NIR dye, and immunochemical techniques. The antibody is immobilized on the FFOI and utilized as a recognition component for trace amounts of specific antigen. The FFOI is constructed to utilize an antibody sandwich technique. The assay involves the immobilization of the capture antibody on the sensing tip of the FFOI followed by the exposure of the immobilized sensing tip to the antigen. The antigen-coated FFOI is then introduced to a second antibody previously labeled with the NIR dye. Typical measurements are performed in about 15 min. A semiconductor laser provides the excitation (780 nm) of the immune complex. The resulting emission is detected by a silicon photodiode detector (820 nm). The intensity of the resulting fluorescence is directly proportional to the concentration of the antigen. The sensitivity of the analysis reaches 10 ng/ml and the response time is 10–15 min.     

NMR and EPR structural delineation of copper(II) complexes formed by kanamycin A in water

The complexes formed by kanamycin A at three different pH values (5.5, 7.4 and 12.0) were investigated by NMR and EPR spectroscopy. Paramagnetic relaxation contributions to proton relaxation rates were measured using a combination of the TOCSY sequence with the inversion recovery experiment in order to gain signal resolution in the bulk region. Measured contributions were converted into distances and used for structural determination by restrained simulated annealing where all possible chair and boat conformations of the rings were taken into account. The interaction of the Cu(II) ion with the nitrogen of the C ring is apparent at all pH values. At higher pH also the amino group of ring A starts to be involved in the metal coordination sphere. This is accompanied by a switch in conformation of ring C. Structures are consistent with the involvement in the coordination sphere either of the 2' or 4' hydroxyl oxygens at pH 5.5 and the 5 and the 6' hydroxyl oxygens (or the ring oxygen) at pH 12.0.     

Combining cationic ring‐opening polymerization and click chemistry for the design of functionalized polyurethanes

A straightforward strategy for the synthesis and functionalization of polyurethanes (PUs) via the use of alkyne‐functionalized polytetrahydrofuran (PTHF) diols is described. The alkyne groups have been introduced into the PTHF chains by the cationic ring‐opening copolymerization of tetrahydrofuran and glycidyl propargyl ether. These PTHF prepolymers were combined with 1,4‐butanediol and hexamethylene diisocyanate for the synthesis of linear PUs with latent functionalization sites. The polyether segments of the PUs have then been coupled with several types of functionalized azides by the copper‐catalyzed azide‐alkyne “click” chemistry, for example with phosphonium containing azides for their antibacterial properties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Influence of (phospho)lipases on properties of mica supported phospholipid layers

The effect of enzymes: lipase from Candida cylindracea (L_Cc), phospholipase A₂ from hog pancreas (PLA₂) and phospholipase C from Bacillus cereus (PLC) to modulate wetting properties of solid supported phospholipid bilayers was studied via advancing and receding contact angle measurements of water, formamide and diiodomethane, and calculation of the surface free energy and its components from van Oss et al. (LWAB) and contact angle hysteresis (CAH) approaches. Simultaneously, topography of the studied layers was determined by Atomic Force Microscopy (AFM). The investigated lipid bilayers were transferred on mica plates from subphase of pure water by means of Langmuir-Blodgett and Langmuir-Schaefer techniques. The investigated phospolipid layers were: saturated DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine), unsaturated DOPC (1,2-dioleoyl-sn-glycero-3-phosphocholine), and their mixture DPPC/DOPC. The obtained results revealed that the lipid membrane degradation by the enzymes caused increase in its surface free energy due to the amphiphilic hydrolysis products, which may accumulate in the lipid bilayer. In result activity of the enzymes may increase and then break down the bilayer structure takes place. It is likely that after dissolution of the hydrolysis reaction products in the bulk phase, patches of bare mica surface are accessible, which contribute to the apparent surface free energy changes. Comparison of AFM images and the free energy changes of the layers gives better insight into changes of their properties. The observed gradual increase in the layer surface free energy allows controlling of the hydrolysis process to obtain the surfaces of defined properties.     

A novel hydroxy functionalized polyester obtained by ring opening copolymerization of L‐lactide with a pyrolysis product of cellulose

A hydroxylactone ((1R,5S)‐1‐hydroxy‐3,6‐dioxabicyclo [3.2.1] octan‐2‐one, abbreviated as LAC) obtained from catalytic pyrolysis of cellulose was investigated as a monomer in the synthesis of polyesters by ring‐opening polymerization (ROP) with L ‐lactide. Although stannous octoate resulted inactive, ROP initiated by zirconium (IV) acetylacetonate afforded novel copolyesters from LAC and lactide mixtures in the bulk at 110 °C. Copolymers were obtained with different LAC content (from 19 to 45%) with a random microstructure as established by detailed NMR analysis. FTIR spectrometry confirmed the presence in the polymer chain of the OH groups originally present in LAC, which do not react during polymerization due to steric hindrance and inter/intramolecular hydrogen bonding. Reaction with trichloroacetylisocyanide proved that OH groups of the polyesters can be readily derivatized. The application of LAC as a comonomer enables the insertion of the alcohol functionality in polylactide avoiding protection/deprotection steps and potentially expanding the realm of biomaterials affordable from carbohydrate feedstock. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 247–257, 2009     

Equations of Hurwitz schemes in the infinite Grassmannian

The main result proved in the paper is the computation of the explicit equations defining the Hurwitz schemes of coverings with punctures as subschemes of the Sato infinite Grassmannian. As an application, we characterize the existence of certain linear series on a smooth curve in terms of soliton equations. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Are Gait and Balance Problems in Neurological Patients Interdependent? Enhanced Analysis Using Gait Indices,Cyclograms, Balance Parameters and Entropy

Background: Balance and locomotion are two main complex functions, which require intact and efficient neuromuscular and sensory systems, and their proper integration. In many studies the assumption of their dependence is present, and some rehabilitation approaches are based on it. Other papers undermine this assumption. Therefore the aim of this study was to examine the possible dependence between gait and balance in patients with neurological or sensory integration problems, which affected their balance. Methods: 75 patients (52 with neurological diseases, 23 with sensory integration problems) participated in the study. They underwent balance assessment on Kistler force plate in two conditions, six tests on a Balance Biodex System and instrumented gait analysis with VICON. The gait and balances parameters and indices, together with entropy and cyclograms were used for the analysis. Spearman correlation, multiple regression, cluster analysis, and discriminant analysis were used as analytical tools. Results: The analysis divided patients into 2 groups with 100% correctly classified cases. Some balance and gait measures are better in the first group, but some others in the second. Conclusions: This finding confirms the hypothesis that there is no direct link between gait and balance deficits.     

Repair of (6‐4) Lesions in DNA by (6‐4) Photolyase: 20 Years of Quest for the Photoreaction Mechanism

Exposure of DNA to ultraviolet (UV) light from the Sun or from other sources causes the formation of harmful and carcinogenic crosslinks between adjacent pyrimidine nucleobases, namely cyclobutane pyrimidine dimers and pyrimidine(6–4)pyrimidone photoproducts. Nature has developed unique flavoenzymes, called DNA photolyases, that utilize blue light, that is photons of lower energy than those of the damaging light, to repair these lesions. In this review, we focus on the chemically challenging repair of the (6–4) photoproducts by (6–4) photolyase and describe the major events along the quest for the reaction mechanisms, over the 20 years since the discovery of (6‐4) photolyase.     

Graded cellular bases for Temperley–Lieb algebras of type A and B

We show that the Temperley–Lieb algebra of type A and the blob algebra (also known as the Temperley–Lieb algebra of type B) at roots of unity are \(\mathbb{Z}\) -graded algebras. We moreover show that they are graded cellular algebras, thus making their cell modules, or standard modules, graded modules for the algebras.     

Synthesis of partially benzylated arabinofuranosides,NMR analysis,and application to oligosaccharide synthesis

The preparation and NMR analysis of 2,3-di-O-benzyl arabinofuranosides have been described. In DMSO-d₆, the sugar adopts a conformation in which the hydroxyl groups are in an equatorial position; the equilibrium composition is determined by steric factors. In CDCl₃, the sugar adopts a conformation in which the intramolecular hydrogen bonding plays an important role in determining the equilibrium composition. The use of 2,3-di-O-benzyl arabinose in the synthesis of oligoarabinofuranosides enabled the synthesis of α- or β-linked furanosides.