Formation of Polymer Nanolayers with Special Properties at Polymer Surfaces

A principal possibility of the utilization of polymer peroxides for the modification of polymer surfaces that provides an immobilization of the tailored quantity of peroxide groups at them has been established. The processes of polymer surface activation with following “grafting from” or “grafting to” utilizing immobilized peroxide groups has been studied using a FTIR-ATR spectroscopy, ellipsometry and measurements of contact angles. The proposed technique of polymer surface activation is based on the universal ability of carbon chain polymer to participate the free radical reactions.     

Chiral Monolithic Silica-Based HPLC Columns for Enantiomeric Separation and Determination: Functionalization of Chiral Selector and Recognition of Selector-Selectand Interaction

This review draws attention to the use of chiral monolithic silica HPLC columns for the enantiomeric separation and determination of chiral compounds. Properties and advantages of monolithic silica HPLC columns are also highlighted in comparison to conventional particle-packed, fused-core, and sub-2-µm HPLC columns. Nano-LC capillary monolithic silica columns as well as polymeric-based and hybrid-based monolithic columns are also demonstrated to show good enantioresolution abilities. Methods for introducing the chiral selector into the monolithic silica column in the form of mobile phase additive, by encapsulation and surface coating, or by covalent functionalization are described. The application of molecular modeling methods to elucidate the selector–selectand interaction is discussed. An application for enantiomeric impurity determination is also considered.     

Synthesis,Anticancer, and QSAR Studies of 2‐Alkyl(aryl,hetaryl)quinazolin‐4(3H)‐thione's and [1,2,4]Triazolo[1,5‐c]quinazoline‐2‐thione's Thioderivatives

Considering the frightening high level of mortality from cancer, studies of anticancer agents are vital nowadays. The 24 thioderivatives of 2‐alkyl(aryl)‐quinazolin‐4(3H)‐thiones and 20 thioderivatives of [1,2,4]triazolo[1,5‐c]quinazoline‐2‐thiones were synthesized and evaluated for preliminary in vitro anticancer activity with subsequent in silico QSAR analysis. The substance 18 had the best results inhibiting growth of eight cancer cell lines: CCRF‐CEM of leukemia; SF‐539, SNB‐75, and U251 of CNS cancer; 786, RXF393, and UO‐31 of renal cancer; and MDA‐MB‐231/ATCC of breast cancer (?31.50 – 47.41% of cell growth) with low procancer effect. Calculated QSAR‐models for CCRF‐CEM of leukemia, T‐47D and HS 578T of breast cancer, and mean cell growth demonstrated good rate of anticancer activity prediction (r² = 0.7 – 0.8,  = 0.5 – 0.7).     

A simple and cost-effective molecular diagnostic system and DNA probes synthesized by light emitting diode photolithography

This work introduces a novel chip to be used in the future as a simple and cost-effective method for creating DNA arrays using light emission diode (LED) photolithography. The DNA chip platform contains 24 independent reaction sites, which allows for the testing of a corresponding amount of patients’ samples in hospital. An array of commercial UV LEDs and lens systems was combined with a microfluidic flow system to provide patterning of 24 individual reaction sites, each with 64 independent probes. Using the LED array instead of conventional laser exposure systems or micro-mirror systems significantly reduces the cost of equipment. The microfluidic system together with microfluidic flow cells drastically reduces the amount of used reagents, which is important due to the high cost of commercial reagents. The DNA synthesis efficiency was verified by fluorescence labeling and conventional hybridization.     

Binary volume phase masks in photo-thermo-refractive glass

Permanent binary phase masks with planar surfaces and high tolerance to laser radiation are recorded in the volume of photo-thermo-refractive glass using the contact copying technique and binary amplitude master masks. Conversion of a Gaussian beam to higher order modes is shown.     

Generation of diversiform gold nanostructures inspired by honey's components: Growth mechanism, characterization, and shape separation by the centrifugation-assisted sedimentation

The green synthesis of irregular-shaped nanomaterials used for various applications in nanoplasmonics, medicine, and biotechnology creates an economical and environmental challenge. We describe the rapid wet-chemical approach to synthesis of stable and water-soluble gold nanostructues at room temperature. In addition to spherical and road-like nanoparticles, gold decahedra and triangular plates were grown using the one-step synthesis process of HAuCl(4) in the presence of honey, in which main components act as reducing (glucose) and stabilizing (fructose) agents; the mechanism of the process is discussed in details. The requirements for anisotropic phase boundaries for generation of polyhedral gold nanocrystals in solutions are highlighted. The synthesis, morphology, and separation procedure of gold nanoparticles are examined using the techniques of optical spectroscopy, transmission electron microscopy, and atomic force microscopy. We demonstrate that centrifugation can be used for efficient separation of nanoparticles with different shapes from a mixture. It was found that while centrifuging, the spheres sediment at the bottom of the tube, segregating from rods that form a deposit on the side wall, whereas polygons remain in the solution.     

Synthesis of 5‐methyl‐4‐oxo‐2‐(coumarin‐3‐yl)‐N‐aryl‐3,4‐dihydrothieno[2,3‐d]‐pyrimidine‐6‐carboxamides

Possible approaches to synthesis of 5‐methyl‐4‐oxo‐2‐(coumarin‐3‐yl)‐N‐aryl‐3,4‐dihydrothieno[2,3‐d]pyrimidine‐6‐carboxamides 4 have been discussed. It is shown that the preferable approach is cyclization of 2‐iminocoumarin‐3‐carboxamides 1 , utilizing 5‐amino‐3‐methyl‐N²‐arylthiophene‐2,4‐dicarboxamides 2 as binucleophilic reagents. The proposed procedure allowed us to easily obtain 4 in two stages, using common reagents. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:341–346, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20303     

Homotopy Types of Stabilizers and Orbits of Morse Functions on Surfaces

Let M be a smooth compact surface, orientable or not, with boundary or without it, P either the real line ℝ ¹ or the circle S ¹, and D(M) the group of diffeomorphisms of M acting on C^∞(M, P) by the rule h⋅ f = f ∘ h ⁻¹ for h ∊ D(M) and f ∊ C^∞ (M,P). Let f: M → P be an arbitrary Morse mapping, Σ _f the set of critical points of f, D(M,Σ _f ) the subgroup of D(M) preserving Σ _f , and S(f), S (f,Σ _f ), O(f), and O(f,Σ _f ) the stabilizers and the orbits of f with respect to D(M) and D(M,Σ _f ). In fact S(f) = S(f,Σ _f ).In this paper we calculate the homotopy types of S(f), O(f) and O(f,Σ _f ). It is proved that except for few cases the connected components of S(f) and O(f,Σ _f ) are contractible, π _k O(f) = π _k M for k ≥ 3, π₂ O(f) = 0, and π₁ O(f) is an extension of π₁ D(M) ⊕ Z ^k (for some k ≥ 0) with a (finite) subgroup of the group of automorphisms of the Kronrod-Reeb graph of f.We also generalize the methods of F. Sergeraert to give conditions for a finite codimension orbit of a tame smooth action of a tame Lie group on a tame Fréchet manifold to be a tame Fréchet manifold itself. In particular, we obtain that O(f) and O(f, Σ _f ) are tame Fréchet manifolds. Communicated by Peter Michor Vienna Mathematics Subject Classifications (2000): 37C05, 57S05, 57R45.     

From smart polymer molecules to responsive nanostructured surfaces

A heteroarm star block copolymer made from seven polystyrene and seven poly(2-vinylpyridine) arms was grafted onto a solid substrate to fabricate a responsive polymer surface consisting of a densely packed monolayer of copolymer molecules. The grafted layer demonstrates a two-level hierarchical response upon external stimuli combining core-shell transitions of single stars with cooperative transitions of the interacting arms between "dimple" and "ripple" morphologies of the monolayer. The response allows for the switching of the surface properties upon changing solvent selectivity or pH of the aqueous environment.     

Double- and triple-consecutive O-insertion into tert-butyl and triarylmethyl structures

[reaction: see text] The concecutive Criegee rearrangement reactions were studied for tert-butyl trifluoroacetate, triarylcarbinols, and benzophenone ketales with trifluoroperacetic acid (TFPAA) in trifluoroacetic acid (TFA). The formation of methyl acetate and methyl trifluoroacetate indicates that the consecutive double-O-insertion process has taken place for tert-butyl trifluoroacetate. The intermediate dimethoxymethylcarbonium ion was detected below 5 degrees C. A consecutive triple-O-insertion process has been observed for triarylmethanols and benzophenone ketals. A new high yield method of corresponding diaryl carbonates synthesis was developed.