Surface energetics of poly(N-vinyl-2-pyrrolidone)/chitosan blend films

Poly(N-vinyl-2-pyrrolidone) (PVP) and chitosan (CTS) with three different molecular weights (MW: 150,000, 400,000 and 600,000 g/mol) blends were prepared as films having 13, 20, 33, 43 and 50% (w/w) CTS by solution casting method. Surface properties of the films were analyzed by contact-angle measurements and scanning electron microscopy (SEM). The contact angles of water, glycerol, ethylene glycol, formamide and paraffin oil drop were measured on these films. The contact-angle results were evaluated in terms of surface free energy components by using Van Oss-Good methodology. It was found that all PVP/CTS blend surfaces are enriched in low surface free energy component, i.e. CTS. This conclusion was further confirmed by the cross-sectional SEM images observation of these blends.     

Kinetic analysis of surface‐initiated SET‐LRP of poly(N‐isopropylacrylamide)

The single‐electron transfer living radical polymerization (SET‐LRP) of N‐isopropylacrylamide (NIPAM) from silicon wafer modified with an initiator layer composed of 2‐bromopropionyl bromide (2‐BPB) fragments is described. The amount of Cu(0) generated in situ by the disproportination of Cu(I) to Cu(0) and Cu(II) in the presence of 2,2′‐bipyridine (2,2′‐bpy) ligand and N,N‐dimethylformamide (DMF) solvent at 90 °C is dependent on the ratio of [CuBr]/[CuBr₂]. By proper selection of the [CuBr]/[CuBr₂] ratio, well‐controlled SET‐LRP polymerization of NIPAM was observed such that the thickness of the layer consisting of chains grown from the surface increased linearly with the molecular weight of chains polymerized in solution in identical. In addition, the calculation of grafting parameters, including surface coverage, σ (mg/m²); grafting density, Σ (chain/nm²); and average distance between grafting sites, D (nm), from the number‐average molecular weight, M _n (g/mol), and ellipsometric thickness, h (nm), values indicated the synthesis of densely grafted poly(NIPAM) films and allowed us to predict a “brush‐like” conformation. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Construction of hydroxyl‐terminated poly(N‐isopropylacrylamide) brushes on silicon wafer via surface‐initiated atom transfer radical polymerization

Surface‐initiated atom transfer radical polymerization (SI‐ATRP) of N‐isopropylacrylamide (NIPAM) on silicon wafer in the presence of 2‐mercaptoethanol (ME) chain transfer agent was conducted in attempt to create controllable hydroxyl‐terminated brushes. The initiator‐immobilized substrate, was prepared by the esterification of hydroxyl groups on silicon wafer with 2‐bromopropionyl bromide (2‐BPB); followed by the ATRP of NIPAM using a catalyst system, that is, Cu(I)Br/2,2′‐bipyridine (2,2′‐bpy) and a chain transfer agent, that is, ME. The formation of homogeneous tethered poly(N‐isopropylacrylamide) (poly(NIPAM) brushes with hydroxyl end‐group, whose thickness can be tuned by chancing ME concentration, is evidenced by using the combination of grazing angle attenuated total reflectance‐Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, ellipsometry, atomic force microscopy, gel permeation chromatography, and water contact‐angle measurements. The calculation of grafting parameters from experimental measurements indicated the synthesis of densely grafted poly(NIPAM) films with hydroxyl end‐group on silicon wafer and allowed us to predict a ME concentration for forming a “brush” conformation for the chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3880–3887, 2010     

Extremely sensitive sandwich assay of kanamycin using surface-enhanced Raman scattering of 2-mercaptobenzothiazole labeled gold@silver nanoparticles

Herein, we report the development of extremely sensitive sandwich assay of kanamycin using a combination of anti-kanamycin functionalized hybrid magnetic (Fe₃O₄) nanoparticles (MNPs) and 2-mercaptobenzothiazole labeled Au-core@Ag-shell nanoparticles as the recognition and surface-enhanced Raman scattering (SERS) substrate, respectively. The hybrid MNPs were first prepared via surface-mediated RAFT polymerization of N-acryloyl-l-glutamic acid in the presence of 2-(butylsulfanylcarbonylthiolsulfanyl) propionic acid-modified MNPs as a RAFT agent and then biofunctionalized with anti-kanamycin, which are both specific for kanamycin and can be collected via a simple magnet. After separating kanamycin from the sample matrix, they were sandwiched with the SERS substrate. According to our experimental results, the limit of detection (LOD) was determined to be 2 pg mL⁻¹, this value being about 3–7 times more than sensitive than the LOD of previously reported results, which can be explained by the higher SERS activity of silver coated gold nanoparticles. The analysis time took less than 10 min, including washing and optical detection steps. Furthermore, the sandwich assay was evaluated for investigating the kanamycin specificity on neomycin, gentamycin and streptomycin and detecting kanamycin in artificially contaminated milk.     

Amethyst and morion quartz gemstone raw materials from Turkey: color saturation and enhancement by gamma,neutron and beta irradiation

Color-enhancement investigations without using heating treatment from dull or pale to ideal saturation and/or changes to the formation of the rarer attractive colors are widely conducted to revalue abandoned gem material sources in the world. Such an investigation is carried out on pale or dull purple-colored amethyst and smoky-colored morion samples, which are two important gem species of the crystalline quartz (SiO₂) mineral that are currently abandoned in natural deposits in Turkey because of their unattractive coloration. The results of color enhancements observed on these samples, after irradiation with artificial gamma, neutron and beta beams, were examined by comparing with samples with the ideal color saturation and also with colorless samples, using optical absorption (OA) and radioluminescence (RL) spectroscopy. The ICP-AES analyses reveal that the main impurity elements of over 100 ppm in abundance in these quartz species are aluminum, iron and titanium for amethyst, and aluminum, iron, titanium and manganese for morion. The OA spectra indicate that vivid purple coloration of amethyst is due to the transmittance at about 395–420 nm band gap as a result of absorbance peaks at 375, 480 and 530 nm. These absorbances may be related to the unusual oxidized small proportions of certain impurity ions, after being exposed mainly to gamma irradiation, such as Al(IV) from the total aluminum, Ti(V) from the total titanium and Fe(IV) from the total iron, respectively. However, the RL spectroscopy of amethyst samples before and after they were exposed to artificial gamma, neutron and beta radiation beams demonstrates that the ions most affected by irradiation are Fe(IV) first and Al(IV) and Ti(V) second, and these ions represent the RL peaks at 600, 720 and 495 nm, respectively. The OA spectra indicate that dark smoky coloration in morion is due to a lack of transmittance at the visible region as a result of the absorbance peaks at 375, 450–490, 620 and 730 nm. These absorbances also may be related to the unusual oxidized small proportions of certain impurity ions by irradiation, such as Al(IV) from the total aluminum, Ti(V) from the total titanium and Mn(III) from the total manganese, respectively. In addition, the buoyancies of these absorbance peaks in the visible region produce the color hues between light smoky and dark smoky colorations in morion samples. These oxidized ion states are more resistant and stable against environmental destructive conditions in comparison with amethyst. Thus, the dark smoky coloration of morion becomes dull or pale after relatively longer periods. But, the RL spectroscopy of morion before and after being exposed to gamma, neutron and beta irradiation beams demonstrates that the most induced ions from the irradiation are Mn(III) and Al(IV) first and Ti(V) second. These ions represent the RL peaks at about 400, 720 and about 500 nm, respectively.     

1,14‐Dioxa‐5,10‐di­aza‐2,3:12,13‐dibenzo­cyclo­octadeca‐2,12‐diene monohydrate

The title compound, C₂₂H₃₀N₂O₂·H₂O, is an 18‐membered di­aza‐crown ether ligand containing two ether O and two aza N atoms. In the macrocyclic ring, the mean N⋯O distance is 4.526 (4) Å. The macrocyclic inner‐hole size, estimated as twice the mean distance of the donor atoms from their centroid, is ∼2.29 Å.     

Preparation of a Novel Polymer‐Modified Si Surface for DNA Immobilization

The design of a novel polymer‐modified overlayer composed of PPAPE and GPMS on a silicon wafer for immobilization of DNA molecules is described. After hydroxylation of Si(100) surfaces, GPMS molecules were self‐assembled onto these surfaces. PPAPE molecules were then covalently attached to the epoxy‐terminated surfaces. The incubation time and concentration of PPAPE was found to effect both layer thickness and water CA. The type of organic solvent and the pH were found to change the nature of the PPAPE‐modified surface for DNA immobilization. It is concluded that PPAPE‐modified surfaces show advantages for DNA immobilization by electrostatic interactions between DNA molecules and positively charged free amino groups of the PPAPE‐modified surfaces at the appropriate pH values.

     

Dependence of Protein Recognition of Temperature‐Sensitive Imprinted Hydrogels on Preparation Temperature

Temperature‐sensitive imprinted and non‐imprinted hydrogels composed of N‐isopropylacrylamide (NIPA) and 2‐acrylamido‐2‐methyl‐propanosulfonic acid (AMPS) have been prepared by free‐radical crosslinking copolymerization in aqueous solution at three different temperatures: 10 °C (below the lower critical solution temperature, LCST), 33 °C (at the LCST), and 40 °C (above the LCST). Myoglobin (Mb, MW 17 kDa) is used as the template biomolecule. The effects of the initial concentration and adsorption time over the Mb adsorption capacity of the hydrogels have been analyzed and found to be strongly dependent on the preparation temperature (T_prep). The maximum Mb adsorption for the imprinted hydrogel prepared at 10 °C is 97.40 ± 2.35 mg Mb · g⁻¹ dry gel in 0.32 mg · mL⁻¹ Mb solution at 22 °C. Moreover, batch adsorption equilibrium and selectivity studies have been performed using a reference molecule, hemoglobin (Hb, MW 65 kDa). The imprinted hydrogels have a 2.8–3.3 times higher adsorption capacity for Mb than the non‐imprinted hydrogels prepared at the same T_preps, and also have a 1.8–2.7 times higher selectivity for the imprinted molecule.