Surface Initiated Polymerization from Substrates of Low Initiator Density and Its Applications in Biosensors

Surface initiated polymerization (SIP) has become an attractive method for tailoring physical and chemical properties of surfaces for a broad range of applications. Most of those application relied on the merit of a high density coating. In this study we explored a long overlooked field of SIP. SIP from substrates of low initiator density. We combined ellipsometry with AFM to investigate the effect of initiatior density and polymerization time on the morphology of polymer coatings. In addition, we carefully adjusted the nanoscale separation of polymer chains to achieve a balance between nonfouling and immobilization capacities. We further tested the performance of those coating on various biosensors, such as quartz crystal microbalance, surface plasmon resonance, and protein microarrays. The optimized matrices enhanced the performance of those biosensors. This report shall encourage researches to explore new frontiers in SIP that go beyond polymer brushes.

Quartz crystal microbalance study of the kinetics of surface initiated polymerization

Surface initiated polymerization (SIP) is a valuable tool in synthesizing functional polymer brushes, yet the kinetic understanding of SIP lags behind the development of its application. We apply quartz crystal microbalance (QCM) to address two issues that are not fully addressed yet play a central role in the rational design of functional polymer brushes, namely quantitative determination of the kinetics and the initiator efficiency (IE) of SIP. SIP are monitored online using QCM. Two quantitative frequency-thickness (f-T) relations make the direct determination and comparison of the rate of polymerization possible even for different monomers. Based on the bi-termination model, the kinetics of SIP is simply described by two variables, which are related to two polymerization constants, namely a = 1/(k (p,s,app)-[M][R center dot](0)) and b = k (t,s,app)/(k (p,s,app)[M]). Factors that could alter the kinetics of SIP are studied, including (i) the molecular weight of monomers, (ii) the solvent used, (iii) the initial density of the initiator, (iv) the concentration of monomer, [M], and (v) the catalyst system (ratio among the ingredients, metal, ligands, and additives). The dynamic nature of IE is also described by these two variables, IE = a/(a + bt). Instead of the molecular weight and the polydispersity, we suggest that film thickness, the two kinetic parameters (a and b), and the initial density of the initiator and IE be the parameters that characterize ultra-thin polymer brushes. Besides the kinetics study of SIP, the reported method has many other applications, for example, in the fast screening of catalyst system for SIP and other polymerization systems.

Electrochemical polymerization and characterization of polypyrrole nanowires and nanotubules

Polypyrrole nanostructure arrays, including simultaneously large quantities of nanowires and small quantities of partially filled nanotubules have been electrochemically synthesized in home-made etched ion-track polycarbonate (PC) templates. Diameter of the prepared nanostructures varies from 45 to 320 nm with their lengths up to 30 microns. Morphological studies of these nanostructures were performed by field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and Raman spectroscopy. While optical absorption properties were studied by ultraviolet-visible-near infrared spectrophotometry (UV-vis-NIR). It has been observed that the absorption maximum of polypyrrole shifts to the longer wavelength side as the diameter of these nanostructures (nanowires and nanotubules) increases. (C) 2010 Elsevier B.V. All rights reserved.

Light alkenes preparation by the gas phase oxidative cracking or catalytic oxidative cracking of high hydrocarbons

The preparation of light alkenes by the gas phase oxidative cracking (GOC) or catalytic oxidative cracking (COC) of model high hydrocarbons ( hexane, cyclohexane, isooctane and decane in the GOC process and hexane in the COC process) was investigated in this paper. The selection for the feed in the GOC process was flexible. Excellent conversion of hydrocarbons ( over 85%) and high yield of light alkenes ( about 50%) were obtained in the GOC of various hydrocarbons including cyclohexane at 750 degreesC. In the GOC process, the utilization ratio of the carbon resources was high; CO dominated the produced COX (the selectivity to CO2 was always below 1%); and the total selectivity to light alkenes and CO was near or over 70%. In the COC of hexane over three typical catalysts (HZSM-5, 10% La2O3/HZSM-5 and 0.25% Li/MgO), the selectivity to COX was hard to decrease and the conversion of hexane and yield of light alkenes could not compete with those in the GOC process. With the addition of H-2 in the feed, the selectivity to COX was reduced below 5% over 0.1% Pt/HZSM-5 or 0.1% Pt/MgAl2O4 catalyst. The latter catalyst was superior to the former catalyst due to its perfect performance at high temperature, and with the latter, excellent selectivity to light alkenes ( 70%) and the conversion of hexane (92%) were achieved at 850 degreesC ( a yield of light alkenes of 64%, correspondingly).

The remarkable effect of In2O3 on the catalytic activity of In/HZSM-5 for the reduction of NO with CH4

In/HZSM-5/ln(2)O(3) catalyst that contained two different kinds of In induced by the impregnating and the physical mixing method respectively has shown remarkable activity for the CH4-SCR of NOx comparing with In/HZSM-5. The addition of In2O3 into In/HZSM-5 improved the NO conversion through enhancing the adsorption of NOx over In/HZSM-5.

Pd/sulfated alumina - a new effective catalyst for the selective catalytic reduction of NO with CH4

Sulfated alumina (SA) is firstly found to be an effective support for Pd catalyst used in the SCR of NO with methane. The sulfation is important to increase support's acidity which is essential for the reduction of NO over Pd catalysts. On consideration of the lower cost and easier availability of SA, we believe that SA is more promising to act as the commercial support for Pd catalyst used in the SCR of NO with methane.

Probing into the catalytic nature of Co/sulfated zirconia for selective reduction of NO with methane

In this work, the structural and surface properties of Co-loaded sulfated zirconia (SZ) catalysts were studied by X-ray diffraction (XRD), N-2 adsorption, NH3-TPD, FT-IR spectroscopy, H-2-TPR, UV-vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), and NO-TPD. NH3-TPD and FT-IR spectra results of the catalysts showed that the sulfation process of the support resulted in the generation of strong Bronsted and Lewis acid sites, which is essential for the SCR of NO with methane. On the other hand, the N-2 adsorption, H-2-TPR, UV/vis DRS, and XPS of the catalysts demonstrated that the presence of the SO42- species promoted the dispersion of the Co species and prevented the formation Of Co3O4. Such an increased dispersion of Co species suppressed the combustion reaction of CH4 by O-2 and increased the selectivity toward NO reduction. The NO-TPD proved that the loading of Co increased the adsorption of NO over SZ catalysts, which is another reason for the promoting effect of Co. (C) 2004 Elsevier Inc. All rights reserved.

The reaction route and active site of catalytic decomposition of hydrazine over molybdenum nitride catalyst

The catalytic properties of the passivated, reduced passivated, and fresh bulk molybdenum nitride for hydrazine decomposition were evaluated in a microreactor. The reaction route of hydrazine decomposition over molybdenum nitride catalysts seems to be the same as that of Ir/gamma-Al2O3 catalysts. Below 673 K, the hydrazine decomposes into N-2 and NH3. Above 673 K, the hydrazine decomposes into N-2 and NH3 first, and then the produced NH3 further dissociates into N-2 and H-2. From the in situ FT-IR spectroscopy, hydrazine is adsorbed and decomposes mainly on the Mo site of the Mo2N/gamma-Al2O3 catalyst. (C) 2004 Elsevier Inc. All rights reserved.

Trichloroisocyanuric acid: A convenient oxidation reagent for phase-transfer catalytic epoxidation of enones under non-aqueous conditions

Trichloroisocyanuric acid (TCCA) is a cheap, safe and readily available alternative to the commonly used hydrogen peroxide and hypochlorite for the phase-transfer catalytic epoxidation of alpha,beta-enones under non-aqueous conditions. A variety of chalcone derivatives give the corresponding epoxides with quantitative conversion and satisfactory yields in just a few hours under mild conditions. An asymmetric variant of the epoxidation can be carried out in the presence of chiral N-anthracenylmethylcinchonidine bromide catalyst giving 73-93% ees and 76-94% yields.

Catalytic performance of MCM-22 zeolite for alkylation of toluene with methanol

MCM-22 zeolite with mid-strong acidity and openings of 10-membered ring channels may obtain a high catalytic activity and selectivity for alkylation of toluene with methanol. The acidic sites, for catalyzing alkylation of toluene with methanol, are weaker than that for catalyzing toluene disproportionation. Compared with silicon as a modifier, modification of MCM-22 with La(NO3)(3) is a promising way to improve the catalytic selectivity of para-xylene. In addition, the experimental results also clearly indicate the characteristics of MCM-22 structure consisting of large intracrystalline cages, some of which may locate on surface of MCM-22. (C) 2004 Elsevier B.V. All rights reserved.

Effect of drying methods on the structure and catalytic combustion activity of Mn-substituted hexaaluminate catalysts

Conventional oven drying (COD) and supercritical drying (SCD) methods were applied to the preparation of Mn-substituted hexaaluminate (BaMnA(11)O(19-alpha)) catalysts. The effect of drying methods on phase composition, specific surface area, pore structure and combustion activity of the samples was investigated. The samples obtained by SCD have higher surface area, narrower pore size distribution, and higher combustion activity than those obtained by COD.