Electroacoustic and Potentiometric Studies of the Hematite/Water Interface

The basic charging properties of nearly spherical hematite particles were studied by using potentiometric titration and the electroacoustic technique. Both the pH and the ionic strength dependence of the surface charge and the ζ-potential were studied in detail. For calculating the ζ-potential from mobility data a few different theories were used and obtained differences are discussed. At pH values higher than 7 and at high electrolyte concentrations (50 mM and 100 mM NaNO₃), it was difficult to fit the mobility data by using the full mobility spectra including both magnitude and phase angle at several frequencies. In this regime the best fits were obtained by using a theory for aggregated complexes (porous particles). From potentiometric titrations in 0.01, 0.1, and 1.0 M NaNO₃, parameters for a 1-pK Basic Stern Model were determined. The model was used to examine the possibility of correlating the experimentally determined ζ-potentials to the model-calculated potentials at the Stern plane. Qualitatively, the model predicted the correct ionic strength dependence of the ζ-potentials, and there was also a rather good quantitative agreement at high ionic strengths (50 and 100 mM NaNO₃). However, at lower ionic strengths the model predicted values up to 40% higher than those found from the electroacoustic study. Surface conduction behind the slip plane was discussed as a possible cause for this discrepancy.     

A far infrared investigation of anionic species present in solution during the crystallization of a polynuclear bromocuprate(I) cluster containing three-coordinated copper (I)

Ethanolic solutions of tetrapropylammonium bromide and copper(I) bromide, from which bis(tetrapropylammonium) hexa--bromo-tetrahedro-tetracuprate(I), [N(C₃H₇)₄]₂[Cu₄Br₆], a bromocuprate(I) cluster comprised of three-coordinated copper(I), crystallizes have been shown, by means of far i.r. spectroscopy, to contain the centrosymmetric, monomeric [CuBr₂]^– anion as the major, and probably the sole, bromocuprate(I) species, ₃=323 cm^–1. Crystalline [N(C₃H₇)₄]₂[Cu₄Br₆], [N(CH₃)₄]₃[Cu₂Br₅] and [P(CH₃)₄]₂[CuBr₃], all of which contain anions in which copper(I) is three-coordinated, dissolve in nitro-methane to give solutions of the dibromocuprate(I) monomer. Variation of the coordination number of copper(I) in bromocuprates(I) crystallizing with symmetrically substituted quaternary ammonium and related unipositive cations is discussed in terms of dilution of the bromide ions by the cations, and a tentative mechanism for the formation of such compounds is proposed.Toward the end of the precipitation of [N(C₃H₇)₄]₂[Cu₄Br₆] from the ethanolic solution of tetrapropylammonium bromide and copper(I) bromide, a few crystals of a second bromocuprate(I) phase were obtained. This compound has been identified as tetrapropylammonium dibromocuprate(I), and its crystal structure determined from X-ray diffraction data. [N(C₃H₇)₄][CuBr₂] crystallizes in space groupP2/n, witha=13.010(15),b=7.577(5),c=8.858(4) Å,=91.09(7)° andZ=2. The anion is a monomer in which Cu-Br is 2.194(3) Å and Br-Cu-Br 178.4(1)°, copper(I) being situated on a twofold axis.     

Lipase-catalyzed asymmetric acylation in the chemoenzymatic synthesis of furan-based alcohols

Eight racemic 1-(furan-2-yl)ethanols were prepared from the corresponding carbonyl compounds for enantioselective acylation studies, and seven of them were used in preparative-scale kinetic resolutions with Candida antarctica lipase B (Novozym 435) and vinyl acetate in dried diisopropyl ether. Mechanism-based competition between the (R)-acetate (enzymatic acylation product), vinyl acetate (added acylating reagent), and acetic acid (enzymatic hydrolysis product) toward CAL-B, together with the residual water of the lipase were shown to be potential reasons for side reactions, which affected the course of the kinetic resolution of 1-[5-(2-chlorophenyl) and (4-bromophenyl)furan-2-yl]ethanols. Clear effects were not observed with the other alcoholic substrates. Alcoholysis of the enantiomerically enriched (R)-acetates with methanol and CAL-B in diisopropyl ether was shown to be a potential method for the deprotection of the (R)-acetates and the formation of (R)-alcohols.     

Intra-cavity frequency-doubled Yb:KYW laser using periodically poled Rb-doped KTP with a volume Bragg grating input coupler

An Yb:KYW laser intra-cavity frequency doubled to the green at 514.7 nm using a periodically poled Rb:KTP crystal with an output power exceeding 1 W is presented. Spectral narrowing and locking at the fundamental wavelength has been achieved by using a volume Bragg grating as the input coupler.     

Dynamic material parameters in an anisotropic plate estimated by phase-stepped holographic interferometry

Material parameters in an anisotropic plate are determined using two non-destructive measuring techniques: real-time phase-stepped electronic speckle pattern interferometry and dual-reference-beam pulsed holographic interferometry. The first technique is used to measure the lower modes of vibration of the plate with free-free boundary conditions. Finite element analysis is then used to determine two effective Young's moduli and the in-plane shear modulus. The second technique is used to detect transient bending waves propagating in the plate and acoustic waves propagating in the surrounding air. A double-pulsed laser is used both to generate the waves and to make holographic recordings of the wave fields. The stiffness of the plate is estimated using the measured deformation field and an analytical solution to the plate impact problem.     

Poly(methyl methacrylate-co-ethyl acrylate) latex particles with poly(ethylene glycol) grafts: structure and film formation

Water-based copolymer dispersions were prepared using methyl methacrylate (MMA), ethyl acrylate (EA) (MMA/EA = 1:2), and a series of nonionic polymerizable surfactants, i.e., "surfmers" based on poly(ethylene glycol)-(meth)acrylates. The latexes were compared with the behavior of a conventionally stabilized (nonionic nonylphenol ethoxylate, NP100 with 84 ethylene oxide units) dispersion with the same MMA-EA composition (PMMAEA). A number of techniques were employed in order to characterize structure, dynamics, and film formation properties: solution/solid-state NMR, dynamic/static light scattering (DLS/SLS), differential scanning calorimetry (DSC), tensile/shear mode dynamic mechanical thermal analysis (DMTA), and atomic force microscopy (AFM). The surfmers were found to be miscible with the MMA-EA copolymer at room temperature, with 46-85 mol % of the reacted surfmer detected at the particle surfaces, and the remaining part buried in the particle bulk. In contrast, the NP100 surfactant formed a separate interphase between the copolymer particles with no mixing detected at room temperature or at 90 degrees C. For a 4.0% dry weight concentration, NP100 phase separated and further crystallized at room temperature over a period of several months. Composition fluctuations related to a limited blockiness on a length scale above approximately 2 nm were detected for PMMAEA particles, whereas the surfmer particles were found to be homogeneous also below this limit. On a particle-particle level, the dispersions tended to form colloidal crystals unless hindered by a broadened particle size distribution or, in the case of PMMAEA, by the action of NP100. Finally, a surface roughness (Rq) master plot was constructed for data above the glass transition temperature (Tg) from Tg + 11 degrees C to Tg + 57 degrees C and compared with the complex shear modulus over 11 frequency decades. Shift factors from the 2 methods obeyed the same Williams-Landel-Ferry (WLF) temperature dependence, thus connecting the long-time surface flattening process to the rheological behavior of the copolymer.     

Surfactant enhanced lipase containing films characterized by confocal laser scanning microscopy

An environmentally benign method for the synthesis of noble metal nanoparticles has been reported using aqueous solution of gum kondagogu (Cochlospermum gossypium). Both the synthesis, as well as stabilization of colloidal Ag, Au and Pt nanoparticles has been accomplished in an aqueous medium containing gum kondagogu. The colloidal suspensions so obtained were found to be highly stable for prolonged period, without undergoing any oxidation. SEM–EDXA, UV–vis spectroscopy, XRD, FTIR and TEM techniques were used to characterize the Ag, Au and Pt nanoparticles. FTIR analysis indicates that –OH groups present in the gum matrix were responsible for the reduction of metal cations into nanoparticles. UV–vis studies showed a distinct surface plasmon resonance at 412 and 525 nm due to the formation of Au and Ag nanoparticles, respectively, within the gum network. XRD studies indicated that the nanoparticles were crystalline in nature with face centered cubic geometry. The noble metal nanoparticles prepared in the present study appears to be homogeneous with the particle size ranging between 2 and 10 nm, as evidenced by TEM analysis. The Ag and Au nanoparticles formed were in the average size range of 5.5 ± 2.5 nm and 7.8 ± 2.3 nm; while Pt nanoparticles were in the size range of 2.4 ± 0.7 nm, which were considerably smaller than Ag and Au nanoparticles. The present approach exemplifies a totally green synthesis using the plant derived natural product (gum kondagogu) for the production of noble metal nanoparticles and the process can also be extended to the synthesis of other metal oxide nanoparticles.     

Cephalosporin-3'-diazeniumdiolates: Targeted NO-Donor Prodrugs for Dispersing Bacterial Biofilms

Just say NO to biofilms: NO-donors are used to disperse a bacterial biofilm so that co-administered antibiotics will kill the more susceptible unattached cells. The chemically stable cephalosporin-3'-diazeniumdiolate NO-donor prodrug is activated by bacterial β-lactamases and facilitates this two-step biofilm erradication.     

PIV analysis of merging flow in a simplified model of a rotary kiln

Rotary kilns are used in a variety of industrial applications. The focus in this work is on characterizing the non-reacting, isothermal flow field in a rotary kiln used for iron ore pelletization. A downscaled, simplified model of the kiln is experimentally investigated using particle image velocimetry. Five different momentum flux ratios of the two inlet ducts to the kiln are investigated in order to evaluate its effect on the flow field in general and the recirculation zone in particular. Time-averaged and phase-averaged analyses are reported, and it is found that the flow field resembles that of two parallel merging jets, with the same characteristic flow zones. The back plate separating the inlet ducts acts as a bluff body to the flow and creates a region of reversed flow behind it. Due to the semicircular cross-section of the jets, the wake is elongated along the walls. Conclusions are that the flow field shows a dependence on momentum flux ratio of the jets; as the momentum flux ratio approaches unity, there is an increasing presence of von Kármán-type coherent structures with a Strouhal number of between 0.16 and 0.18. These large-scale structures enhance the mixing of the jets and also affect the size of the recirculation zone. It is also shown that the inclination of the upper inlet duct leads to a decrease in length of the recirculation zone in certain cases.