Evaluation of formaldehyde in foundry waste sands using liquid chromatography

The industrial manufacturing of metallic objects results in a high level of foundry waste sands that may contain toxic compounds such as formaldehyde. The formaldehyde content of foundry waste sands was evaluated by liquid chromatography. Samples were collected during various steps of the industrial processes. Results showed that the phenolic alkaline process generated waste sands with higher formaldehyde content than the furanic process; the highest value was 7.6×10-3% (w/w). In this work, formaldehyde content decreased with time in all of the samples studied, revealing that most formaldehyde was released to the occupational environment.

An insight into dapsone co-crystals: sulfones as participants in supramolecular interactions

Agência Financiadora: Fundação para a Ciência e a Tecnologia - Pest-OE/QUI/UI0100/2013; PTDC/CTM-BPC/122447/2010; RECI/QEQ-QIN/0189/2012; SFRH/BPD/78854/2011

Determination of free formaldehyde in foundry resins as its 2,4-dinitrophenylhydrazone by liquid chromatography

Formaldehyde is a toxic component that is present in foundry resins. Its quantification is important to the characterisation of the resin (kind and degradation) as well as for the evaluation of free contaminants present in wastes generated by the foundry industry. The complexity of the matrices considered suggests the need for separative techniques. The method developed for the identification and quantification of formaldehyde in foundry resins is based on the determination of free carbonyl compounds by derivatization with 2,4-dinitrophenylhydrazine (DNPH), being adapted to the considered matrices using liquid chromatography (LC) with UV detection. Formaldehyde determinations in several foundry resins gave precise results. Mean recovery and R.S.D. were, respectively, >95 and 5%. Analyses by the hydroxylamine reference method gave comparable results. Results showed that hydroxylamine reference method is applicable just for a specific kind of resin, while the developed method has good performance for all studied resins.

Biomimetic sensors of molecularly-imprinted polymers for chlorpromazine determination

A new man-tailored biomimetic sensor for Chlorpromazine host-guest interactions and potentiometric transduction is presented. The artificial host was imprinted within methacrylic acid, 2-vinyl pyridine and 2-acrylamido-2-methyl-1-propanesulfonic acid based polymers. Molecularly imprinted particles were dispersed in 2-nitrophenyloctyl ether and entrapped in a poly(vinyl chloride) matrix. Slopes and detection limits ranged 51–67 mV/decade and 0.46–3.9 μg/mL, respectively, in steady state conditions. Sensors were independent fromthe pHof test solutionswithin 2.0–5.5.Good selectivitywas observed towards oxytetracycline, doxytetracycline, ciprofloxacin, enrofloxacin, nalidixic acid, sulfadiazine, trimethoprim, glycine, hydroxylamine, cysteine and creatinine. Analytical features in flowing media were evaluated on a double-channel manifold, with a carrier solution of 5.0×10−2 mol/L phosphate buffer. Near-Nernstian response was observed over the concentration range 1.0×10−4 to 1.0×10−2 mol/L. Average slopes were about 48 mV/decade. The sensors were successfully applied to field monitoring of CPZ in fish samples, offering the advantages of simplicity, accuracy, automation feasibility and applicability to complex samples.

New sensing materials of molecularly-imprinted polymers for the selective recognition of Chlortetracycline

As a result of the stressful conditions in aquaculture facilities there is a high risk of bacterial infections among cultured fish. Chlortetracycline (CTC) is one of the antimicrobials used to solve this problem. It is a broad spectrum antibacterial active against a wide range of Gram-positive and Gram-negative bacteria. Numerous analytical methods for screening, identifying, and quantifying CTC in animal products have been developed over the years. An alternative and advantageous method should rely on expeditious and efficient procedures providing highly specific and sensitive measurements in food samples. Ion-selective electrodes (ISEs) could meet these criteria. The only ISE reported in literature for this purpose used traditional electro-active materials. A selectivity enhancement could however be achieved after improving the analyte recognition by molecularly imprinted polymers (MIPs). Several MIP particles were synthesized and used as electro-active materials. ISEs based in methacrylic acid monomers showed the best analytical performance according to slope (62.5 and 68.6 mV/decade) and detection limit (4.1×10−5 and 5.5×10−5 mol L−1). The electrodes displayed good selectivity. The ISEs are not affected by pH changes ranging from 2.5 to 13. The sensors were successfully applied to the analysis of serum, urine and fish samples.

Trimethoprim-selective electrodes with molecularly imprinted polymers acting as ionophores and potentiometric transduction on graphite solid-contact

This work proposes a new biomimetic sensor material for trimethoprim. It is prepared by means of radical polymerization, having trimethylolpropane trimethacrylate as cross-linker, benzoyl peroxide as radicalar iniciator, chloroform as porogenic solvent, and methacrylic acid and 2-vinyl pyridine as monomers. Different percentages of sensor in a range between 1 and 6% were studied. Their behavior was compared to that obtained with ion-exchanger quaternary ammonium salt (additive tetrakis(p-chlorophenyl)borate or tetraphenylborate). The effect of an anionic additive in the sensing membrane was also tested. Trimethoprim sensors with 1% of imprinted particles from methacrylic acid monomers showed the best response in terms of slope (59.7 mV/decade) and detection limit (4.01×10−7 mol/L). These electrodes displayed also a good selectivity towards nickel, manganese aluminium, ammonium, lead, potassium, sodium, iron, chromium, sulfadiazine, alanine, cysteine, tryptophan, valine and glycine. The sensors were not affected by pH changes from 2 to 6. They were successfully applied to the analysis of water from aquaculture.

Transport mechanism in ionic liquid membranes and the study of thiomersal biodegradation

The initial goal of this work was the development of a supported liquid membrane (SLM) bioreactor for the remediation of vaccine production effluents contaminated with a highly toxic organomercurial – thiomersal. Therefore, two main aspects were focused on: 1) the development of a stable supported liquid membrane – using room temperature ionic liquids (RTILs) – for the selective transport of thiomersal from the wastewater to a biological compartment, 2) study of the biodegradation kinetics of thiomersal to metallic mercury by a Pseudomonas putida strain. The first part of the work focused on the evaluation of the physicochemical properties of ionic liquids and on the SLMs’ operational stability. The results obtained showed that, although it is possible to obtain a SLM with a high stability, water possesses nonnegligible solubility in the RTILs studied. The formation of water clusters inside the hydrophobic ionic liquid was identified and found to regulate the transport of water and small ions. In practical terms, this meant that, although it was possible to transport thiomersal from the vaccine effluent to the biological compartment, complete isolation of the microbial culture could not be guaranteed and the membrane might ultimately be permeable to other species present in the aqueous vaccine wastewater. It was therefore decided not to operate the initially targeted integrated system but, instead, the biological system by itself. Additionally, attention was given to the development of a thorough understanding of the transport mechanisms involved in the solubilisation and transport of water through supported liquid membranes with RTILs as well as to the evaluation of the effect of water uptake by the SLM in the transport mechanisms of water-soluble solutes and its effect on SLM performance. The results obtained highlighted the determinant role played by water – solubilised inside the ionic liquids – on the transport mechanism. It became clear that the transport mechanism of water and water-soluble solutes through SLMs with [CnMIM][PF6] RTILs was regulated by the dynamics of water clusters inside the RTIL, rather than by molecular diffusion through the bulk of the ionic liquid. Although the stability tests vi performed showed that there were no significant losses of organic phase from the membrane pores, the formation of water clusters inside the ionic liquid, which constitute new, non-selective environments for solute transport, leads to a clear deterioration of SLM performance and selectivity. Nevertheless, electrical impedance spectroscopy characterisation of the SLMs showed that the formation of water clusters did not seem to have a detrimental effect on the SLMs’ electrical characteristics and highlighted the potential of using this type of membranes in electrochemical applications with low resistance requirements. The second part of the work studied the kinetics of thiomersal degradation by a pure culture of P. putida spi3 strain, in batch culture and using a synthe tic wastewater. A continuous ly stirred tank reactor fed with the synthetic wastewater was also operated and the bioreactor’s performance and robustness, when exposed to thiomersal shock loads, were evaluated. Finally, a bioreactor for the biological treatment of a real va ccine production effluent was set up and operated at different dilution rates. Thus it was possible to treat a real thiomersal-contaminated effluent, lowering the outlet mercury concentration to values below the European limit for mercury effluent discharges.

Fractional dynamics in liquid manipulation

This paper presents a fractional calculus perspective in the study of signals captured during the movement of a mechanical manipulator carrying a liquid container. In order to study the signals an experimental setup is implemented. The system acquires data from the sensors, in real time, and, in a second phase, processes them through an analysis package. The analysis package runs off-line and handles the recorded data. The results show that the Fourier spectrum of several signals presents a fractional behavior. The experimental study provides useful information that can assist in the design of a control system and the trajectory planning to be used in reducing or eliminating the effect of vibrations.

Calix[4]arene-carbazole-containing polymers: synthesis and properties

New highly fluorescent calix[4]arene-containing phenylene-alt-ethynylene-3,6- and 2,7-carbazolylene polymers (CALIX-PPE-CBZs) have been synthesized for the first time and their photophysical properties evaluated. Both polymers were obtained in good isolated yields (70-84%), having M-w ranging from 7660-26,700 g mol(-1). It was found that the diethynyl substitution (3,6- or 2,7-) pattern on the carbazole monomers markedly influences the degree of polymerization. The amorphous yellow polymers are freely soluble in several nonprotic organic solvents and have excellent film forming abilities. TG/DSC analysis evidences similar thermal behaviors for both polymers despite their quite different molecular weight distributions and main-chain connectivities (T-g, in the range 83-95 degrees C and decomposition onsets around 270 degrees C). The different conjugation lengths attained by the two polymers dictates much of their photophysical properties. Thus, whereas the fully conjugated CALIX-PPE-2,7-CBZ has its emission maximum at 430 nm (E-g = 2.84 eV; Phi(F) = 0.62, CHCl3), the 3,6-linked counterpart (CALIX-PPE-3,6-CBZ) fluoresces at 403 nm with a significant lower quantum yield (E-g = 3.06 eV; Phi(F) = 0.31, CHCl3). The optical properties of both polymers are predominantly governed by the intrachain electronic properties of the conjugated backbones owing to the presence of calix[4]arenes along the polymer chain which disfavor significant interchain interactions, either in fluid- or solid-state.

Growth of (Perylene)(2) [PD(MNT)(2)] crystals

The conditions for [pd(mnt)(2)]he growth of [pd(mnt)(2)]Perylene) [pd(mnt)(2)] [Pd(mnt) [pd(mnt)(2)]] crystals either by chemical oxidation and electrochemical routes are [pd(mnt)(2)]escribed. The electrocrystallisation is limited by close [pd(mnt)(2)]roximity of [pd(mnt)(2)]he oxidation [pd(mnt)(2)]otentials of [pd(mnt)(2)]he [pd(mnt)(2)]erylene [pd(mnt)(2)]onor and [Pd(mnt) [pd(mnt)(2)]] - anion, and [pd(mnt)(2)]epending on [pd(mnt)(2)]he experimental conditions [pd(mnt)(2)]ifferent [pd(mnt)(2)]orphologies can be obtained. [pd(mnt)(2)]Per) [pd(mnt)(2)] [Pd(mnt) [pd(mnt)(2)]] crystals obtained by elecrocrystallisation were found [pd(mnt)(2)]o be [pd(mnt)(2)]ainly of [pd(mnt)(2)]he β-polymorph with [pd(mnt)(2)]roperties comparable [pd(mnt)(2)]o [pd(mnt)(2)]he Cu, Ni and Pt analogues [pd(mnt)(2)]reviously [pd(mnt)(2)]escribed at variance with [pd(mnt)(2)]hose obtained by chemical oxidation which are [pd(mnt)(2)]ainly of [pd(mnt)(2)]he α-polymorph.

Liquid crystal beads constrained on thin cellulosic fibers: Electric field induced microrotors and N-I transition

We directly visualize the response of nematic liquid crystal drops of toroidal topology threaded in cellulosic fibers, suspended in air, to an AC electric field and at different temperatures over the N-I transition. This new liquid crystal system can exhibit non-trivial point defects, which can be energetically unstable against expanding into ring defects depending on the fiber constraining geometries. The director anchoring tangentially near the fiber surface and homeotropically at the air interface makes a hybrid shell distribution that in turn causes a ring disclination line around the main axis of the fiber at the center of the droplet. Upon application of an electric field, E, the disclination ring first expands and moves along the fiber main axis, followed by the appearance of a stable "spherical particle" object orbiting around the fiber at the center of the liquid crystal drop. The rotation speed of this particle was found to vary linearly with the applied voltage. This constrained liquid crystal geometry seems to meet the essential requirements in which soliton-like deformations can develop and exhibit stable orbiting in three dimensions upon application of an external electric field. On changing the temperature the system remains stable and allows the study of the defect evolution near the nematic-isotropic transition, showing qualitatively different behaviour on cooling and heating processes. The necklaces of such liquid crystal drops constitute excellent systems for the study of topological defects and their evolution and open new perspectives for application in microelectronics and photonics.

Properties of patchy colloidal particles close to a surface: a Monte Carlo and density functional study

We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheim's first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.

Post-processing Techniques in Free Boundary Flows during Liquid Composite Moulding Processes

Post-processing a finite element solution is a well-known technique, which consists in a recalculation of the originally obtained quantities such that the rate of convergence increases without the need for expensive remeshing techniques. Postprocessing is especially effective in problems where better accuracy is required for derivatives of nodal variables in regions where Dirichlet essential boundary condition is imposed strongly. Consequently such an approach can be exceptionally good in modelling of resin infiltration under quasi steady-state assumption by remeshing techniques and with explicit time integration, because only the free-front normal velocities are necessary to advance the resin front to the next position. The new contribution is the post-processing analysis and implementation of the freeboundary velocities of mesolevel infiltration analysis. Such implementation ensures better accuracy on even coarser meshes, which in consequence reduces the computational time also by the possibility of employing larger time steps.

Numerical Method to Predict Void Formation during The Liquid Composite Molding Process

Void formation during the injection phase of the liquid composite molding process can be explained as a consequence of the non-uniformity of the flow front progression. This is due to the dual porosity within the fiber perform (spacing between the fiber tows is much larger than between the fibers within in a tow) and therefore the best explanation can be provided by a mesolevel analysis, where the characteristic dimension is given by the fiber tow diameter of the order of millimeters. In mesolevel analysis, liquid impregnation along two different scales; inside fiber tows and within the open spaces between the fiber tows must be considered and the coupling between the flow regimes must be addressed. In such cases, it is extremely important to account correctly for the surface tension effects, which can be modeled as capillary pressure applied at the flow front. Numerical implementation of such boundary conditions leads to illposing of the problem, in terms of the weak classical as well as stabilized formulation. As a consequence, there is an error in mass conservation accumulated especially along the free flow front. A numerical procedure was formulated and is implemented in an existing Free Boundary Program to reduce this error significantly.

Catalytic oxidation of cyclohexane with hydrogen peroxide and a tetracopper(II) complex in an ionic liquid

The catalytic peroxidative oxidation (with H2O2) of cyclohexane in an ionic liquid (IL) using the tetracopper(II) complex [(CuL)2(μ4-O,O′,O′′,O′′′-CDC)]2·2H2O [HL = 2-(2-pyridylmethyleneamino)benzenesulfonic acid, CDC = cyclohexane-1,4-dicarboxylate] as a catalyst is reported. Significant improvements on the catalytic performance, in terms of product yield (up to 36%), TON (up to 529), reaction time, selectivity towards cyclohexanone and easy recycling (negligible loss in activity after three consecutive runs), are observed using 1-butyl-3-methylimidazolium hexafluorophosphate as the chosen IL instead of a molecular organic solvent including the commonly used acetonitrile. The catalytic behaviors in the IL and in different molecular solvents are discussed.