Ion chromatograph with three-dimensional printed absorbance detector for indirect ultraviolet absorbance detection of phosphate in effluent and natural waters

An ion chromatography system employing a low-cost three-dimensional printed absorbance detector for indirect ultraviolet detection towards portable phosphate analysis of environmental and industrial waters has been developed. The optical detection cell was fabricated using stereolithography three-dimensional printing of nanocomposite material. Chromatographic analysis and detection of phosphate were carried out using a CS5A 4 × 250 mm analytical column with indirect ultraviolet detection using a 255 nm light-emitting diode. Isocratic elution using a 0.6 mM potassium phthalate eluent combined with 1.44 mM sodium bicarbonate was employed at a flow rate of 0.75 mL/min. A linear calibration range of 0.5 to 30 mg/L PO₄³⁻ applicable to environmental and wastewater analysis was achieved. For retention time and peak area repeatability, relative standard deviation values were 0.68 and 4.09%, respectively. Environmental and wastewater samples were analyzed with the optimized ion chromatography platform and the results were compared to values obtained by an accredited ion chromatograph. For the analysis of environmental samples, relative errors of <14 % were achieved. Recovery analysis was also carried out on both freshwater and wastewater samples and recovery results were within the acceptable range for water analysis using standard ion chromatography methods.     

Structural effects in pyrazolidinone-mediated organocatalytic Diels-Alder reactions

A range of pyrazolidin-3-ones have been prepared and their activity as catalysts for iminium-ion promoted Diels-Alder reactions evaluated. Systematic variation of the C(5)- and N(2)-substituents indicates that the incorporation of an electron withdrawing substitutent at N(2) and either a Ph or CF₃ substitution at C(5) results in optimal catalytic activity. The diastereoisomeric resolution of a model C(5)-Ph substituted pyrazolidinone and its ability to impart modest levels of asymmetric induction in the organocatalytic Diels-Alder reaction is also demonstrated.     

Synthesis of aryl ring-fused benzimidazolequinones using 6-exo-trig radical cyclizations

The preparation of alicyclic ring-fused tetracyclic and pentacyclic benzimidazoles containing one and two fused aryl rings, respectively, is achieved conveniently in three steps, including Bu₃SnH-mediated 6-exo-trig cyclization of σ-aryl radicals generated from 1-allyl-2-(ω-bromoaryl)benzimidazoles. Inclusion of 4,7-dimethoxy substituents on the radical precursors allows access to aryl ring-fused benzimidazolequinones, a unique family of potential bioreductive anti-cancer agents.     

Ultralow phase noise microwave generation with an Er:fiber-based optical frequency divider

We present an optical frequency divider based on a 200 MHz repetition rate Er:fiber mode-locked laser that, when locked to a stable optical frequency reference, generates microwave signals with absolute phase noise that is equal to or better than cryogenic microwave oscillators. At 1 Hz offset from a 10 GHz carrier, the phase noise is below -100 dBc/Hz, limited by the optical reference. For offset frequencies >10 kHz, the phase noise is shot noise limited at -145 dBc/Hz. An analysis of the contribution of the residual noise from the Er:fiber optical frequency divider is also presented.     

Robust Damping in Self-Excited Mechanical Systems

A technique to optimize the stability of a general mechanical system is outlined. The method relies on decomposing the damping matrix into several component matrices, which may have some special structure or physical relevance. An optimization problem can then be formulated where the ratio of these are varied to either stabilize or make more stable the equilibrium state subject to sensible constraints. For the purpose of this study, we define a system to be more stable if its eigenvalue with largest real part is as negative as possible. The technique is demonstrated by applying it to an introduced non-dimensionalized variant of a known minimal wobbling disc brake model. In this case, it is shown to be beneficial to shift some damping from the disc to the pins for a system optimized for stability. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Biphasic synthesis of Au@SiO2 core-shell particles with stepwise ligand exchange

We report the synthesis of well-dispersed core-shell Au@SiO(2) nanoparticles with minimal extraneous silica particle growth. Agglomeration was suppressed through consecutive exchange of the stabilizing ligands on the gold cores from citrate to L-arginine and finally (3-mercaptopropyl)triethoxysilane. The result was a vitreophilic, stable gold suspension that could be coated with silica in a biphasic mixture through controlled hydrolysis of tetraethoxysilane under L-arginine catalysis. Unwanted condensation of silica particles without gold cores was limited by slowing the transfer across the liquid-liquid interface and reducing the concentration of the L-arginine catalyst. In-situ dynamic light scattering and optical transmission spectroscopy revealed the growth and dispersion states during synthesis. The resulting core-shell particles were characterized via dynamic light scattering, optical spectroscopy, and electron microscopy. Their cores were typically 19 nm in diameter, with a narrow size distribution, and could be coated with a silica shell in multiple steps to yield core-shell particles with diameters up to 40 nm. The approach was sufficiently controllable to allow us to target a shell thickness by choosing appropriate precursor concentrations.     

The synthesis of P-stereogenic MOP analogues and their use in rhodium catalysed asymmetric addition

The synthesis is reported of novel P-stereogenic binaphthyl substituted monophosphines via a short five-step synthesis using a nickel coupling reaction with separation of the borane-protected diastereomeric products. Extensive coordination studies of these ligands with a number of well-known metal precursors were performed to more effectively understand their behaviour during catalysis.These ligands and some previously reported P-stereogenic ligands were tested in the rhodium catalysed asymmetric addition of phenyl boronic acid to napthaldehyde. These studies in asymmetric catalysis were used to compare the chiral induction of ligands that combine both axial and central chirality with ligands lacking P-stereogenicity.     

Spaces of matrices without non-zero eigenvalues in their field of definition, and a question of Szechtman

Let V be a vector space of dimension n over any field F. Extreme values for the possible dimension of a linear subspace of End_F(V) with a particular property are considered in two specific cases. It is shown that if E₁ is a subspace of End_F(V) and there exists an endomorphism g of V, not in E₁, such that for every hyperplane H of V some element of E₁ agrees with g on H, then E₁ has dimension at least . This answers a question that was posed by Szechtman in 2003. It is also shown that a linear subspace of M_n(F) in which no element possesses a non-zero eigenvalue in F may have dimension at most . The connection between these two properties, which arises from duality considerations, is discussed.     

Practical mm-Wave pHEMT Frequency Multiplier

Details on a broadband MMIC frequency doubler targeting the MVDS market are presented. The design evolution from an individual pHEMT device to the complete practical doubler realisation is discussed. The doubler MMIC, which has been fabricated using the GMMT H40 GaAs process, has been evaluated in a customised package. An output power of +10 dBm at 40 GHz has been achieved with an associated conversion gain of 1.5 dB. The measured and predicted performance responses are compared. This chip is ideally suited to use in a number of emerging mm-wave applications.