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.     

Dendrimers Functionalized with Palladium Complexes of N-, N,N-, and N,N,N-Ligands

Pyridine, pyridine imine, and bipyridine imine ligands functionalized by a phenol have been synthesized and characterized, in many cases by X-ray diffraction. Several of these N-, N,N-, and N,N,N,-ligands have been grafted onto the surface of phosphorhydrazone dendrimers, from generation 1 to generation 3. The complexation ability of these monomers and dendrimers towards palladium(II) has been assayed. The corresponding complexes have been either isolated or prepared in situ. In both cases, the monomeric and dendritic complexes have been tested as catalysts in Heck couplings and in Sonogashira couplings. In some cases, a positive dendritic effect has been observed, that is, an increase of the catalytic efficiency proportional to the dendrimer generation.     

Narrow-line phase-locked quantum cascade laser in the 9.2 microm range

We report the operation of a 50 mW continuous-wave quantum cascade laser (QCL) in the 9.2 microm range, phase locked to a single-mode CO(2) laser with a tunable frequency offset. The wide free-running emission spectrum of the QCL (3-5 MHz) is strongly narrowed down to the kilohertz range, making it suitable for high-resolution molecular spectroscopy.     

[2]Catenane Synthesis via Covalent Templating

After earlier unsuccessful attempts, this work reports the application of covalent templating for the synthesis of mechanically interlocked molecules (MiMs) bearing no supramolecular recognition sites. Two linear strands were covalently connected in a perpendicular fashion by a central ketal linkage. After subsequent attachment of the first strand to a template via temporary benzylic linkages, the second was linked to the template in a backfolding macrocyclization. The resulting pseudo[1]rotaxane structure was successfully converted to a [2]catenane via a second macrocyclization and cleavage of the ketal and temporary linkages.     

A well-balanced and asymptotic-preserving scheme for the one-dimensional linear Dirac equation

The numerical approximation of one-dimensional relativistic Dirac wave equations is considered within the recent framework consisting in deriving local scattering matrices at each interface of the uniform Cartesian computational grid. For a Courant number equal to unity, it is rigorously shown that such a discretization preserves exactly the \(L^2\) norm despite being explicit in time. This construction is well-suited for particles for which the reference velocity is of the order of \(c\), the speed of light. Moreover, when \(c\) diverges, that is to say, for slow particles (the characteristic scale of the motion is non-relativistic), Dirac equations are naturally written so as to let a “diffusive limit” emerge numerically, like for discrete 2-velocity kinetic models. It is shown that an asymptotic-preserving scheme can be deduced from the aforementioned well-balanced one, with the following properties: it yields unconditionally a classical Schrödinger equation for free particles, but it handles the more intricate case with an external potential only conditionally (the grid should be such that \(c \Delta x\rightarrow 0\)). Such a stringent restriction on the computational grid can be circumvented easily in order to derive a seemingly original Schrödinger scheme still containing tiny relativistic features. Numerical tests (on both linear and nonlinear equations) are displayed.     

Direct Evidence for Intermolecular Oxidative Addition of σ(SiSi) Bonds to Gold

Oxidative addition plays a major role in transition‐metal catalysis, but this elementary step remains very elusive in gold chemistry. It is now revealed that in the presence of GaCl₃, phosphine gold chlorides promote the oxidative addition of disilanes at low temperature. The ensuing bis(silyl) gold(III) complexes were characterized by quantitative ³¹P and ²⁹Si NMR spectroscopy. Their structures (distorted Y shape) and the reaction profile of σ(Si? Si) bond activation were analyzed by DFT calculations. These results provide evidence for the intermolecular oxidative addition of σ(Si? Si) bonds to gold and open promising perspectives for the development of new gold‐catalyzed redox transformations.     

Predicting New Ugi–Smiles Couplings: A Combined Experimental and Theoretical Study

Following our previous mechanistic studies of multicomponent Ugi‐type reactions, theoretical calculations have been performed to predict the efficiency of new substrates in Ugi–Smiles couplings. First, as predicted, 2,4,6‐trichlorophenol experimentally gave the corresponding aryl‐imidate. Theoretical predictions of nitrosophenols as good acidic partners were then successfully confirmed by experiments. In the latter case, the reaction offers a new access to benzimidazoles.     

On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen,Ni(N2)2

The electronic ground and excited states of the coordinatively unsaturated complex Ni(η¹‐N₂)₂, isolated in an Ar matrix, are analyzed in detail by vibrational and electronic absorption and emission spectroscopies allied with quantum chemical calculations. The bond force constants are determined from a normal coordinate analysis and compared with those of the isoelectronic carbonyl complex. The consequences for the bond properties are discussed, and the trend in the force constants is compared with the standard formation enthalpies. The linear complex Ni(η¹‐N₂)₂ with two terminal dinitrogen ligands can be photoisomerized to two isomeric, metastable forms Ni(η¹‐N₂)(η²‐N₂) and Ni(η²‐N₂)₂, with one and two side‐on coordinated dinitrogen ligands, respectively.