First Step Towards a Devil's Staircase in Spin‐Crossover Materials

The unprecedented bimetallic 2D coordination polymer {Fe[(Hg(SCN)₃)₂](4,4′‐bipy)₂}_n exhibits a thermal high‐spin (HS)?low‐spin (LS) staircase‐like conversion characterized by a multi‐step dependence of the HS molar fraction γ_HS. Between the fully HS (γ_HS=1) and LS (γ_HS=0) phases, two steps associated with different ordering appear in terms of spin‐state concentration waves (SSCW). On the γ_HS≈0.5 step, a periodic SSCW forms with a HS‐LS‐HS‐LS sequence. On the γ_HS≈0.34 step, the 4D superspace crystallography structural refinement reveals an aperiodic SSCW, with a HS‐LS sequence incommensurate with the molecular lattice. The formation of these different long‐range spatially ordered structures of LS and HS states during the multi‐step spin‐crossover is discussed within the framework of “Devil's staircase”‐type transitions. Spatially modulated phases are known in various types of materials but are uniquely related to molecular HS/LS bistability in this case.     

2D Porphyrinic Metal-Organic Frameworks Featuring Rod-Shaped Secondary Building Units

Metal-organic frameworks (MOFs) encompass a rapidly expanding class of materials with diverse potential applications including gas storage, molecular separation, sensing and catalysis. So-called ‘rod MOFs’, which comprise infinitely extended 1D secondary building units (SBUs), represent an underexplored subclass of MOF. Further, porphyrins are considered privileged ligands for MOF synthesis due to their tunable redox and photophysical properties. In this study, the Cu^II complex of 5,15-bis(4-carboxyphenyl)-10,20-diphenylporphyrin (H₂L-Cu^II, where H₂ refers to the ligand’s carboxyl H atoms) is used to prepare two new 2D porphyrinic rod MOFs PROD-1 and PROD-2. Single-crystal X-ray analysis reveals that these frameworks feature 1D Mn^II- or Co^II-based rod-like SBUs that are coordinated by labile solvent molecules and photoactive porphyrin moieties. Both materials were characterised using infrared (IR) spectroscopy, powder X-ray diffraction (PXRD) spectroscopy and thermogravimetric analysis (TGA). The structural attributes of PROD-1 and PROD-2 render them promising materials for future photocatalytic investigations.     

Electrochemical preparation of distinct polyaniline nanostructures by surface charge control of polystyrene nanoparticle templates

A family of nanostructured polyaniline (PANI) materials including polystyrene (PS)/PANI core/shell particles, PANI hollow spheres, PANI/PS nanocomposite and nanoporous PANI, were conveniently prepared by surface charge control of PS nanoparticle templates which resulted in different polymer growth mechanisms when PANI was electropolymerized around the templates.     

Characterisation and Classification of Foodborne Bacteria Using Reflectance FTIR Microscopic Imaging

This work investigates the application of reflectance Fourier transform infrared (FTIR) microscopic imaging for rapid, and non-invasive detection and classification between Bacillus subtilis and Escherichia coli cell suspensions dried onto metallic substrates (stainless steel (STS) and aluminium (Al) slides) in the optical density (OD) concentration range of 0.001 to 10. Results showed that reflectance FTIR of samples with OD lower than 0.1 did not present an acceptable spectral signal to enable classification. Two modelling strategies were devised to evaluate model performance, transferability and consistency among concentration levels. Modelling strategy 1 involves training the model with half of the sample set, consisting of all concentrations, and applying it to the remaining half. Using this approach, for the STS substrate, the best model was achieved using support vector machine (SVM) classification, providing an accuracy of 96% and Matthews correlation coefficient (MCC) of 0.93 for the independent test set. For the Al substrate, the best SVM model produced an accuracy and MCC of 91% and 0.82, respectively. Furthermore, the aforementioned best model built from one substrate was transferred to predict the bacterial samples deposited on the other substrate. Results revealed an acceptable predictive ability when transferring the STS model to samples on Al (accuracy = 82%). However, the Al model could not be adapted to bacterial samples deposited on STS (accuracy = 57%). For modelling strategy 2, models were developed using one concentration level and tested on the other concentrations for each substrate. Results proved that models built from samples with moderate (1 OD) concentration can be adapted to other concentrations with good model generalization. Prediction maps revealed the heterogeneous distribution of biomolecules due to the coffee ring effect. This work demonstrated the feasibility of applying FTIR to characterise spectroscopic fingerprints of dry bacterial cells on substrates of relevance for food processing.     

Beam quality of a nonideal atom laser

We study the propagation of a noninteracting atom laser distorted by the strong lensing effect of the Bose-Einstein condensate (BEC) from which it is outcoupled. We observe a transverse structure containing caustics that vary with the density within the residing BEC. Using the WKB approximation, Fresnel-Kirchhoff integral formalism, and ABCD matrices, we are able to describe analytically the atom-laser propagation. This allows us to characterize the quality of the nonideal atom-laser beam by a generalized M2 factor defined in analogy to photon lasers. Finally we measure this quality factor for different lensing effects.     

Evaluation of near-infrared chemical imaging for the prediction of surface water quality parameters

Near-infrared (NIR) chemical imaging is an emerging technique with the potential for the detection of contaminants in the environmental field. In this study the potential of NIR chemical imaging (NIR-CI) to predict concentrations of nutrients (total nitrogen, total phosphorus) and indicator microorganisms (Escherichia coli) in surface water was investigated. Chemical images of multiple samples were obtained simultaneously using a pushbroom imaging system operating in the 950–1650 nm wavelength range with spectral resolution of 7 nm. Using partial least squares regression models, the relationship between these pollutants and NIR spectral data extracted from the chemical images in samples of aqueous surface water and filtered residue from surface water was assessed. When calibration models were tested on an independent data set, it was found that models developed on filtered residue spectra outperformed those developed on aqueous samples. For samples of filtered residue, the performance of the calibrations achieved for total nitrogen was reasonable (R² > 0.75); however, performance for total phosphorus and E. coli was poor (R² < 0.5). Lower concentrations of these parameters were detected in the surface water samples included in the study (<1 mg L^?1 and <20 colony-forming units per 100 mL, respectively), a likely reason for the poor performance. The results indicate that NIR-CI has the potential for screening samples in which the contaminant concentration exceeds 1 mg L^?1.     

Nucleophilic substitution at silicon: influence of the nature of the leaving group on the stereochemistry

The stereochemistries observed for nucleophilic substitutions on optically active bromo- and thiophenyl-silanes are compared with those reported for Cl, F, OR and H leaving groups. They allow the completion of the previously proposed empirical order for the dependence of stereochemistry in the nature of the leaving group viz.; predominant stereochemistry: IN → RN; ease of substitution: Br ? Cl ? SR ? F ? OMe > H.     

New reactive fluorophores in the 1,2,3-triazine series

A one-pot synthesis of new fluorescent 2,5-dihydro-1,2,3-triazines with reactive functional groups and a large Stokes shift of 200 nm is described.     

Microthermographie infrarouge et decomposition des solides

Infrared microthermography was used to study dynamically the decomposition of single cristalline platelets (surface 1 cm²) of copper sulfate pentahydrate. The measurement of the local self cooling allows to plot the thermal profiles in front of the reaction and yields the temperature of the reactive interface. It is also possible to plot the thermal maps of the samples for their evolution, and thereby gets permitted knowledge of the gradients of temperature in those reactions. The evolution of these values with pressure, orientation of the platelets or of the reactive interface is envisaged.

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Zusammenfassung Die Infrarotmikrothermographie wurde zur dynamischen Untersuchung der Zersetzung von Kupfersulfat-Pentahydrat in Form von Einkristallplättchen (Oberfläche 1 cm²) herangezogen. Die Messung der lokalen Selbstabkühlung ermöglicht, die thermischen Profile in der Reaktionsfront aufzuzeichnen und die Temperatur der reaktiven Grenzfläche zu erhalten. Es ist auch möglich, die thermischen Karten der Proben darzustellen und damit eingehende Kenntnisse über die Temperaturgradienten bei solchen Reaktionen zu gewinnen. Untersuchungen sind vorgesehen, um zu klären, wie Druck und Orientierung der Plättchen oder der reaktiven Grenzfläche diese Werte beeinflussen.

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