Infrared chemical imaging: Spatial resolution evaluation and super-resolution concept

Chemical imaging systems help to solve many challenges in various scientific fields. Able to deliver rapid spatial and chemical information, modern infrared spectrometers using Focal Plane Array detectors (FPA) are of great interest. Considering conventional infrared spectrometers with a single element detector, we can consider that the diffraction-limited spatial resolution is more or less equal to the wavelength of the light (i.e. 2.5-25 μm). Unfortunately, the spatial resolution of FPA spectroscopic setup is even lower due to the detector pixel size. This becomes a real constraint when micron-sized samples are analysed. New chemometrics methods are thus of great interest to overcome such resolution drawback, while keeping our far-field infrared imaging spectrometers. The aim of the present work is to evaluate the super-resolution concept in order to increase the spatial resolution of infrared imaging spectrometers using FPA detectors. The main idea of super-resolution is the fusion of several low-resolution images of the same sample to obtain a higher-resolution image. Applying the super-resolution concept on a relatively low number of FPA acquisitions, it was possible to observe a 30% decrease in spatial resolution.     

Application of Sol–Gel Based Poly(ethylene glycol)/Multiwalled Carbon Nanotubes Coated Fiber for SPME of Methyl tert-Butyl Ether in Environmental Water Samples

In this research, the sol–gel technology was applied for the preparation of solid-phase microextraction fibers for extracting of methyl tert-butyl ether (MTBE) from environmental water samples. For this purpose, two different polymers such as poly(ethylene glycol) (PEG) and combination of PEG and multiwall carbon nanotubes (MWCNTs) were prepared using sol–gel technology as coating procedure for the fibers. The pre-concentration process followed by GC–FID determination was used and the results evidenced that pre-concentration factor for PEG/CNTs fiber was approximately five times higher than PEG. Parameters affecting the extraction efficiency such as temperature, extraction time, stirring speed and salt effect for each fiber were investigated and optimized. On the optimal conditions, the linear range for MTBE with PEG and PEG/CNT fibers were 10–3,000 and 1–1,000 ng mL^?1 and the detection limits (S/N = 3) were 1.0 and 0.3 ng mL^?1, respectively. The sol–gel PEG/CNTs fiber has good performance and therefore relatively better figures of merit and experimental results such as thermal stability (up to 320 °C), average of life time (over 150 times) and repeatability (RSD < 4) in comparison to conventional PDMS/Carboxen fiber, which was already reported for determination of MTBE.     

[Sn(TPP)(BF4)2]: An efficient and reusable catalyst for chemoselective trimethylsilylation of alcohols and phenols with hexamethyldisilazane

Tin(IV)tetraphenylporphyrinato tetrafluoroborate, [Sn^IV(TPP)(BF₄)₂], was used as an efficient catalyst for trimethylsilylation of alcohols and phenols with hexamethyldisilazane (HMDS). High-valent [Sn^IV(TPP)(BF₄)₂] catalyzes trimethylsilylation of primary, secondary and tertiary alcohols as well as phenols, and the corresponding TMS-ethers were obtained in high yields and short reaction times at room temperature. While, under the same reaction conditions [Sn^IV(TPP)Cl₂] is less efficient to catalyze these reactions. One important feature of this catalyst is its ability in the chemoselective silylation of primary alcohols in the presence of secondary and tertiary alcohols and phenols. The catalyst was reused several times without loss of its catalytic activity.     

High-valent [Sn(Br8TPP)(OTf)2] as a highly efficient and reusable catalyst for selective methoxymethylation of alcohols and phenols: The effect of substituted bromines on the catalytic activity

High-valent tin(IV)octabromotetraphenylporphyrinato trifluoromethanesulfonate, [Sn^IV(Br₈TPP)(OTf)₂], was used for selective methoxymethylation of alcohols and phenols with formaldehyde dimethyl acetal (FDMA) at room temperature. Different primary, secondary and tertiary alcohols as well as phenols were converted to their corresponding methoxymethyl ethers with FMDA in the presence of an electron deficient tin(IV) porphyrin. The catalyst was reused several times without significant loss of its activity.     

Efficient and selective hydrocarbon oxidation with sodium periodate catalyzed by supported manganese(III) porphyrin

Manganese(III) tetrakis(p-sulfonatophenyl)porphyrin was successfully bound to silica modified with zirconium. The heterogeneous catalyst, MnTPPS-silica, was characterized by SEM, FT-IR and diffuse reflectance UV-Vis spectroscopic techniques. MnTPPS-silica catalyzes alkene epoxidation and alkanes hydroxylation with sodium periodate under agitation with magnetic stirring and ultrasonic irradiation in the presence of imidazole as an axial ligand. This catalytic system shows a good activity in the epoxidation of linear alkenes. Alkyl aromatic and cycloalkanes were efficiently oxidized to their corresponding alcohols and ketones in the presence of this catalyst. This new heterogeneous catalyst is of high stability and reusability in the oxidation reactions and can be reused several times without loss of its activity.     

A comprehensive Monte Carlo simulation of styrene atom transfer radical polymerization

<正>An optimized and high-performance Monte Carlo simulation is developed to take thorough account of four different cases of termination in styrene ATRP.According to the simulation results,the bimolecular termination rate constant sharply drops throughout the polymerization when either chain-length dependency of termination rate constant,gel effect,or both together is applied to the simulation.In addition,as expected,the initiator is quickly decomposed at the early stages of the polymerization.The concentration of the catalyst in lower oxidation state decreases at first and then plateaus at higher conversion;furthermore,the steady concentration of M_t~nY/L in the polymerization is the highest when the chain-length-dependent diffusion-controlled termination rate constant is employed in the simulation.The rates of deactivation and chain end degradation reactions are also smaller in this case.Therefore,the fraction of dormant chains is higher throughout the reaction and consequently the portion of dead polymers decreases.Besides,molecular weight increases linearly with conversion;however,when neither gel effect nor chain-length dependency of termination rate constant is considered,the molecular weight deviates from linearity at the end of the reaction.The peak of chain length distribution shifts toward higher molecular weight too during the reaction.Finally,the molecular weight distribution broadens at higher conversion;however, the chain length distribution of polymers produced under conditions of applying chain-length-dependent diffusion-controlled termination rate constant is narrower.     

Signature of non-Fickian solute transport in complex heterogeneous porous media

We simulate transport of a solute through three-dimensional images of different rock samples, with resolutions of a few microns, representing geological media of increasing pore-scale complexity: a sandpack, a Berea sandstone, and a Portland limestone. We predict the propagators (concentration as a function of distance) measured on similar cores in nuclear magnetic resonance experiments and the dispersion coefficient as a function of Péclet number and time. The behavior is explained using continuous time random walks with a truncated power-law distribution of travel times: transport is qualitatively different for the complex limestone compared to the sandstone or sandpack, with long tailing, an almost immobile peak concentration, and a very slow approach to asymptotic dispersion.     

One-pot synthesis of 1,2,3-triazole linked dihydropyrimidinones via Huisgen 1,3-dipolar/Biginelli cycloaddition

The combination of the Biginelli reaction with click chemistry has been used for the one-pot synthesis of 1,2,3-triazole linked dihydropyrimidinones from azides, aromatic aldehydes containing a propargyl ether group, urea, and 1,3-dicarbonyl compounds using Cu(OAc)₂/sodium ascorbate as catalyst in acetic acid under mild reaction conditions.     

FIXED POINT RESULTS ON METRIC-TYPE SPACES

In this paper we obtain fixed point and common fixed point theorems for self- mappings defined on a metric-type space, an ordered metric-type space or a normal cone metric space. Moreover, some examples and an application to integral equations are given to illustrate the usability of the obtained results.     

Exact boundary controllability of vibrating non-classical Euler–Bernoulli micro-scale beams

This study investigates the exact controllability problem for a vibrating non-classical Euler–Bernoulli micro-beam whose governing partial differential equation (PDE) of motion is derived based on the non-classical continuum mechanics. In this paper, it is proved that via boundary controls, it is possible to obtain exact controllability which consists of driving the vibrating system to rest in finite time. This control objective is achieved based on the PDE model of the system which causes that spillover instabilities do not occur.