Digital holographic microscopy of spiropyran-based dynamic materials.

Spiropyran (SP)-based dynamic materials undergo structural changes in response to external stimuli. In this paper, we show that digital holographic microscopy (DHM) is an effective candidate for characterisation of SPs (embedded in polymer matrices) and for monitoring of their dynamical changes. The polymer matrices are polylactic acid (PLA) and poly(methyl methacrylate) (PMMA) films, which are decorated with SPs and immobilised on graphene quantum dots (GQDs). GQDs are modified by benzylamines prior to the loading of SP species because of the enhancement of hydrophobic characteristics. UV irradiation is used as the external stimulus and the dynamical changes of the samples before and after UV irradiation are measured. DHM is arranged on a novel self-referencing setup, which substantially reduces the sensitivity of DHM to environmental vibrations. Morphometric information for characterisation of the samples is obtained by analysis of the recorded digital holograms. The experimental results demonstrate the potential of the presented technique to serve as an alternative technique for surface measurement methodologies such as atomic force microscope and stylus profiler for surface characterisation of similar materials.

Imidazolium-based mesoporous organosilicas with bridging organic groups for microextraction by packed sorbent of phenoxy acid herbicides, polycyclic aromatic hydrocarbons and chlorophenols.

The authors describe the preparation of two kinds of periodic mesoporous organosilicas (PMOs). The first kind is monofunctional and has a bridged alkyl imidazolium framework (PMO-IL). The other is a two-dimensional (2D) hexagonal bifunctional periodic mesoporous organosilica (BFPMO) with bridged IL-phenyl or -ethyl units. The CPMOs were utilized as highly sensitive and stable sorbents for microextraction by packed sorbent. The materials were characterized by SEM, TEM, FT-IR, and N2 adsorption-desorption analysis. The adsorption capacities of the sorbents were investigated by using phenoxy acid herbicides as model analytes. The effects of bifunctionality and type of additional surface groups (phenyl or ethyl) on the efficiency of the extraction is emphasized. Three kinds of environmental contaminants, viz. phenoxy acid herbicides (CPAs), polycyclic aromatic hydrocarbons and chlorophenols were then studied with respect to their extraction by the sorbents. The interactions between the CPAs and the sorbents were evaluated by pH-changing processes to explore the interactions that play a major role. The selectivity of the sorbents was investigated by extraction of other types of analytes of with various polarity and charge. The BFPMOs display the typical good chemical stability of silica materials. The extraction properties are much better compared to commercial silicas. This is assumed to be due to the highly ordered mesoporous structures and the different types of probable interactions with analytes. The performance of the method was evaluated by extraction of CPAs as model analytes from aqueous samples, and quantification by GC with FID detection. Under optimized conditions, low limits of detection (0.1-0.5 µg.L-1) and a wide linearity (0.5-200 µg.L-1) were obtained. The method was applied to the trace analysis of CPAs in farm waters and rice samples. Graphical abstract Monofunctional periodic mesoporous organosilica with bridged alkyl imidazolium frameworks and bi-functional periodic mesoporous organosilica containing bridged ionic liquids and phenyl or -ethyl, have been successfully synthesized and utilized in microextractions by packed sorbent sorbents.

Controllable synthesis of hollow mesoporous organosilica nanoparticles with pyridine-2,6-bis-imidazolium frameworks for CO2 conversion.

A series of hard-template-derived hollow mesoporous organosilica nanoparticles (HMONs) with pyridine-2,6-bis-imidazolium frameworks have been described for the first time. As a part of the investigation, to evaluate the effects of the hard template nature, the Si/CTAB and organosilica/TEOS molar ratios, and the stepwise addition of precursors, four reaction conditions denoted as methods A-D were designed. In the presence of polystyrene latex as a hard template, the HMONs that we wished to synthesize were not yielded with a Si/CTAB molar ratio of 3 (method A), but we could synthesize the desired HMONs with a Si/CTAB molar ratio of 9 and an organosilica : TEOS ratio of 1 : 99 (method B). The ratio of organosilica to TEOS could be improved up to 2.5 : 97.5 if the precursor additions are made in a stepwise manner rather than by simultaneous additions (method C). Using sSiO2 as a hard template, a yolk-shell morphology was observed by adopting a Si/CTAB molar ratio of 3 (method D). The HMONs were modified by iodide ions and their activity was explored toward the coupling of CO2 with epoxides. Among the catalysts, I-HMON-L-C-2.5 exhibited excellent results under mild reaction conditions. Well-oriented pore sizes and short channel length facilitated easy mass transfer from one side and the integration of the interior hollow regions of the catalyst particles from the other side improved the CO2 retention time around pores where the imidazolium organocatalysts were located, which made I-HMON-L-C-2.5 an effective catalyst for title CO2 utilization. The catalyst was reused at least six times without exhibiting any changes in its activity. HMONs can also be used as solid CNC ligands for the preparation of copper catalysts for the click reaction between phenyl acetylene and benzyl azide.

Direct coupling of CO2 with epoxides catalyzed by lanthanum(III) supported on magnetic mesoporous organosilica nanoparticles.

Lanthanum(III) supported on the magnetic mesoporous organosilica nanoparticle (La@MON) has been described as an efficient, simple, and durable heterogeneous catalyst for the synthesis of 5-membered cyclic carbonates from carbon dioxide (CO2) and epoxides. Under optimized reaction conditions, various terminal epoxides have been converted to the corresponding carbonates in the presence of 0.3 mol% La@MON and 0.5 mol% tetrabutylammonium iodide (TBAI) as co-catalyst at relatively mild reaction conditions. It was also found that La@MON catalysts had significantly higher catalytic activity than some selected reference catalysts, which can be explained by the abundance of lanthanum(III) species acting as Lewis acidic sites for activating both carbon dioxide and epoxide molecules, along with the fact that the catalyst channels are short and provided facile mass transfer. The catalyst showed good reusability for at least five reaction cycles while the magnetic core of the catalyst helps the easy separation of the catalyst by just using an external magnet.

Synthesis and characterization of alkyl-imidazolium-based periodic mesoporous organosilicas: a versatile host for the immobilization of perruthenate (RuO4-) in the aerobic oxidation of alcohols.

The preparation and characterization of a set of periodic mesoporous organosilicas (PMOs) that contain different fractions of 1,3-bis(3-trimethoxysilylpropyl)imidazolium chloride (BTMSPI) groups uniformly distributed in the silica mesoporous framework is described. The mesoporous structure of the materials was characterized by powder X-ray diffraction, transmission electron microscopy, and N(2) adsorption-desorption analysis. The presence of propyl imidazolium groups in the silica framework of the materials was also characterized by solid-state NMR spectroscopy and diffuse-reflectance Fourier-transform infrared spectroscopy. The effect of the BTMSPI concentration in the initial solutions on the structural properties (including morphology) of the final materials was also examined. The total organic content of the PMOs was measured by elemental analysis, whereas their thermal stability was determined by thermogravimetric analysis. Among the described materials, it was found that PMO with 10% imidazolium content is an effective host for the immobilization of perruthenate through an ion-exchange protocol. The resulting Ru@PI-10 was then employed as a recyclable catalyst in the highly efficient aerobic oxidation of various types of alcohols.

3D monitoring of the surface slippage effect on micro-particle sedimentation by digital holographic microscopy.

In several phenomena in biology and industry, it is required to understand the comprehensive behavior of sedimenting micro-particles in fluids. Here, we use the numerical refocusing feature of digital holographic microscopy (DHM) to investigate the slippage effect on micro-particle sedimentation near a flat wall. DHM provides quantitative phase contrast and three-dimensional (3D) imaging in arbitrary time scales, which suggests it as an elegant approach to investigate various phenomena, including dynamic behavior of colloids. 3D information is obtained by post-processing of the recorded digital holograms. Through analysis of 3D trajectories and velocities of multiple sedimenting micro-particles, we show that proximity to flat walls of higher slip lengths causes faster sedimentation. The effect depends on the ratio of the particle size to (1) the slip length and (2) its distance to the wall. We corroborate our experimental findings by a theoretical model which considers both the proximity and the particle interaction to a wall of different hydrophobicity in the hydrodynamic forces.

Plugged bifunctional periodic mesoporous organosilica as a high-performance solid phase microextraction coating for improving extraction efficiency of chlorophenols in different matrices.

In this study, a sensitive solid phase microextraction (SPME) coating was developed based on two kinds of plugged and non-plugged bifunctional periodic mesoporous organosilicas (BFPMO) with ionic liquid and ethyl units. The extraction efficiency of all plugged and unplugged sorbents was investigated for the extraction of chlorophenols (CPs) in water and honey samples by emphasizing the effect of different physicochemical properties. The separation and determination of the CPs was performed by gas chromatography-mass spectrometry (GC-MS). The extraction results showed that plugged BFPMO coating exhibited outstanding enrichment ability for the extraction of CPs as model analytes with different polarities. This can be attributed to a valuable hydrophobic-hydrophilic balance in the mesochanels of the plugged BFPMO, which is the result of the combination of plug technology and bridged organic groups. Low limits of detection in the range of 5-70 ng L-1, wide linearity, and good reproducibility (RSD = 8.1-10.1 % for n = 6) under the optimized extraction conditions were achieved. Finally, the BFPMOs coated fiber was successfully used for determination of CPs in real water samples. The relative recoveries for the five CPs were in the range of 92.3-104.0 %, which proved the applicability of the method.

Aerobic Oxidation of Alcohols Catalyzed by in Situ Generated Gold Nanoparticles inside the Channels of Periodic Mesoporous Organosilica with Ionic Liquid Framework.

In situ generated gold nanoparticles inside the nanospaces of periodic mesoporous organosilica with an imidazolium framework (Au@PMO-IL) were found to be highly active, selective, and reusable catalysts for the aerobic oxidation of activated and nonactivated alcohols under mild reaction conditions. The catalyst was characterized by nitrogen adsorption-desorption measurement, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), elemental analysis (EA), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The catalyst exhibited excellent catalytic activity in the presence of either Cs2CO3 (35 °C) or K2CO3 (60 °C) as reaction bases in toluene as a reaction solvent. Under both reaction conditions, various types of alcohols (up to 35 examples) including activated benzylic, primary and secondary aliphatic, heterocyclic, and challenging cyclic aliphatic alcohols converted to the expected carbonyl compounds in good to excellent yields and selectivity. The catalyst was also recovered and reused for at least seven reaction cycles. Data from three independent leaching tests indicated that amounts of leached gold particles were negligible (<0.2 ppm). It is believed that the combination of bridged imidazolium groups and confined nanospaces of PMO-IL might be a major reason explaining the remarkable stabilization and homogeneous distribution of in situ generated gold nanoparticles, thus resulting in the highly active and recyclable catalyst system.

One-Pot Preparation of Propargylamines Catalyzed by Heterogeneous Copper Catalyst Supported on Periodic Mesoporous Organosilica with Ionic Liquid Framework.

Copper supported on periodic mesoporous organosilica (PMO) with alkylimidazolium frameworks is a highly efficient and recoverable catalyst for the preparation of propargylamines through the three-component coupling reaction of aldehydes, alkynes, and amines. The new catalyst is characterized using N2 adsorption/desorption analysis, transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT-IR), and elemental analysis. The catalyst is easily recovered by a simple filtration process and subsequently reused in the seven reaction cycles without any loss of catalytic activity.

Tungstate Supported on Periodic Mesoporous Organosilica with Imidazolium Framework as an Efficient and Recyclable Catalyst for the Selective Oxidation of Sulfides.

A catalyst based on immobilization of tungstate ions (WO4 2- ) inside the mesochannels of periodic mesoporous organosilica comprising bridged ionic liquid (1,3-bis(3-trimethoxysilylpropyl)imidazolium chloride) has been synthesized and characterized. This catalyst was then employed for the selective oxidation of organic sulfides to the corresponding sulfoxides or sulfones. The final synthesized catalyst was characterized by various techniques such as nitrogen sorption analysis, transmission electron microscopy, and thermogravimetric analysis. The catalyst was also applied to the selective oxidation of sulfides containing readily oxidizable functional groups such as hydroxyl, allylic, and even challenging aliphatic sulfides. Interestingly, it was found that on changing the reaction medium from aqueous methanol to aqueous acetonitrile, the product selectivity was changed successfully from sulfoxide to sulfone with good to excellent yields. Moreover, the catalyst can also be recovered and reused efficiently in nine subsequent reaction cycles without any remarkable decrease in the catalyst activity and selectivity.

Highly efficient three-component coupling reaction catalyzed by gold nanoparticles supported on periodic mesoporous organosilica with ionic liquid framework.

A novel gold nanoparticle supported periodic mesoporous organosilica with alkylimidazolium framework, Au@PMO-IL, was shown to be a highly active and recyclable catalyst for three-component coupling reaction of aldehyde, alkyne and amine to give the corresponding propargylamine.