Organic Matrixes Research Articles

Eu-phen Bonded Titanium Oxo-Clusters, Precursors for a Facile Preparation of High Luminescent Materials and Films.

Incorporation of Eu complexes into various organic or inorganic matrixes is one of the acceptable strategies to obtain displaying materials having practical applications. In this work, we report a convenient approach to preparing high luminescent organic-inorganic hybrid materials and films from the europium-titanium oxo-clusters (EuTOCs) having photoactive antenna ligands. Three Eu2Ti4 oxo-clusters were synthesized and crystallographically characterized. They are the first reported lanthanide-TOCs coordinated with 1,10-phenanthroline (phen) and 2,2'-bipyridine (bpy) as photoactive ligands, Eu2Ti4O6(phen)2(pa)10 (1) (pa = propionate), Eu2Ti4O6(bpy)2(pa)10 (2), and Eu2Ti4O6(phen)2(MA)10 (3) (MA = methacrylate). Benefitting from the photoactive antenna ligands and the rigid cluster structures, these clusters showed bright red luminescence with quantum yield in the range of 60-80% and long lifetime up to 3.0 ms. Unlike those physically mixed polymeric materials, the MA coordinated compound 3 can be self-polymerized to form a brilliant luminescent film. The film coated slide was used to develop a fluorescence sensor for biomolecule ascorbic acid (AA). The low detection limit and reusable properties suggest great potential for such EuTOC films in real applications.

The regulatory effects of the number of VP(N-vinylpyrrolidone) function groups on macrostructure and photochromic properties of polyoxometalates/copolymer hybrid films

Abstract Nanocomposite films were synthesized by introducing phosphotungstic acid (PWA) into the poly (vinylpyrrolidone and methyl acrylate) (P (VP(N-vinylpyrrolidone)coMA(methyl acrylate))). FT-IR curves illustrated that non-covalent bond interaction was built between PWA particles and organic matrixes. In combination the results of SEM, TG-DTA and DSC, it was conducted that the ratio of functional groups of VP had a critical effect on the surface morphology, thermal stability of the hybrid films. Irradiated with ultraviolet light, the transparent thin hybrid films change from colorless to blue. Stored in air, the hybrid films could recover colorless gradually. The analysis of kinetics told us that higher VP content within the different systems always accompanied more superior photochromic performance, faster coloring and fading speed. Appearance of W5+ in ESR spectra indicated that the photo-reduction process between PWA and copolymer matrix occurred.

Water Dramatically Accelerates the Decomposition of α-Hydroxyalkyl-Hydroperoxides in Aerosol Particles.

α-Hydroxyalkyl-hydroperoxides (α-HHs), from the addition of water to Criegee intermediates in the ozonolysis of olefins, are reactive components of organic aerosols. Assessing the fate of α-HHs in such media requires information on the rates and products of their reactions in aqueous organic matrixes. This information, however, is unavailable due to the lack of analytical techniques for the detection and identification of labile α-HHs. Here, we report the mass spectrometric detection (as Cl– adducts) of the α-HH produced in the ozonolysis of a C15 diolefin in water (W):acetonitrile (AN) mixtures of variable composition containing inert NaCl. α-HH decays into a gem-diol + H2O2 within τ1/e ≈ 52 min in 50% (v:v) water, but persists longer than a day in ≤10% water mixtures. The strong nonlinear dependence of τ1/e on solvent composition reveals that water content is a major factor controlling the fate of α-HHs in atmospheric particles. It also suggests that α-HH decomposes while embedded in WnANm clusters rather than randomly dissolved in molecularly homogeneous W:AN mixtures.

In-situ fabrication of a UHMWPE nanocomposite reinforced by SiO2 nanospheres and its tribological performance

In-situ fabrication of nanocomposites facilitates the dispersion of nanofillers in organic matrixes by decreasing the agglomeration of nanofillers compared to a mechanical mixing method. UHMWPE nanocomposites filled SiO2 nanospheres (SNS) were in-situ fabricated by a sol-gel method in this work. Their sliding coefficient of friction and wear rate were determined by a high-speed ring-block wear test apparatus against 45# steel under dry friction conditions, and the tribological behaviors at elevated temperature were tested by a slurry abrasion wear configuration. The in-situ filled SiO2 nanospheres presented an excellent dispersion on UHMWPE, and the fabricated SNS/UHMWPE nanocomposites were found a remarkable enhancement in stiffness, glass transition temperature and hydrophobicity. Furthermore, the SNS/UHMWPE nanocomposites exhibited markedly improved tribological performances than the matrix UHMWPE and the referenced sample prepared by a mechanical mixing method: the sliding coefficient of friction was reduced by over 50% than that of the pristine UHMWPE against a 45# steel ring under dry friction, and the mass wear rate was ca. 59% of the UHMWPE matrix determined by a water-bath mortar at an elevated temperature.

Undoped and Eu3+ Doped Magnesium-Aluminium Layered Double Hydroxides: Peculiarities of Intercalation of Organic Anions and Investigation of Luminescence Properties.

The Mg3/Al and Mg3/Al0.99Eu0.01 layered double hydroxides (LDHs) were fabricated using a sol-gel chemistry approach and intercalated with different anions through ion exchange procedure. The influence of the origin of organic anion (oxalate, laurate, malonate, succinate, tartrate, benzoate, 1,3,5-benzentricarboxylate (BTC), 4-methylbenzoate (MB), 4-dimethylaminobenzoate (DMB) and 4-biphenylacetonate (BPhAc)) on the evolution of the chemical composition of the inorganic-organic LDHs system has been investigated. The obtained results indicated that the type and arrangement of organic guests between layers of the LDHs influence Eu3+ luminescence in the synthesized different hybrid inorganic–organic matrixes. For the characterization of synthesis products X-ray diffraction (XRD) analysis, infrared (FTIR) spectroscopy, fluorescence spectroscopy (FLS), and scanning electron microscopy (SEM), were used.

Characterization of low-shrinkage dental composites containing methacrylethyl-polyhedral oligomeric silsesquioxane (ME-POSS)

The aim of this study was to characterize low-shrinkage dental composites containing methacrylethyl-polyhedral oligomeric silsesquioxane (ME-POSS). Four experimental composites were manufactured, two of which contained organic matrixes of BisGMA-TEGDMA (70/30 wt% - BGC) and BisEMA-TEGDMA (80/20 wt% - BEC). The two other experimental composites replaced BisGMA and BisEMA with 25 wt% of ME-POSS (BGP and BEP). The composites also contained 70 wt% of 0.7 µm silanized BaBSi particles. The following properties were evaluated: Degree of conversion (DC%), volumetric polymerization shrinkage (VS%), polymerization shrinkage stress (Pss), flexural strength (FS), Flexural modulus (FM), hardness (KHN), water sorption (Wsp), water solubility (Wsl), diffusion coefficient (D), and wear. The DC% was not influenced by the presence of ME-POSS, with BEC (75.6%) and BEP (74.8%) presenting higher DC% than BGC (60.6%) and BGP (55.6%). The ME-POSS-containing composites (BGP and BEP) presented significantly lower VS% and Pss. The FS ranged from 92.7 to 142.0 MPa and the FM from 3.6 to 10.3 GPa. ME-POSS did not influence the KHN. BEC and BEP presented lower Wsp and Wsl when compared to BGC and BGP. D ranged from 1.0 × 10−6 to 7.4 × 10−6 cm2 m−1. Incorporation of ME-POSS significantly decreased the wear for both binary matrices (p < 0.05). With the exception of FS and FM for BGP, the incorporation of ME-POSS decreased the VS% and Pss without jeopardizing the other properties of the experimental dental composites.

Nitrogen and Sulfur Co-doped Carbon-Dot-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Imaging for Profiling Bisphenol S Distribution in Mouse Tissues.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry imaging (MALDI-TOF MSI) is rapidly maturing as an innovative technique for spatial molecule ( m/ z > 1000 Da) profiling. However, direct identification of low-molecular-weight compounds ( m/ z < 600 Da) by MALDI-TOF MSI using conventional organic matrixes remains a challenge because of ionization suppression and serious matrix-related background interference. Furthermore, the heterogeneous cocrystallization that is inherent to organic matrixes can degrade spatial resolution in MSI. Herein, we developed a negative ion surface-assisted laser desorption/ionization time-of-flight mass spectrometry imaging (SALDI-TOF MSI) protocol to detect bisphenol S (BPS) and map its spatial distribution in mouse tissues by applying nitrogen- and sulfur-co-doped carbon dots (N,S-co-doped CDs) as a new matrix through spraying. The SALDI-TOF MS and imaging parameters, such as matrix concentration, ionization mode, and matrix deposition, were optimized to improve imaging performance. In comparison to organic matrixes, the use of N,S-co-doped CDs in negative ion mode exhibited free matrix background interference, enhanced MS signal intensity, and provided high spatial resolution (acquired at ∼50 μm) in the analysis of BPS, which allowed sensitive detection of the target compound on the surfaces of tissue sections. Quantitative assessment was also made by spotting BPS standards directly onto the tissue surface, and a good correlation between the color change and BPS concentrations was found. The corresponding detection limit as low as the ∼pmol level for BPS was observed with the direct visualization from MS images. Furthermore, the feasibility of the proposed SALDI-TOF MSI method was extended for in situ identification of exogenous BPS in the different tissues of mouse involving liver, kidney, spleen, and heart for exposure and profiling its spatial localization at different administration times. In addition, the general applicability of the proposed method was also evaluated by SALDI-TOF MSI analysis of BPAF in tissues. These successful applications of SALDI-TOF MSI not only demonstrated its promising potential as an alternative to MALDI-TOF MSI in profiling small molecules in tissue sections but also provided tremendous insight into the assessment of BPS exposure.

Analysis of coke beverages by total-reflection X-ray fluorescence

The influence of the organic content, sample preparation process and the morphology of the depositions of two types of Coke beverage, traditional and light Coke, have been investigated by mean of Total-reflection X-ray Fluorescence (TXRF) spectrometry. Strong distortions of the nominal concentration values, up to 128% for P, have been detected in the analysis of traditional Coke by different preparation methods. These differences have been correlated with the edge X-ray energies of the elements analyzed being more pronounced for the lighter elements. The influence of the organic content (mainly sugar) was evaluated comparing traditional and light Coke analytical TXRF results. Three sample preparation methods have been evaluated as follows: direct TXRF analysis of the sample only adding internal standard, TXRF analysis after open vessel acid digestion and TXRF analysis after high pressure and temperature microwave-assisted acid digestion. Strong correlations were detected between quantitative results, methods of preparation and energies of the X-ray absorption edges of quantified elements. In this way, a decay behavior for the concentration differences between preparation methods and the energies of the X-ray absorption edges of each element were observed. The observed behaviors were modeled with exponential decay functions obtaining R2 correlation coefficients from 0.989 to 0.992. The strong absorption effect observed, and even possible matrix effect, can be explained by the inherent high organic content of the evaluated samples and also by the morphology and average thickness of the TXRF depositions observed. As main conclusion of this work, the analysis of light elements in samples with high organic content by TXRF, i.e. medical, biological, food or any other organic matrixes should be taken carefully. In any case, the direct analysis is not recommended and a previous microwave-assisted acid digestion, or similar, is mandatory, for the correct elemental quantification by TXRF.

Room Temperature Magnesite Precipitation

Magnesite (MgCO3) is one of the most stable sinks for carbon dioxide (CO2) and is therefore of great interest for long-term carbon storage. Although magnesite is the thermodynamically stable form of magnesium carbonate, the kinetic inhibition of low-temperature precipitation has hindered the development of carbon sequestration strategies that can be economically conducted under ambient temperature. Here, we document the precipitation of magnesite from waters (magnesite saturation index = 1.45) in batch reactors at room temperature with the aid of carboxylated polystyrene microspheres over the course of 70 days. Microspheres provide surfaces with a high density of carboxyl groups that act to bind and dehydrate Mg2+ ions in solution, thereby minimizing the kinetic barrier and facilitating magnesite formation. Magnesite crystals are observed on sphere surfaces and their organic matrixes. Mineral identification was confirmed by X-ray diffraction and selected area electron diffraction of a thin section obtaine...

Counterion-mediated Ca2 + accumulation on cationic Langmuir-Blodgett films as template for CaCO3 growth

Negatively charged macromolecules play a starring role in Ca2+ saturation at interfaces: they act as organized points for biomineral growth in nature. However, the role positively charged interfaces play in biomineralization remains unknown. Therefore, we decided to use a cationic Langmuir-Blodgett (LB) film composed of dioctadecyldimethylammonium bromide (DOMA) and type-I collagen in the presence of CaCl2 solutions to guide CaCO3 growth on titanium surfaces. Ca2+ was able to interact with DOMA monolayers, leading to impressive cation excess at the film surface, as evidenced by the increased positive zeta potential of the LB films. Additionally, molecular dynamics simulations showed that Ca2+ co-ions were able to accumulate on the positively charged LB interface, especially because configurations like R-N(+)-counterion-Ca2+ existed therein. Counterion-mediated Ca2+ accumulation on the surface was mainly driven by Cl− ions, which were much closer to Ca2+ ions than Br− ions. Ca2+ excess on the surface was sufficient to grow continuous and particulate CaCO3 films on titanium surfaces. In addition, collagen presence induced changes in CaCO3 film morphology and organization. Finally, we were able to confirm that positively charged organic interfaces can act as templates for biomineral growth because counterion-mediated Ca2+ accumulation on these surfaces can drive subsequent crystal growth. This study provides insight into biomineralization templated by positively charged organic matrixes and into the design of bioinspired coatings for metallic surfaces.

Cross-Talk Characterization in Passive Neutron Coincidence Counting of Radioactive Waste Drums With Plastic Scintillators

This paper reports on a numerical feasibility study of a passive neutron coincidence counting system for radioactive waste drums with plastic scintillators. The motivation is to replace $^{3}\text{He}$ gas counters generally used for this type of measurement. Indeed, plastic scintillators present several advantages for the measurement of neutron coincidences such as a good efficiency for detecting fast neutrons, short detection time, and low cost comparatively to $^{3}\text{He}$ . However, unlike $^{3}\text{He}$ counters, their high sensitivity to gamma rays and cross talk constitutes a drawback as parasite random and true coincidences are detected together with the useful signal of plutonium. Simulations are performed using the Monte Carlo transport code MCNPX-PoliMi v2.0 coupled to data processing algorithms developed with ROOT data analysis software. Performances of the coincidence counting system are studied for the case of a vitrified waste drum containing Pu and $^{241}\text{Am}$ , focusing particularly on multiplicity 1 and 2, i.e., 2 or 3 pulses recorded in a short time gate in different detectors. Cross talk induced by neutrons and gamma rays has been characterized in terms of time and distance between detectors, and strategies to limit this phenomenon are reported, consisting of ignoring neighboring detectors signal. A significant improvement of the Pu to $^{241}\text{Am}$ ratio for multiplicity 2 coincidences has thus been obtained, at the expense of counting statistics. Alternative case studies with organic and metallic matrixes of technological wastes are also reported, for which the part of useful signal of plutonium is significantly higher, showing the feasibility of the measurement method.

Laser Desorption Ionization Mass Spectrometry Imaging of Drosophila Brain Using Matrix Sublimation versus Modification with Nanoparticles.

Laser desorption ionization mass spectrometry (LDI-MS) is used to image brain lipids in the fruit fly, Drosophila, a common invertebrate model organism in biological and neurological studies. Three different sample preparation methods, including sublimation with two common organic matrixes for matrix-assisted laser desorption ionization (MALDI) and surface-assisted laser desorption ionization (SALDI) using gold nanoparticles, are examined for sample profiling and imaging the fly brain. Recrystallization with trifluoroacetic acid following matrix deposition in MALDI is shown to increase the incorporation of biomolecules with one matrix, resulting in more efficient ionization, but not for the other matrix. The key finding here is that the mass fragments observed for the fly brain slices with different surface modifications are significantly different. Thus, these approaches can be combined to provide complementary analysis of chemical composition, particularly for the small metabolites, diacylglycerides, phosphatidylcholines, and triacylglycerides, in the fly brain. Furthermore, imaging appears to be beneficial using modification with gold nanoparticles in place of matrix in this application showing its potential for cellular and subcellular imaging. The imaging protocol developed here with both MALDI and SALDI provides the best and most diverse lipid chemical images of the fly brain to date with LDI.

Characterization of an experimental resin composite organic matrix based on a tri-functional methacrylate monomer.

This study evaluated the potential of a tri-functional monomer (trimethylolpropane trimethacrylate -TMPTMA) for inclusion in a dental composite organic matrix. Initially, four ternary matrixes with different concentrations (wt%) of bi-functional monomers [BisGMA (G), Bis-EMA (E) and TEGDMA (T)] were analyzed: GET523, GET532, EGT523 and EGT532 (the numbers (n) represent n×10 wt% of each monomer). The following properties were evaluated: degree of conversion, flexural strength, elastic modulus, hardness, absorption, solubility, diffusion coefficient of water and crosslink density. Based on the best overall results obtained for EGT532, all properties were re-evaluated in a matrix where TEGDMA (T) was replaced by a tri-functional monomer, TMPTMA (A)-EGA532. EGA532 presented the best results for flexural strength, hardness, absorption and crosslink density. EGT523, EGT532 and EGA532 presented the lowest diffusion coefficients of water. The overall results indicated that TMPTMA could be useful in formulating organic matrixes suitable for dental restorative composites.

Post-treatment sludge analyses and purification of paint effluent by coag-flocculation method

Tympanotonos fuscatus shell (T. fuscatus shell), an abundant eco-friendly waste was used as a precursor for the production of Tympanotonos fuscatus coagulant (TFC) for the purification of paint effluent (PE). Tympanotonos fuscatus shells (TFS) are of crustacean origin consisting mainly of chitin, calcium carbonate, entrained protein and other organic matrixes. Influence of pH, dosage and settling time on treatment efficiency was studied. Scanning electron microscopic, Fourier transform infra red, X-ray diffraction and differential scanning calorimetric/thermogravimetric analyses were carried out to investigate, respectively, the surface morphology, functional group, crystalline/lattice structure and thermal stability of TFS, TFC and settled sludge after treatment. The PE was optimally treated at 2 g/L TFC dosage, pH 5 and 97 % efficiency. Results indicated that TFC could be an efficient treatment agent for PE at the conditions of the experiment.

New occurrences of Sphenothallus in the lower Cambrian of South China: Implications for its affinities and taphonomic demineralization of shelly fossils

Sphenothallus , a tubular fossil that occurs in Paleozoic strata around the world, may be related to cnidarians or ‘worms,’ but its affinities remain controversial due to preservational variations among localities. Here, to test hypotheses regarding Sphenothallus taphonomy and affinities, we investigate the preservation of new fossils from the lower Cambrian Shuijingtuo Formation at Heziao and Jijiapo (Hubei Province) and the equivalent Niutitang Formation at Siduping (Hunan Province) in South China. Morphology and allometry suggest that the fossils represent a single species, and their biostratinomy and authigenic mineralization indicate that they underwent similar pre-burial and early diagenetic processes, particularly transport and focused degradation via microbial sulfate reduction. However, the compositions and microstructures of the tests vary among localities. The Heziao tests consist of lamellar phosphatic material covered interiorly and exteriorly by layers of carbonaceous material. In contrast, the Siduping tests consist of non-lamellar phosphatic material associated with carbonaceous material, and the Jijiapo tests consist entirely of carbonaceous material. Based on these observations and experimental taphonomic data—which show that hydrochloric acid treatment of Heziao samples produces fossils that compositionally and microstructurally resemble the Jijiapo specimens—we propose that the new tests constitute a taphonomic continuum between shelly and carbonaceous preservation. This taphonomic model suggests that the preservation of shells as carbonaceous fossils results from kerogenization of the organic matrixes and subsequent or concomitant demineralization of the biomineralized microstructures of the shells. Hence, variations in Sphenothallus test composition and microstructure among localities may reflect varying extents of test demineralization, and the carbonaceous layers in Heziao specimens may have formed via demineralization of the tests' exterior and interior phosphatic lamellae. Our reconstruction based on this model indicates that pristine Sphenothallus tests consist of exteriorly sculptured and interiorly unsculptured organophosphatic lamellae. Thus, Sphenothallus microstructurally resembles and may be related to conulariids, and potentially, cnidarians. • Sphenothallus fossils in Shuijingtuo and Niutitang formations of Hubei and Hunan. • We provide data on their taphonomy, allometry, compositions, and microstructures. • Data illuminate Sphenothallus affinities and taphonomic diversity of Cambrian shells. • Sphenothallus microstructurally resembles conulariids and may be a cnidarian. • Data support taphonomic model for preservation of shells as carbonaceous fossils.

Influence of feeding mixture composition in batch anaerobic co-digestion of stabilized municipal sludge and waste from dairy farms

Waste anaerobic co-digestion applications are particularly useful in Southern Mediterranean areas where large quantities of agricultural waste materials and waste from agro-industries are produced. This waste can be added to urban waste together with the sludge produced by wastewater treatment processes, which, when combined, guarantee the supply of organic matrixes for treatment throughout the year. The implementation of facilities to service vast areas of the agricultural economy and which are heterogeneous in terms of production can provide a good solution. We present an experimental investigation into the anaerobic co-digestion of municipal sludge and bio-waste produced in the Mediterranean area. We conducted anaerobic treatability tests, with measures of biogas production and pH of the mixture in digestion. Our main aims were to identify an optimal mix of substrates for the production of biogas, and to analyse the influence on the composition of biogas and the variation in pH values of the substrates. This analysis was conducted considering the variation of the input, in particular due to the addition of waste acids, such as biological sewage sludge.

First-Principles Study of Lead Iodide Perovskite Tetragonal and Orthorhombic Phases for Photovoltaics

Methylammonium lead iodide perovskite, CH3NH3PbI3, has attracted particular attention because of its fast increase in efficiency as solid-state solar cells. We performed first-principles calculations with the nonlocal van der Waals (vdW) correlation to investigate the crystal structures and electronic and optical properties of CH3NH3PbI3. The calculated results show that the distribution of methylammonium ions, which further changes the vdW interaction and hydrogen bonds of organic and inorganic matrixes, plays a vital role in both the geometry stability and the electronic structure. The vdW correlation is critical to provide appropriate descriptions of the interaction between the organic and the inorganic parts. The phase transformation from orthorhombic to tetragonal phase causes the decrease of the band gap and the red shift of the optical absorption coefficient.

Preparation and Characterization of Transparent and UV‐Shielding Epoxy/SR‐494/APTMS/ZnO Nanocomposites with High Heat Resistance and Anti‐Static Properties

AbstractThis research is to develop transparent and UV‐shielding Epoxy/SR‐494/APTMS/ZnO nanocomposite materials with high heat resistant and anti‐static properties. Firstly, the APTMS (3‐(acryloxypropyl)trimethoxysilane) performs the silanol intermediates by hydrolysis in pH 4∼5 acid solution. The inorganic anti‐static fillers of powder ZnO can be successfully coupled and crosslinked to Epoxy/SR‐494 organic matrixes with these silanols of APTMS coupling agents. The remained active ‐OH functional groups of the APTMS/ZnO complexes can network bonding with epoxy prepolymers. Therefore, the Epoxy/APTMS/ZnO complexes with good anti‐static composites will be successfully prepared. Finally, in order to improve the thermal resistant and mechanical properties, the polyfunctionalized SR‐494 (pentaery‐thritol tetracrylate) acrylate monomers and the Epoxy/APTMS/ZnO composites are chain polymerized to form an excellent cross‐linking structure of organic/inorganic nanocomposites.The chemical bonding formation and the best weight contents of reaction components are identified by FT‐IR spectra. The thermal resistance, transparence, surface electric resistance, and hardness of these nanocomposites are measured by TGA, DSC, UV‐Visible, surface resistant meter, and pencil hardness tester respectively. Experimental results show that these nanocomposites have 90% transmittance and the best Td value is 389.3 °C which is 109.0 °C and 78.6 °C higher than those of pure epoxy resin and pure SR‐494 acrylate resin respectively. The glass transition temperature is not detected below 200 °C. The surface electric resistances of Epoxy/SR‐494/APTMS/ZnO hybrid thin films are decreased from 3.14 × 1013 to 5.13 × 107 Ω/cm2. The hardness of these nanocomposites is as high as 8H, and those hybrid films have high UV‐shielding properties. The morphology structures of the hybrid thin films are estimated by SEM. The results show that the optical thin films are evenly distributed with inorganic colloidal particles and the average particle size of these nanocomposites is 45∼80 nm, while the powder ZnO (particle size: 2∼5 μm) was used as inorganic filler.

HETEROGENEOUS CATALYSTS BASED ON SULPHONATED PHTHALOCYANINE MACROHETEROCYCLES AND SOLID MATRIXES

Hybrid materials containing sulfo-substituted cobalt(II) phthalocyanines and various pre-treated solid organic and inorganic matrixes (poly(methyl methacrylate), polypropylene, silicon dioxide) have been obtained. It is shown that the plasma chemical activated polypropylene matrix results 85-90 % attachment of the macrocycles. Attaching the sulphonated cobalt(II) phthalocyanines to silicon dioxide matrix, ~65 % of the macrocycles were found to be bound.

Silver(I) and zinc(II) organometallic intermediates, catalysing coupling reactions of polysubstituted benzoic acids – Experimental and theoretical study

The paper highlighted AgI- and ZnII-organometallic catalysing CC coupling processes of polysubstituted benzoic acids in polar protic solutions. Six novel interaction products of substituted biphenyl, 6H-benzo-[c]-chromene[6]-one, chromeno[5,4,3-cde]chromene-5,10-dione, and 4,10-dioxa-pyrene-5,9-dione are isolated. The study, therefore impact the fields of inorganic, metal–organic and organometallic chemistry, catalysis, semi-synthetic natural products and materials research, polymer science, and more. The mechanistic aspects of the reactions with participation of nine MC bonded organometallic precursors (M=ZnII, AgI/AgII) and four metal-organic coordination compounds are comprehensively discussed. The factors stabilizing the metal ion – containing systems in polar environment and gas–phase are elucidated, employing the method of quantum chemistry and variety of mass spectrometric approaches, utilizing the ESI-, APCI- and MALDI-methods. These latters provided experimental physical evidences for formation of ZnII and AgI-containing organometallics species with closed d10 shell electronic configuration of the metal ions. The data reported are of methodological importance for the field of the mass spectrometry as well. Due to the matrix-analyte sample preparation techniques in UV–MALDI–MS method widely utilize polysubstituted benzoic acids as organic matrixes. The study contributed as well to the fundamentals of CT- and MLCT-effects in coordination compounds of metal ions with closed d10-electronic configuration. Electronic absorption spectroscopy, single crystal X-ray diffraction and nuclear magnetic resonance methods are also utilized.