Complex isomerism influencing the textural properties of organometallic [Cu(salen)] porous polymers: paramagnetic solid-state NMR characterization and heterogeneous catalysis.

Although organometallic porous polymer networks are recognized as promising heterogeneous catalysts, the relationship between ligand/monomer geometry and network parameters is usually not well understood due to the lack of atom-resolved characterization methods for the amorphous network matrix. In this work, a series of copper(II) salen-type metal complexes was synthesized, using trans- and cis-1,2-diaminocyclohexane segments, and thoroughly characterized by single-crystal X-ray diffraction and solution- and solid-state NMR spectroscopy. Terminal ethynyl groups of the complexes were then transformed into polyacetylene chains by coordination chain-growth homopolymerization, resulting in highly porous (458-655 m2 g-1) organometallic polymer networks with a copper(II) ion content of about 12 wt%. The presence of paramagnetic copper(II) moieties in these complexes and respective polymer networks required the application of tailored NMR techniques, which together with X-ray crystallography and DFT calculations of the paramagnetic NMR shifts made it possible to investigate the differences in the complex geometry in liquid, powder and crystalline form and compare it with the complex geometry in polymer networks. All prepared organometallic polymer networks were also tested as heterogeneous catalysts for styrene oxidation with uncommonly high substrate conversions and compared with their low-molecular-weight analogues. The high reusability of such heterogeneous polymer-based catalysts was also proven.

Combining Polymerization and Templating toward Hyper-Cross-Linked Poly(propargyl aldehyde)s and Poly(propargyl alcohol)s for Reversible H2O and CO2 Capture and Construction of Porous Chiral Networks.

Two series of hyper-cross-linked microporous polyacetylene networks containing either -[CH=C(CH=O)]- or -[CH=C(CH2OH)]- monomeric units are reported. Networks are prepared by chain-growth copolymerization of acetal-protected propargyl aldehyde and acetal-protected propargyl alcohol with a 1,3,5-triethynylbenzene cross-linker followed by hydrolytic deprotection/detemplating. Deprotection not only liberates reactive CH=O and CH2OH groups in the networks but also modifies the texture of the networks towards higher microporosity and higher specific surface area. The final networks with CH=O and CH2OH groups attached directly to the polyene main chains of the networks have a specific surface area from 400 to 800 m2/g and contain functional groups in a high amount, up to 9.6 mmol/g. The CH=O and CH2OH groups in the networks serve as active centres for the reversible capture of CO2 and water vapour. The water vapour capture capacities of the networks (up to 445 mg/g at 297 K) are among the highest values reported for porous polymers, making these materials promising for cyclic water harvesting from the air. Covalent modification of the networks with (R)-(+)-3-aminopyrrolidine and (S)-(+)-2-methylbutyric acid enables the preparation of porous chiral networks and shows networks with CH=O and CH2OH groups as reactive supports suitable for the anchoring of various functional molecules.

Historical ferrous slag induces modern environmental problems in the Moravian Karst (Czech Republic).

Ferrous slag produced by a historic smelter is washed from a slagheap and transported by a creek through a cave system. Slag filling cave spaces, abrasion of cave walls / calcite speleothems, and contamination of the aquatic environment with heavy metals and other toxic components are concerns. We characterize the slag in its deposition site, map its transport through the cave system, characterize the effect of slag transport, and evaluate the risks to both cave and aqueous environments. The study was based on chemical and phase analysis supported laboratory experiments and geochemical modeling. The slag in the slagheap was dominated by amorphous glass phase (66 to 99 wt%) with mean composition of 49.8 ± 2.8 wt% SiO2, 29.9 ± 1.6 wt% CaO, 13.4 ± 1.2 wt% Al2O3, 2.7 ± 0.3 wt% K2O, and 1.2 ± 0.1 wt% MgO. Minerals such as melilite, plagioclase, anorthite, and wollastonite / pseudowollastonite with lower amounts of quartz, cristobalite, and calcite were detected. Slag enriches the cave environment with Se, As, W, Y, U, Be, Cs, Sc, Cd, Hf, Ba, Th, Cr, Zr, Zn, and V. However, only Zr, V, Co, and As exceed the specified limits for soils (US EPA and EU limits). The dissolution lifetime of a 1 mm3 volume of slag was estimated to be 27,000 years, whereas the mean residence time of the slag in the cave is much shorter, defined by a flood frequency of ca. 47 years. Consequently, the extent of slag weathering and contamination of cave environment by slag weathering products is small under given conditions. However, slag enriched in U and Th can increase radon production as a result of alpha decay. The slag has an abrasive effect on surrounding rocks and disintegrated slag can contaminate calcite speleothems.

Microporous Hyper-Cross-Linked Polymers with High and Tuneable Content of Pyridine Units: Synthesis and Application for Reversible Sorption of Water and Carbon Dioxide.

New hyper-cross-linked porous organic polymers (POPs) with a high content of pyridine segments (7.86 mmol pyridine g-1 ), and a micro/mesoporous texture are reported. The networks are achieved by the chain-growth homopolymerization of 2,6- and 3,5-diethynylpyridines. The pyridine segments form links interconnecting the polyacetylene main chains in these networks. The content of pyridine segments in the networks can be tuned by copolymerizing diethynylpyridines with 1,3-diethynylbenzene. The pyridine rings in the networks serve as base and hydrophilic centers for the sorption of CO2 and water. The homopolymer pyridine networks are highly efficient in the low-pressure adsorption/desorption of CO2 . This sorption mode is promising for the postcombustion removal of CO2 from the fuel gas. The poly(3,5-diethynylpyridine) network exhibits high efficiency in capturing and releasing water vapor (determined capacity 376 mg g-1 at 298 K and relative humidity (RH) = 90% is one of the highest values reported for POPs) and is a promising material for the cyclic water harvesting from air. The reported networks are characterized by 13 C cross-polarization magic angle spinning NMR, thermogravimetric analysis, and N2 adsorption/desorption and their efficiency in CO2 and H2 O capturing is discussed in relation to the content and type of incorporated pyridine segments.

Hyper-Cross-Linked Polyacetylene-Type Microporous Networks Decorated with Terminal Ethynyl Groups as Heterogeneous Acid Catalysts for Acetalization and Esterification Reactions.

Heterogeneous catalysts based on materials with permanent porosity are of great interest owing to their high specific surface area, easy separation, recovery, and recycling ability. Additionally, porous polymer catalysts (PPCs) allow us to tune catalytic activity by introducing various functional centres. This study reports the preparation of PPCs with a permanent micro/mesoporous texture and a specific surface area SBET of up to 1000 m2 g-1 active in acid-catalyzed reactions, namely aldehyde and ketone acetalization and carboxylic acid esterification. These PPC-type conjugated hyper-cross-linked polyarylacetylene networks were prepared by chain-growth homopolymerization of 1,4-diethynylbenzene, 1,3,5-triethynylbenzene and tetrakis(4-ethynylphenyl)methane. However, only some ethynyl groups of the monomers (from 58 to 80 %) were polymerized into the polyacetylene network segments while the other ethynyl groups remained unreacted. Depending on the number of ethynyl groups per monomer molecule and the covalent structure of the monomer, PPCs were decorated with unreacted ethynyl groups from 3.2 to 6.7 mmol g-1 . The hydrogen atoms of the unreacted ethynyl groups served as acid catalytic centres of the aforementioned organic reactions. To the best of our knowledge, this is first study describing the high activity of hydrogen atoms of ethynyl groups in acid-catalyzed reactions.

Homo- and Copolycyclotrimerization of Aromatic Internal Diynes Catalyzed with Co2 (CO)8 : A Facile Route to Microporous Photoluminescent Polyphenylenes with Hyperbranched or Crosslinked Architecture.

This study reports the first Co2 (CO)8 -catalyzed [2+2+2] polycyclotrimerization by the transformation of internal ethynyl groups of aromatic diyne monomers. The reaction yields polycyclotrimers of polyphenylene-type with either hyperbranched or partly crosslinked architecture. The homopolycyclotrimerization of the monomers with two ethynyl groups per one molecule, namely 1,4-bis(phenylethynyl)benzene, 4,4'-bis(phenylethynyl)biphenyl, and 4-(phenylethynyl)phenylacetylene, gives partly crosslinked, insoluble polyphenylenes. The soluble, hyperbranched polyphenylenes are generated via copolycyclotrimerization of 1,4-bis(phenylethynyl)benzene with 1,2-diphenylacetylene (average number of ethynyl groups per monomer molecule < 2). This one-step polycyclotrimerization path to hyperbranched or partly crosslinked polyphenylenes is an alternative to the synthesis of these polymers by Diels-Alder transformation of substituted cyclopentadienones. All polyphenylenes prepared exhibit photoluminescence with emission maxima ranging from 381 to 495 nm. Polyphenylenes with a less compact packing of segments are microporous (specific surface area up to 159 m2 g-1 ), which is particularly important in the case of soluble polyphenylenes because they can be potentially used to prepare microporous layers.

The capacity and effectiveness of diosmectite and charcoal in trapping the compounds causing the most frequent intoxications in acute medicine: A comparative study.

The aim of the study was to compare the adsorption ability of two adsorbent materials, namely diosmectite and activated charcoal towards selected model compounds that are most commonly involved in acute intoxication. Eleven model compounds were selected: acetylsalicylic acid, α-amanitin, amlodipine, digoxin, phenobarbital, ibuprofen, imipramine, carbamazepine, oxazepam, promethazine, and theophylline. Of the tested compounds, promethazine and imipramine were the most effectively adsorbed to diosmectite. Their adsorption to diosmectite (0.356±0.029mg promethazine/mg diosmectite and 0.354±0.019mg imipramine/mg diosmectite, respectively) was significantly higher than their adsorption to activated charcoal. The effect of temperature and pH on the adsorption efficiencies was also evaluated. In the case of experiments with mixture of both adsorbents, they mostly behaved in a solution independently or in a slightly antagonistic way. Using various methods such as N2 adsorption and thermogravimetric analysis, the structure and texture of diosmectite and activated charcoal were attained.

Unexpectedly Facile Rh(I) Catalyzed Polymerization of Ethynylbenzaldehyde Type Monomers: Synthesis of Polyacetylenes Bearing Reactive and Easy Transformable Pendant Carbaldehyde Groups.

The chain coordination polymerization of (ethynylarene)carbaldehydes with unprotected carbaldehyde groups, namely ethynylbenzaldehydes, 1-ethynylbenzene-3,5-dicarboxaldehyde, and 3-[(4-ethynylphenyl)ethynyl]benzaldehyde, is reported for the first time. Polymerization is catalyzed with various Rh(I) catalysts and yields poly(arylacetylene)s with one or two pendant carbaldehyde groups per monomeric unit. Surprisingly, the carbaldehyde groups of the monomers do not inhibit the polymerization unlike the carbaldehyde group of unsubstituted benzaldehyde that acts as a strong inhibitor of Rh(I) catalyzed polymerization of arylacetylenes. The inhibition ability of carbaldehyde groups in (ethynylarene)carbaldehydes seems to be eliminated owing to a simultaneous presence of unsaturated ethynyl groups in (ethynylarene)carbaldehydes. The reactive carbaldehyde groups make poly[(ethynylarene)carbaldehyde]s promising for functional appreciation via various postpolymerization modifications. The introduction of photoluminescence or chirality to poly(ethynylbenzaldehyde)s via quantitative modification of their carbaldehyde groups in reaction with either photoluminescent or chiral primary amines under formation of the polymers with Schiff-base-type pendant groups is given as an example.

Sedimentary record and anthropogenic pollution of a complex, multiple source fed dam reservoirs: An example from the Nové Mlýny reservoir, Czech Republic.

While numerous studies of dam reservoirs contamination are reported world-wide, we present a missing link in the study of reservoirs sourced from multiple river catchments. In such reservoirs, different point sources of contaminants and variable composition of their sedimentary matrices add to extremely complex geochemical patterns. We studied a unique, step-wise filled Nové Mlýny dam reservoir, Czech Republic, which consists of three interconnected sub-basins. Their source areas are located in units with contrasting geology and different levels and sources of contamination. The aim of this study is to provide an insight into the provenance of the sediment, including lithogenic elements and anthropogenic pollutants, to investigate the sediment dispersal across the reservoir, and to assess the heavy metal pollution in each basin. The study is based on multi-proxy stratigraphic analysis and geochemistry of sediment cores. There is a considerable gradient in the sediment grain size, brightness, MS and geochemistry, which reflects changing hydrodynamic energy conditions and primary pelagic production of CaCO3. The thickness of sediments generally decreases from proximal to distal parts, but underwater currents can accumulate higher amounts of sediments in distal parts near the thalweg line. Average sedimentation rates vary over a wide range from 0.58cm/yr to 2.33cm/yr. In addition, the petrophysical patterns, concentrations of lithogenic elements and their ratios made it possible to identify two main provenance areas, the Dyje River catchment (upper basin) and the Svratka and Jihlava River catchments (middle and lower basin). Enrichment factors (EF) were used for distinguishing the anthropogenic element contribution from the local background levels. We found moderate Zn and Cu pollution (EF ~2 to 5) in the upper basin and Zn, Cu and Pb (EF ~2 to 4.5) in the middle basin with the peak contamination in the late 1980s, indicating that the two basins have different contamination histories.

Polyacetylene-type networks prepared by coordination polymerization of diethynylarenes: new type of microporous organic polymers.

Microporous organic polymers (MOP) of a new type have been synthesised in high yields by a simple coordination polymerization of 1,3-diethynylbenzene, 1,4-diethynylbenzene and 4,4'-diethynylbiphenyl catalysed by [Rh(cod)acac] and [Rh(nbd)acac] complexes. The new MOPs are non-swellable polyacetylene-type conjugated networks consisting of ethynylaryl-substituted polyene main chains that are crosslinked by arylene linkers. Prepared MOP samples have a mole fraction of branching units (by (13)C CP/MAS NMR) from 0.30 to 0.47 and exhibit the BET (Brunaer-Emmett-Teller) surface up to 809 m(2) g(-1) and hydrogen uptake up to 0.69 wt% (77 K, H2 pressure 750 torr).

Morphology and optical responses of SERS active pi-conjugated poly(N-ethyl-2-ethynylpyridinium iodide)/Ag nanocomposite systems.

The influence of the poly(N-ethyl-2-ethynylpyridinium iodide) (PEEP-I) concentration on the morphology and optical properties of nanocomposite systems prepared by mixing the polymer solution with a hydrosol of ca. 9 nm Ag nanoparticles (NPs) was investigated by a combination of surface plasmon extinction (SPE) measurements, transmission electron microscope (TEM) imaging and surface-enhanced Raman spectroscopy (SERS). The PEEP-I concentration was found to have a strong impact on the assembly of Ag NPs and, consequently, on the optical responses of the composite systems. At low polymer concentrations in the composite (corresponding to ca. 50-1800 monomer units/NP), the formation of fractal aggregates was observed. In particular, the average fractal dimension D = 1.9 +/- 0.1 was determined for aggregates in the system with 5 x 10(-6) M polymer concentration. By contrast, in systems with polymer concentrations higher than about 1 x 10(-5) M, relatively small aggregates of Ag NPs with large interparticle distances were formed. The differences in the morphology of the composite systems with various polymer concentrations manifested themselves clearly in their SPE spectra. Furthermore, upon optical excitation with appropriate wavelengths (488.0 and 514.5 nm), the fractal aggregates acted as carriers of "hot spots", i.e. strong, localized, nanoscale optical fields, from which intense and well resolved SERS spectra of the polymer were obtained.

Characterization of substituted polyacetylene microstructure by pyrolysis gas chromatography.

A series of substituted acetylenes has been polymerized with WOC14/Ph4Sn metathesis catalyst and [Rh(cod)OMe]2 insertion catalyst, and the thermal degradation of the polyacetylenes prepared has been studied using pyrolysis capillary gas chromatography (Py-GC) with flame ionization and mass spectrometric detection to obtain information on the effect of the catalyst on the head-tail (H-T) isomerism of polyacetylenes (poly(phenylacetylene), poly[(4-methylphenyl)acetylene], poly(benzylacetylene), poly((2-fluorophenyl)acetylene], poly[(3-fluorophenyl)acetylene], and poly[(4-fluoro-phenyl)acetylenel). Cyclotrimers have been found to be the main pyrolysis products in all cases. Direct Py-MS connection was used to determine the temperature profiles of the released pyrolysis products. 1,3,5-Trisubstituted benzenes were found to be the predominant pyrolysis products of the polymers prepared with the insertion catalyst, which proves the presence of long head-to-tail sequences of monomeric units in these polyacetylenes. On the other hand, both 1,2,4- and 1,3,5-trisubstituted benzenes are present in significant amounts in the pyrolysis products of polymers prepared with the metathesis catalyst, which proves the presence of a significant content of the head-to-head (HH) and tail-to-tail (TT) linkages in these isomers of polyacetylenes. Contents of the regular (HT) and inverse (HH-TT) monomer linkages (RML and IML, respectively) in polymer chains were determined from the relative amounts of di-, tri-, and tetrasubstituted benzenes found in the Py-GC products.

Polybenzimidazole-supported [Rh(cod)Cl]2 complex: effective catalyst for the polymerization of substituted acetylenes.

The first heterogeneous catalyst which affords polymerization of substituted acetylenes into readily available high molecular weight polymers is reported. The catalyst (Rh/PBI) has been prepared by supporting di-mu-chloro-bis(eta4-cycloocta-1,5-diene)dirhodium(I), [Rh(cod)Cl]2, on commercial polybenzimidazole (PBI) porous beads by means of a simple quantitative adsorption from THF solution, and tested in polymerization of phenylacetylene, 4-fluorophenylacetylene, and 4-pentylphenylacetylene. The polymer molecules formed were found to be released from the Rh/PBI to surrounding solution during the polymerization performed in THF. Formation of high molecular weight ((M)w values up to 325,000) polymers in prevailing cis-transoid configuration has been observed with all monomers. In a comparison with free [Rh(cod)Cl]2 used as the homogeneous catalyst, the Rh/PBI can be used repeatedly, exhibits somewhat lower polymerization activity but almost no oligomerization activity, and provides polymers of higher molecular weight.