Hexakis[p-(hydroxymethyl)phenoxy]cyclotriphosphazene as an Environmentally Friendly Modifier for Polyurethane Powder Coatings with Increased Thermal Stability and Corrosion Resistance.

Protection against fire and the corrosion of metals is necessary to ensure human safety. Most of the fire and corrosion inhibitors do not meet the ecological requirements. Therefore, effective and ecological methods of protecting metals are currently a challenge for researchers. In this work, the influence of hexakis(4-(hydroxymethyl)phenoxy)cyclotriphosphazene (HHPCP) on the characteristics of powder coatings was examined. The coatings' properties were investigated by measuring the roughness, hardness, adhesion to the steel surface, cupping, gloss, scratch resistance, and water contact angle. The thermal stability was studied by furnace test and TGA analysis. The corrosion resistance test was carried out in a 3.5% NaCl solution. The distribution of phosphazene-derived segments in the coating was examined by GD-EOS analysis. Modified coatings show better corrosion and thermal resistance and can be used for the protection of the steel surface. Their better corrosion resistance is due to the electroactive properties of the phosphazene ring and its higher concentration at the coating surface, confirmed by GD-EOS analysis. The increase in thermal resistance is due to the effect of the formation of phosphoric metaphosphoric and polyphosphoric acids during the decomposition of HHCPC, which remain in the condensed char phase and play a crucial role in surface protection.

Effect of Shear Stress during Processing on Structure, Morphology, and Properties of Isotactic Polypropylene Nucleated with Silsesquioxane-Based ß-Nucleating Agent.

The study aimed to determine the influence of shear stress during real-life industrial processes such as compression molding and injection molding to different cavities on the crystallization of the isotactic polypropylene nucleated with a novel silsesquioxane-based ß-nucleating agent. Octakis(N2,N6-dicyclohexyl-4-(3-(dimethylsiloxy)propyl)naphthalene-2,6-dicarboxamido)octasilsesquioxane (SF-B01) is a highly effective nucleating agent (NA) based on the hybrid organic-inorganic silsesquioxane cage. The samples containing various amounts of the silsesquioxane-based and commercial iPP ß-nucleants (0.01-0.5 wt%) were prepared by compression molding and injection molding, including forming in the cavities with different thicknesses. The study of the thermal properties, morphology, and mechanical properties of iPP samples allows for obtaining comprehensive information about the efficiency of silsesquioxane-based NA in shearing conditions during the forming. As a reference sample, iPP nucleated by commercial ß-NA (namely N2,N6-dicyclohexylnaphthalene-2,6-dicarboxamide, NU-100) was used. The static tensile test assessed the mechanical properties of pure and nucleated iPP samples formed in different shearing conditions. Variations of the ß-nucleation efficiency of the silsesquioxane-based and commercial nucleating agents caused by shear forces accompanying the crystallization process during forming were evaluated by differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). The investigations of changes in the mechanism of interactions between silsesquioxane and commercial nucleating agents were supplemented by rheological analysis of crystallization. It was found that despite the differences in the chemical structure and solubility of the two nucleating agents, they influence the formation of the hexagonal iPP phase in a similar way, taking into consideration the shearing and cooling conditions.

Siloxane resins as hydrophobic self-cleaning layers for silicon and dye-sensitized solar cells: material and application aspects.

The aim of this study has been to examine in depth three siloxane resins (R1-R3) and two silanes (S1-S2) as hydrophobic self-cleaning layers for silicon and dye-sensitized solar cells. Herein, we focused on creating an active self-cleaning surface system using a combination of material and technical aspects. Siloxane resins were obtained via the hydrolytic polycondensation of methyltrimethoxysilane (R1) or the hydrolytic co-polycondensation of methyltrimethoxysilane, isobutyltrimethoxysilane and 3-methacroiloxypropyltrimethoxysilane (R2) or methyltrimethoxysilane n-octyltriethoxysilane and 3-methacroiloxypropyltrimethoxysilane (R3) under alkaline conditions using tetrahydrofuran. All layers under study did not significantly affect the original optical properties of the glass support, confirming that all these compounds can be used as protective layers on glass surfaces. The hydrophobic nature of formed layers was confirmed by static water contact angle measurements for hexane- and/or dibutyl ether-based starting solutions at various concentrations. The structural defects in created layers were studied via atomic force microscopy and thermal imaging, revealing RMS roughness (R q) values in the range of 0.76-5.25 nm, which varied for different materials. The current-voltage curves of different hydrophobic coatings showed conductive behaviour, demonstrating that principally non-conductive coatings mixed with silver conductive paste showed a certain level of conductivity. This finding suggests that the hydrophobic coating resembles a porous structure, enabling the formation of electrically conductive pathways. Finally, the influence of the presence of a coating layer on silicon and dye-sensitized solar cells was studied, and no negative effect on their photovoltaic parameters was observed after the durability test.

Silicone polyether surfactant enhances bacterial cellulose synthesis and water holding capacity.

The versatility and unique properties of bacterial cellulose (BC) motivate research into enhancing its synthesis. Here a silicone polyether surfactant (SPS) was synthesized and tested as a non-nutritional additive to the cultivation media of Komagataeibacter xylinus. The addition of SPS to the Hestrin-Schramm (HS) medium resulted in a concentration-dependent decrease in surface tension from 59.57 ± 0.37 mN/m to 30.05 ± 0.41 mN/m (for 0.1% addition) that was correlated with an increased yield of BC, up to 37% wet mass for surfactant concentration close to its critical micelle concentration (0.008%). Physicochemical characterization of bacterial cellulose obtained in presence of SPS, showed that surfactant is not incorporated into BC structure and has a moderate effect on its crystallinity, thermal stability. Moreover, the water holding capacity was enhanced by over 40%. Importantly, obtained BC did not affect L929 murine fibroblast cell viability. We conclude that SPS provides an eco-friendly approach to increasing BC yield in static culture, enabling more widespread industrial and biomedical applications.

A terminal neptunium(V)-mono(oxo) complex.

Neptunium was the first actinide element to be artificially synthesized, yet, compared with its more famous neighbours uranium and plutonium, is less conspicuously studied. Most neptunium chemistry involves the neptunyl di(oxo)-motif, and transuranic compounds with one metal-ligand multiple bond are rare, being found only in extended-structure oxide, fluoride or oxyhalide materials. These combinations stabilize the required high oxidation states, which are otherwise challenging to realize for transuranic ions. Here we report the synthesis, isolation and characterization of a stable molecular neptunium(V)-mono(oxo) triamidoamine complex. We describe a strong Np≡O triple bond with dominant 5f-orbital contributions and σu > πu energy ordering, akin to terminal uranium-nitrides and di(oxo)-actinyls, but not the uranium-mono(oxo) triple bonds or other actinide multiple bonds reported so far. This work demonstrates that molecular high-oxidation-state transuranic complexes with a single metal-ligand bond can be stabilized and studied in isolation.

Multifunctional Cotton Fabrics Obtained by Modification with Silanes Containing Esters of Phosphoric Acid as Substituents.

The development of novel flame retardants for cotton textiles that form a stable layer on textile fiber is of high economical and practical relevance. A novel flame retardant fluorinated phosphoric acid esters modified silicone resins for cotton modification were synthesized. The investigated phosphoric acid esters based compounds were substituted by a fluorinated chain or ring, and alkoxysilyl groups. The presence of alkoxysilyl groups allowed the formation of bonds with cellulose, while derivatives of phosphoric esters reduced the flammability of fabrics. Additionally, the presence of fluoride in their structures affected the hydrophobic properties. Cotton fabrics were modified in a simple one-step process by dip-coating method. The flame retardant properties of modified textiles were examined by performing microcalorimetric analysis, thermogravimetry analysis, and measuring oxygen index. The hydrophobicity was evaluated by measuring the water contact angle. The modified fabrics were characterized by SEM-EDS (Scanning Electron Microscopy with Energy Dispersive Spectroscopy) analysis and surface morphology. As a result of the tests, multifunctional fabrics were obtained.

Phosphorus-Containing Silsesquioxane Derivatives as Additive or Reactive Components of Epoxy Resins.

Two phosphorus-containing cage-like silsesquioxane derivatives were synthesized as reactive or additive flame retardants for epoxy resin. The silsesquioxanes were obtained via an epoxide ring-opening reaction using a 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPA). In one derivative containing in its structure 4 glycidoxypropyl and 4 phosphate groups, denoted as 4P4GS, only half of the epoxy rings was reacted with phosphate to obtain a reactive additive, while in the second derivative containing 8 phosphate groups, denoted as 8PS, all epoxy groups were converted, thus an additive modifier was obtained. The silsesquioxanes containing phosphorus atoms and the reactive phosphorus-free silsesquioxane derivative (octakis[(3-glycidoxypropyl)dimethylsiloxy]octasilsesquioxane (8GS)) were used to prepare hybrid materials based on epoxy resin. To compare the impact of the structure of silsesquioxane derivatives on the properties of hybrid materials, a number of samples containing 1, 5, and 10% of the modifiers making a series of epoxy materials containing additive or reactive modifiers, were obtained. The modified epoxies were studied using scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM-EDS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), nanoindentation, water contact angle, and cone calorimetry tests to assess the effects of the modifier structure on the physicochemical properties of the investigated materials.

Pt(0)-Catalysed synthesis of new bifunctional silanes.

We report herein very efficient syntheses of new functional silanes obtained via olefin hydrosilylation. New bifunctional compounds contain attractive functional groups such as epoxy, fluoroalkyl, trisilylamine, chloropropyl, and methacroiloxy which can play different roles in molecular systems. Moreover, the catalytic system proposed by us exhibits high selectivity and tolerance to a wide range of functional groups. It also permitted obtaining total conversions of the starting reagents in a relatively short time under mild conditions.

Preparation of Tri(alkenyl)functional Open-Cage Silsesquioxanes as Specific Polymer Modifiers.

The scientific reports on polyhedral oligomeric silsesquioxanes are mostly focused on the formation of completely condensed T8 cubic type structures and recently so-called double-decker derivatives. Herein, we report on efficient synthetic routes leading to trifunctionalized, open-cage silsesquioxanes with alkenyl groups of varying chain lengths from -vinyl to -dec-9-enyl and two types of inert groups (iBu, Ph) at the silsesquioxane core. The presented methodology was focused on hydrolytic condensation reaction and it enabled obtaining titled compounds with high yields and purity. A parallel synthetic methodology that was based on the hydrosilylation reaction was also studied. Additionally, a thorough characterization of the obtained compounds was performed, also in terms of their thermal stability, melting and crystallization temperatures (TGA and DSC) in order to show the changes in the abovementioned parameters dependent on the type of reactive as well as inert groups at Si-O-Si core. The presence of unsaturated alkenyl groups has a profound impact on the application potential of these systems, i.e., as modifiers or comonomers for copolymerization reaction.

Organosilicons of different molecular size and chemical structure as consolidants for waterlogged archaeological wood - a new reversible and retreatable method.

Ineffectiveness of the chemicals applied so far for waterlogged wood conservation created the need to develop new more, efficient and reliable agents. As an alternative, a new method with the use of organosilicon compounds differing in chemical composition and molecular weight has been investigated. The results obtained show the potential of organosilicons as consolidants in waterlogged wood conservation able to effectively stabilise wood dimensions upon drying. The best wood stabilisers were low-molecular organosilicons enable to penetrate the cell wall as well as chemicals with functional groups capable of interacting with wood polymers and forming stabilising coatings on the cell wall surface. The best anti-shrink efficiency values were obtained for (3-Mercaptopropyl)trimethoxysilane, (3-Aminopropyl)triethoxysilane, 1,3-Bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, reaching 98, 91 and 91%, respectively. Most of the applied organosilicons reduced wood hygroscopicity, which limits the risk of further dimensional changes of wood exposed to a variable air moisture content and potentially reduces wood biodegradation. In the light of our studies, the proposed method of waterlogged wood conservation with organosilicons is potentially reversible in the case of siloxanes and amino-silanes as well as retreatable, which complies with the requirements of the conservation ethics.

Effect of ß-Ketoiminato Ancillary Ligand Modification on Emissive Properties of New Iridium Complexes.

A series of new bis(benzo[h]quinolinato) Ir(III) complexes with modified ß-ketoiminato ancillary ligands were synthesized, and their electrochemical, photophysical properties were determined with the support of theoretical calculations. Moreover, all the synthesized heteroleptic Ir(III) complexes were examined as dopants of the host-guest type emissive layers in solution-processed phosphorescent organic light emitting diodes (PhOLEDs) of a simple structure. As expected on the basis of voltammetry measurements as well as DFT calculations, all the compounds appeared to be green emitters. Their examination showed that alteration of ß-ketoiminato ligand structure causes frontier orbitals' energy levels to be slightly changed, while significantly affecting photoluminescence and electroluminescence efficiencies of iridium phosphors containing these ligands. It was also found that modification of ancillary ligands might enhance charge trapping on the dopant, thus increasing its efficiency, especially in electroluminescence. From among the iridium complexes studied, the compound bearing 1-naphthyl group bonded to the nitrogen atom of the ancillary ligand proved to be the most efficient emitter. The PhOLED fabricated on the basis of this dopant has reached a luminance level of 16000 cd/m2, current efficiency close to 12 cd/A, and an external quantum efficiency around 3.2%.

Complications after proctocolectomy and ileal pouch-anal anastomosis in pediatric patients: A systematic review.

BACKGROUND/PURPOSE: Colectomy with ileal pouch-anal anastomosis (IPAA) is the standard of care for patients with familial adenomatous polyposis (FAP) and refractory ulcerative colitis (UC). The rates of postoperative complications are not well established in children. The objective of this systematic review is to establish benchmark data for morbidity after pediatric IPAA. METHODS: PubMed, Embase, and The Cochrane Library were searched for studies of colectomy with IPAA in patients ≤21 years old. UC studies were limited to the anti-tumor necrosis factor-α agents era (1998-present). All postoperative complications were extracted. RESULTS: Thirteen studies met the inclusion criteria (763 patients). Compared to patients with FAP, UC patients had a higher prevalence of pouch loss (10.6% vs. 1.5%). Other major complications such as anastomotic leak, abscess, and fistula were uncommon (mean prevalence 4.9%, 4.2%, and 5.0%, respectively, for patients with UC; 8.7%, 4.2%, and 4.3% for FAP). The most frequent complication was pouchitis (36.4% of UC patients). CONCLUSIONS: Devastating complications from colectomy and IPAA are rare, but patients with UC have poorer outcomes than those with FAP. Much of the morbidity may therefore stem from patient or disease factors. Multicenter, prospective studies are needed to identify modifiable risks in patients with UC undergoing IPAA. LEVEL OF EVIDENCE: Prognostic, level II.

Solid-State Structure of Tris-Cyclopentadienide Uranium(III) and Plutonium(III).

The organometallic tris-cyclopentadienide actinide(III) (AnCp3 ) complexes were first reported about 50 years ago. However, up until now, only the NpCp3 solid state structure has been studied. Here we report on the solid state structures of UCp3 and PuCp3 which are isostructural to the Np analogue. The structural models are supported by theoretical calculations and compared to their lanthanide analogues. The observed trends in changes of bond lengths might be indicator for an increased covalency in the bonding in the tris-cyclopentadienide actinide(III) complexes (AnCp3 ) compared to their lanthanide homologues.

Organometallic Neptunium Chemistry.

Fifty years have passed since the foundation of organometallic neptunium chemistry, and yet only a handful of complexes have been reported, and even fewer have been fully characterized. Yet, increasingly, combined synthetic/spectroscopic/computational studies are demonstrating how covalently bonding, soft, carbocyclic organometallic ligands provide an excellent platform for advancing the fundamental understanding of the differences in orbital contributions and covalency in f-block metal-ligand bonding. Understanding the subtleties is the key to the safe handling and separations of the highly radioactive nuclei. This review describes the complexes that have been synthesized to date and presents a critical assessment of the successes and difficulties in their analysis and the bonding information they have provided. Because of increasing recent efforts to start new Np-capable air-sensitive inorganic chemistry laboratories, the importance of radioactivity, the basics of Np decay and its ramifications (including the radiochemical synthesis of one organometallic compound), and the available anhydrous starting materials are also surveyed. The review also highlights a range of instances in which important differences in the chemical behavior between Np and its closest neighbors, uranium and plutonium, are found.

Reduction chemistry of neptunium cyclopentadienide complexes: from structure to understanding.

Neptunium complexes in the formal oxidation states II, III, and IV supported by cyclopentadienyl ligands are explored, and significant differences between Np and U highlighted as a result. A series of neptunium(iii) cyclopentadienyl (Cp) complexes [Np(Cp)3], its bis-acetonitrile adduct [Np(Cp)3(NCMe)2], and its KCp adduct K[Np(Cp)4] and [Np(Cp')3] (Cp' = C5H4SiMe3) have been made and characterised providing the first single crystal X-ray analyses of NpIII Cp complexes. In all NpCp3 derivatives there are three Cp rings in η5-coordination around the NpIII centre; additionally in [Np(Cp)3] and K[Np(Cp)4] one Cp ring establishes a µ-η1-interaction to one C atom of a neighbouring Np(Cp)3 unit. The solid state structure of K[Np(Cp)4] is unique in containing two different types of metal-Cp coordination geometries in the same crystal. NpIII(Cp)4 units are found exhibiting four units of η5-coordinated Cp rings like in the known complex [NpIV(Cp)4], the structure of which is now reported. A detailed comparison of the structures gives evidence for the change of ionic radii of ca. -8 pm associated with change in oxidation state between NpIII and NpIV. The rich redox chemistry associated with the syntheses is augmented by the reduction of [Np(Cp')3] by KC8 in the presence of 2.2.2-cryptand to afford a neptunium(ii) complex that is thermally unstable above -10 °C like the UII and ThII complexes K(2.2.2-cryptand)[Th/U(Cp')3]. Together, these spontaneous and controlled redox reactions of organo-neptunium complexes, along with information from structural characterisation, show the relevance of organometallic Np chemistry to understanding fundamental structure and bonding in the minor actinides.

Subtle Interactions and Electron Transfer between U(III) , Np(III) , or Pu(III) and Uranyl Mediated by the Oxo Group.

A dramatic difference in the ability of the reducing An(III) center in AnCp3 (An=U, Np, Pu; Cp=C5 H5 ) to oxo-bind and reduce the uranyl(VI) dication in the complex [(UO2 )(THF)(H2 L)] (L="Pacman" Schiff-base polypyrrolic macrocycle), is found and explained. These are the first selective functionalizations of the uranyl oxo by another actinide cation. At-first contradictory electronic structural data are explained by combining theory and experiment. Complete one-electron transfer from Cp3 U forms the U(IV) -uranyl(V) compound that behaves as a U(V) -localized single molecule magnet below 4 K. The extent of reduction by the Cp3 Np group upon oxo-coordination is much less, with a Np(III) -uranyl(VI) dative bond assigned. Solution NMR and NIR spectroscopy suggest Np(IV) U(V) but single-crystal X-ray diffraction and SQUID magnetometry suggest a Np(III) -U(VI) assignment. DFT-calculated Hirshfeld charge and spin density analyses suggest half an electron has transferred, and these explain the strongly shifted NMR spectra by spin density contributions at the hydrogen nuclei. The Pu(III) -U(VI) interaction is too weak to be observed in THF solvent, in agreement with calculated predictions.

Synthesis of an Open-Cage Structure POSS Containing Various Functional Groups and Their Effect on the Formation and Properties of Langmuir Monolayers.

Recently, silsesquioxanes have been recognized as a new group of film-forming materials. This study has been aimed at determining the effect of the kind of functional groups present in two different open-cage structure POSS molecules on the possibility of the formation of Langmuir monolayers and their properties. To achieve this goal, two new POSS derivatives (of open-cage structures) containing polyether and fluoroalkyl functional groups have been synthesized on the basis of a hydrosilylation process. An optimization of the process was performed, which makes it possible to obtain the above-mentioned derivatives with high yields. In the next step, the Langmuir technique was applied to measurements of the surface pressure (π) - the mean molecular area (A) isotherms during the compression of monolayers formed by molecules of the two POSS derivatives considered. Subsequently, the monolayers were transferred onto quartz plates according to the Langmuir-Blodgett technique. Both derivatives are able to form insoluble Langmuir films at the air-water interface, which can be transferred onto a solid substrate and effectively change its wetting properties.

Organometallic neptunium(III) complexes.

Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on U(III) and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

tert-Butyl(tert-butoxy)zinc hydroxides: hybrid models for single-source precursors of ZnO nanocrystals.

Alkylzinc alkoxides, [RZnOR']4, have received much attention as efficient precursors of ZnO nanocrystals (NCs), and their "Zn4O4 " heterocubane core has been regarded as a "preorganized ZnO". A comprehensive investigation of the synthesis and characterization of a new family of tert-butyl(tert-butoxy)zinc hydroxides, [(tBu)4 Zn4 (µ3-OtBu)x (µ3-OH)4-x], as model single-source precursors of ZnO NCs is reported. The direct reaction between well-defined [tBuZnOH]6 (16) and [tBuZnOtBu]4 (24) in various molar ratios allows the isolation of new mixed cubane aggregates as crystalline solids in a high yield: [(tBu)4 Zn4 (µ3-OtBu)3 (µ3-OH)] (3), [(tBu)4Zn4 (µ3-OtBu)2 (µ3-OH)2] (4), [(tBu)4 Zn4 (µ3-OtBu)(µ3-OH)3] (5). The resulting products were characterized in solution by (1) H NMR and IR spectroscopy, and in the solid state by single-crystal X-ray diffraction. The thermal transformations of 2-5 were monitored by in situ variable-temperature powder X-ray diffraction and thermogravimetric measurements. The investigation showed that the Zn-OH groups appeared to be a desirable feature for the solid-state synthesis of ZnO NCs that significantly decreased the decomposition temperature of crystalline precursors 3-5.

tert-Butylzinc hydroxide as an efficient predesigned precursor of ZnO nanoparticles.

The reaction of (t)Bu(2)Zn with water was investigated which led to isolation of the novel hexameric tert-butylzinc hydroxide. The resulting zinc hydroxide cluster appears to be an ideal predesigned single-source precursor which decomposes smoothly in one step at only ca. 120 °C into ZnO nanoparticles.