Organic Matrixes Research Articles

Modification of Epoxy Coatings with Fluorocontaining Organosilicon Copolymers.

Preparation of hydrophobic coatings is still a challenge for researchers in various fields of science. One of the easiest ways consists of the use of special modifiers. However, usually such modifiers are poorly compatible with organic polymeric matrixes, which leads to segregation of modifiers and deterioration of coating properties. In this work, we have synthesized a number of organosilicon copolymers and studied their compatibility with epoxy matrix and hydrophobic efficiency. It was shown that the increase of phenyl-containing units leads to increase of compatibility but decreases hydrophobic efficiency. Addition of small amounts of such modifiers into commercial epoxy paint material can lead to an increase of contact angle of the final coating from 63 to 87° without deterioration of other physico-mechanical properties. These results open new perspectives in preparation of organosilicon hydrophobic modifiers with directed properties for fields of application such as paints and coating materials.

Exploration of organic matrixes in conductive silver paste: a comprehensive review

Exploration of organic matrixes in conductive silver paste: a comprehensive review

AIEgen orthopalladated hybrid polymers for efficient inactivation of the total coliforms in urban wastewater

Monitorable AIE polymers with a bioactive pattern are employed in advanced biomedical applications such as functional coatings, theranostic probes, and implants. After the global COVID-19 pandemic, interest in developing surfaces with superior antimicrobial, antiproliferative, and antiviral activities dramatically increased. Many formulations for biocide surfaces are based on hybrid organic/inorganic materials. Palladium (II) complexes display relevant activity against common bacteria, even higher when compared to their uncoordinated ligands. This article reports the design and synthesis of two series of orthopalladated polymers obtained by grafting a cyclopalladated fragment on two different O, N chelating Schiff base polymers. Different grafting percentages were examined and compared for each organic polymer. The fluorescence emission in the solid state was explored on organic matrixes and grafted polymers. DFT analysis provided a rationale for the role of the coordination core. The antibacterial response of the two series of hybrid polymers was tested against the total coliform group of untreated urban wastewater, revealing excellent inactivation ability.

Review of Luminescence-Based Light Spectrum Modifications Methods and Materials for Photovoltaics Applications.

The dynamic development of photovoltaic and photo-sensitive electronic devices is constantly stimulated by material and technological advances. One of the key concepts that is highly recommended for the enhancement of these device parameters is the modification of the insulation spectrum. Practical implementation of this idea, although difficult, may be highly beneficial for photoconversion efficiency, photosensitivity range extension, and their cost reduction. The article presents a wide range of practical experiments leading to the manufacturing of functional photoconverting layers, dedicated to low-cost and wide-scale deposition methods. Various active agents, based on different luminescence effects as well as the possible organic carrier matrixes, substrate preparation and treatment procedures, are presented. New innovative materials, based on their quantum effects, are examined. The obtained results are discussed in terms of the application in new generation photovoltaics and other optoelectronic elements.

Treated sediment as substrate component of three containerized ornamental species: effects on marketable and qualitative traits

Carried out within the LIFE17ENV/IT/000347-SUBSED project, this research aimed at investigating the effect of a treated sediment (TS) as substrate component on the quality and marketability of three widespread containerized ornamental species: cherry laurel (Prunus laurocerasus) cv. Novìta, calla lily (Zantedeschia aethiopica) and protea (Protea cynaroides) cv. Little Prince. The TS was mixed with soilless substrates as sphagnum peat, coir, and bark in different proportion (0%, 25% and 50%). In cherry laurel, the TS used in 25 - 50% proportions reduced plant height, slightly altering its attractive vibrant foliage. A positive effect of the TS was evidenced on calla lily, where both tested sediment-based mixtures allowed a copious blooming and flower quality raised as the sediment content increased (TS 50% > TS 25% > TS 0%). Post-harvest longevity and colour of flowers were not affected by substrate composition. The effect of sediment-based substrates on protea growth and blooming showed an opposite trend (TS 0% > TS 25% > TS 50%), with plants grown on 50% v/v TS exhibiting a considerable reduction in plant growth and production of flower clusters, with brighter tones turning towards purple. Based on sale values, the TS proved to be a sustainable alternative for the production of potted ornamentals if properly mixed with other organic matrixes, such as peat and coir.

Intrinsic persistent room temperature phosphorescence derived from 1H-benzo[f]indole itself as a guest

The influence of 1H-benzo[f]indole (Bd) and its derivatives on room temperature phosphorescence (RTP) has raised great concern since they were found to significantly affect RTP of the extensively studied carbazole (Cz) derivatives. However, the role of Bd itself existing in Cz-based or other doping systems was still unclear. In order to clarify its intrinsic phosphorescent property, Bd was introduced as a guest into different organic matrixes including substituted Cz derivatives and polymers. The phosphorescence located in 560–620 nm was confirmed to be derived from Bd itself, which can be detected whatever Bd was doped in the crystal or amorphous state of Cz derivatives. The suitable energy gap between Cz derivatives and Bd is the key to achieve ultralong RTP of Bd. Additionally, when doped in polymers with plenty of hydrogen bonds, RTP of Bd with lifetime over 280 ms was easily obtained. Among them, Bd@PHEMA (poly(hydroxyethyl methacrylate) exhibited superior phosphorescence, with yellow afterglow lasting for over 2.5 s. Therefore, this work demonstrated that a new organic RTP phosphor, Bd, is discovered, and ultralong RTP of Bd can be achieved not only doped in Cz derivatives but also in polymers as the hosts.

Polystyrene nanospheres coated red phosphorus flame retardant for polyamide 66

AbstractAs a halogen‐free flame retardant, red phosphorus (RP) is unstable in air due to its slow oxidation. The shortcomings of RP include strong water absorbing proneness, high friction sensibility and poor thermal stability. The characteristics of polystyrene (PS) are thermostability and fluidity in melt, which can improve the compatibility of RP and the organic matrixes. Using PS as a coating material can improve the characteristics of strong water absorbing proneness of RP. Herein, the polystyrene nanospheres coated RP (PSNS@RP) flame retardant was successfully prepared via emulsion polymerization of styrene. The result shows that the release of phosphine from the PSNS@RP is greatly reduced. The ignition point is increased by about 200°C, and the moisture absorption rate can be reduced by 40 times. The effect of PSNS@RP on the flame retardancy and thermal stability of polyamide 66 (PA66) were studied in detail. Compared with PA66, the limiting oxygen index (LOI) of the PSNS@RP/PA66 composite is increased from 24.8% to 34.2%. The flame retardant grade is enhanced to be UL94 V‐0. The peak heat release rate (PHRR) is decreased from 1444.5 to 420.9 kW m−2, the total heat release (THR) is decreased from 145.8 to 94.2 MJ m−2, and the total smoke production (TSP) is also reduced by 35%. Therefore, the as‐synthesized PSNS@RP has excellent flame retardant and smoke‐suppressing properties for PA66.

How to achieve near unity fluorescence quantum yields on gold(I) benzothiadiazole-based derivatives

The synthesis of three new gold(I) benzothiadiazole derivatives has been carried out by the reaction of 4-ethynyl-7-(4-nonylphenyl)benzo[c] [1,2,5]thiadiazole (L) with three different gold(I)-PR3 (PR3 = triethylphosphane (2), triphenylphosphane (3) and tri-1-naphthylphosphane (4)) sources and their light emitting properties thoroughly investigated.The new compounds display denoted luminescence properties with fluorescence quantum yields above 80% in all cases except for the complex containing the bulkiest PNaph3 phosphane. The resulting emission is mainly dominated by the organic 2,1,3-benzothiadiazole moiety (BTD) and can be modulated following different strategies. On one hand, the emission wavelength of these compounds in solution can be ca. 60 nm shifted varying the polarity of the solvents. Interestingly, quantum yields and lifetimes can be strongly increased by changing the environment conditions, from water:acetonitrile solutions to dispersion of the compounds within organic matrixes. In this way, we have been able to obtain near unity fluorescence quantum yields, with the highest values recorded for gold(I) BTD compounds. The effect of the solvents on the emission changes has been rationalized with the help of the Lippert-Mataga equation and the multiparametric Kamlet-Taft method to analyse the excited state polarity.

Experimental Investigation on Strengthening of Soft Clay Brick Masonry Columns under Compression with Fiber-Reinforced Inorganic and Organic Matrixes

Masonry made with soft clay brick is commonly used in gravity load bearing of construction in India. The masonry piers and walls typically fail by vertical splitting. The purpose of this study is to improve the strength of masonry columns under compression using wrapping for additional confinement. The compressive load carrying performance and capacity of masonry columns wrapped with fiber reinforced composites in organic and inorganic matrixes are compared. For the purpose of overall improvements in cost and durability, glass and basalt fiber reinforcement is used. 30-40% improvement in the compressive performance of masonry prisms was achieved for both Organic and Inorganic matrixes. However, the specimens with inorganic matrixes were found to exhibit higher ductility compared to organic matrixes. Glass fibers were found to be more effective in wrapping masonry specimens compared to Basalt fiber specimens owing to its higher fiber count per unit length. Analytical models for predicting the compressive capacity of masonry columns with wrapping are verified against the experimental results.

Human Bones Solubility in Seawater

Introduction: In January 1968, an Israeli submarine "Dakar" sank in the Mediterranean Sea. The Dakar’s wreckage was not found until May 1999, when it was located between the islands of Cyprus and Crete at depth more than 3,000 m by the Nauticos Corporation, the same company which found a British passenger liner "Titanic" that sank in the North Atlantic Ocean after it collided with an iceberg. The possibility to recover any existing remains of the crew members in the sunken submarine “Dakar” and to give them Jewish burial had been widely discussed in Israel. Background: The human bones consist of mineral and organic matrixes. Therefore, the solubility of the bones in seawater will depend on the behavior of these two matrixes. The main mineral component of human bones is a calcium phosphate mineral which is similar in composition and structure to minerals within the apatite group. Thus, the human bones are rigid body tissue consisting of biological cells embedded in an abundant, hard intercellular material. Objective: The main objective is to study the possibility of solubility of human bones after prolonged time in deep waters. Methods: The solubility of minerals in natural waters can be calculated from thermodynamic considerations provided that the equilibrium constants are known, and ionic activity coefficients can be obtained. Using the approaches developed by Pitzer's scientific school for ionic activity coefficients calculations it was demonstrated in this article that neither hydroxyapatite nor fluorapatite can be dissolved in seawater. Results: It is well known, according to various publications, that no skeleton remains were found in most cases of sunken ships wreckage in deep seawaters. The question is how this contradiction can be explained if mineral constituents of human bones could not be dissolved in seawater, but no skeletons have been found in sunken ships being prolonged time in deep depths. We assume that the reason for this phenomenon is that skeleton bones in addition to mineral matrix contain organic constituents which can be dissolved in seawater due to various natural biological and chemical processes. After the dissolution of the organic constitutes of the bones, the bones remains could not be preserved as a whole in sunk ships. Conclusion: It can be assumed that due to the dissolution of human bones' organic contents in seawater, human bodies’ remains cannot be found in most cases in sunken ships after a prolonged time in deep waters.

Degradation of iopamidol by silicate-based microfiltration membrane activated peroxymonosulfate in aqueous solution: Efficiency, mechanism and degradation pathway

Iopamidol (IPM) was frequently detected in drinking water and effluents from wastewater treatment plants (WWTPs). A silicate-based microfiltration membrane (SFM) was successfully synthesized using silicate cement as raw material and pore-forming agent. In this study, peroxymonosulfate (PMS) was activated by SFM for the first time to effectively degrade and mineralize IPM. The removal efficiency and mineralization rate of IPM were 99.7% and 49.5% respectively within 30 min in the SFM/PMS process, which were higher than those obtained by PMS oxidation only (12.8% and 1.26%) and SFM adsorption (negligible). The effects of solution pH, PMS dosage, reaction temperature, natural organic matter (NOM), chloride ion (Cl−), bicarbonate (HCO− 3), and water matrixes on the degradation of IPM were systematically evaluated. Based on radical inhibition examinations and X-ray photoelectron spectroscopy (XPS) analysis, the potential activation mechanism was elucidated. It was found that the Fe(II) and alkaline hydration products on the surface of SFM could promote the activation of PMS. Radical scavenging tests and electron spin resonance (ESR) experiments suggested that hydroxyl radicals (•OH), sulfate radicals (SO4·−), singlet oxygen (1O2) and superoxide radicals (O2·−) generated in SFM/PMS system played a critical role for IPM degradation. Finally, eleven intermediates in the degradation process of IPM were identified and five degradation pathways were proposed, mainly including hydroxyl oxidation, amide hydrolysis, amino oxidation, hydroxyl substitution and dehydroxylation. The results show that the SFM/PMS process with its excellent catalytic activity is a promising strategy for effectively removing and mineralizing organic contaminants.

Tissue dermal equivalent – а cellular product based on human dermal keratinocytes and fibroblasts: the properties of equivalent components and perspectives of practical application

The nature and ways of isolation and cultivation in vitro of keratinocytes and fibroblasts, the main cellular components of skin to prepare a new biomedical product, tissue dermal equivalent were considered. The main attention was payed to optimization of upbuilding dermal cell biomass including selection of medium compositions and conditions of cultivation. The information was given on main parameters of cell cultures as proliferation activity, viability and phenotype of the cells. Genotoxicity of fibroblasts and biocompatibility of the cells with organic matrixes to find the optimal carrier for cellular elements of tissue dermal equivalent were studied. The composition, the process of preparation of tissue dermal equivalent and perspectives of its practical application were discussed.

Uterine Metabolomic Analysis for the Regulation of Eggshell Calcification in Chickens.

Eggshell quality is economically important for table eggs and functionally indispensable for hatching eggs. During the formation of eggshell in the uterus, organic matrixes in uterine fluid can control and modify the formation of calcified eggshell. At present, there are limited studies focusing on the effect of uterine organic metabolites on eggshell quality. In this study, an LC-MS-based metabolomic technology was performed to identify the crucial uterine metabolites that differently presented in hens producing eggs with divergent eggshell quality (eggshell strength, thickness, and weight). More than 1000 metabolites were identified in uterine fluid, and six putative metabolites, including phosphatidylcholine, diacylglycerol, verapamil, risedronate, coproporphyrinogen III, and biliverdin, were screened to play crucial roles in eggshell calcification. Then, two trials for oral administration and in vitro calcite crystal growth were conducted to verify the effect of potential different metabolites on the eggshell quality. Verapamil has a temporary effect on decreasing eggshell strength and eggshell thickness. Coproporphyrinogen III could induce smaller calcite crystals to improve eggshell strength while biliverdin could modify crystal morphology by forming rougher faces and rounder edges to strengthen the eggshell. The present study gives us new insight to understand the role of uterine fluid matrixes in eggshell calcification.

Reversible formation of coordination bonds in Sn-based metal-organic frameworks for high-performance lithium storage

Sn-based compounds with buffer matrixes possessing high theoretical capacity, low working voltage, and alleviation of the volume expansion of Sn are ideal materials for lithium storage. However, it is challenging to confine well-dispersed Sn within a lithium active matrix because low-melting-point Sn tends to agglomerate. Here, we apply a metal-organic framework (MOF) chemistry between Sn-nodes and lithium active ligands to create two Sn-based MOFs comprising Sn2(dobdc) and Sn2(dobpdc) with extended ligands from H4dobdc (2,5-dioxido-1,4-benzenedicarboxylate acid) to H4dobpdc (4,4’-dioxidobiphenyl-3,3’-dicarboxylate acid) with molecule-level homodispersion of Sn in organic matrixes for lithium storage. The enhanced utilization of active sites and reaction kinetics are achieved by the isoreticular expansion of the organic linkers. The reversible formation of coordination bonds during lithium storage processes is revealed by X-ray absorption fine structure characterization, providing an in-depth understanding of the lithium storage mechanism in coordination compounds.

Strong Enhancement of Nanoconfined Water Mobility by a Structure Breaking Salt.

For the majority of the water present on earth, the two most important factors influencing its behavior are confinement, in either inorganic or organic matrixes, and the presence of solutes. Here, we investigate the effect of confinement in 3 nm pores on water diffusivity in aqueous solutions with archetypical solutes, a structure making (kosmotrope) NaCl and a structure breaking (chaotrope) KCl, up to 1.0 M in concentration. The water diffusivity in bulk aqueous solutions in such a concentration range is known to decrease very slightly in the presence of NaCl and increase very slightly in the presence of KCl. However, here we observe the water diffusivity in confined H2O-KCl increases by a factor of 2 compared to the pure water diffusivity in the same confinement. This unusually strong cumulative effect of confinement and a structure breaking additive may have profound implications for the mobility and transport of aqueous species in nature.

Gold(i)-doped films: new routes for efficient room temperature phosphorescent materials.

The synthesis of four novel gold(i)-phosphane complexes coordinated to 9-phenanthrene chromophore has been carried out through the reaction of 9-phenanthreneboronic acid and the corresponding AuClPR3 (PR3 = PPh3 for triphenylphosphane (1a); 1,4-bis(diphenylphosphanyl)butane or dppb (2b); bis(diphenylphosphanyl)acetylene or dppa (2c); (AuCl)2(diphos) (diphos = bis(diphenylphosphanyl)methane or dppm (3)) sources. The X-ray crystal structures of compounds 1a and 2b show the existence of MOF-like intermolecular assemblies that contain empty inner cavities in the absence of aurophilic contacts. In contrast, the formation of a tetranuclear complex with intramolecular aurophilic interactions was evidenced for 3. Photophysical characterization indicates dual emission in all gold(i) complexes when oxygen is removed from the sample, while only fluorescence emission is recorded for the uncoordinated ligand. The introduction of the compounds within PMMA and Zeonex was assayed, and luminescent films containing gold(i) complexes where phosphorescence is the sole pathway for emission are obtained, instead of the dual emission (with significant fluorescence contribution) recorded in solution.

Effect of Gold(I) on the Room-Temperature Phosphorescence of Ethynylphenanthrene.

The synthesis of two series of gold(I) complexes with the general formulae PR3 -Au-C≡C-phenanthrene (PR3 =PPh3 (1 a/2 a), PMe3 (1 b/2 b), PNaph3 (1 c/2 c)) or (diphos)(Au-C≡C-phenanthrene)2 (diphos=1,1-bis(diphenylphosphino)methane, dppm (1 d/2 d), 1,4-bis(diphenylphosphino)butane, dppb (1 e/2 e)) has been realized. The two series differ in the position of the alkynyl substituent on the phenanthrene chromophore, being at the 9-position (9-ethynylphenanthrene) for the L1 series and at the 2-position (2-ethynylphenanthrene) for the L2 series. The compounds have been fully characterized by 1 H, 31 P NMR, and IR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction resolution in the case of compounds 1 a, 1 e, 2 a, and 2 c. The emissive properties of the uncoordinated ligands and corresponding complexes have been studied in solution and within organic matrixes of different polarity (polymethylmethacrylate and Zeonex). Room-temperature phosphorescence (RTP) is observed for all gold(I) complexes whereas only fluorescence can be detected for the pure organic chromophore. In particular, the L2 series presents better luminescent properties regarding the intensity of emission, quantum yields, and RTP effect. Additionally, although the inclusion of all the compounds in organic matrixes induces an enhancement of the observed RTP owing to the decrease in non-radiative deactivation, only the L2 series completely suppresses the fluorescence, giving rise to pure phosphorescent materials.

Bioactive Core-Shell CaF2 Upconversion Nanostructure for Promotion and Visualization of Engineered Bone Reconstruction.

Inorganic ion metabolism plays significant roles in various life processes including signal transduction, substance exchange, and cellular constructions. Regulation and monitoring of ion metabolism offer great promise to modulate biological activities and provide insights into related mechanisms. Here, a synergistic nanodepot based on a bioactive core-shell CaF2 upconversion nanostructure that integrates multiple mineral ions for metabolic regulation was built for the acceleration and monitoring of the biomineralization process. Multiple mineral ions released from the nanodepots can accelerate the growth of inorganic crystals and enhance the production of organic matrixes, synergistically facilitating the regeneration of bone defects in vivo. During the process, such a nanodepot can be constructed to specifically recognize osteoblasts for the monitoring of biomineralization. This nanoprobe represents an efficient strategy to promote and monitor biomineralization-related metabolic activities with applications in fundamental research, disease diagnosis, and regenerative medicine.

Co3O4/Bi4O5I2/Bi5O7I C-Scheme Heterojunction for Degradation of Organic Pollutants by Light-Emitting Diode Irradiation.

Remediation of organic pollutant matrixes from wastewater by photodegradation using different heterojunctions is extensively studied to improve performance for potential application. Brilliant black (BB) and p-nitrophenol (PNP) have been detected in the environment and implicated as directly or indirectly carcinogenic to human health. This work analyzes their elimination from aqueous solutions under visible-light irradiation with composites of cobalt(II, III) oxide and bismuth oxyiodides (Co3O4/Bi4O5I2/Bi5O7I). The synthesized nanomaterial properties were investigated using various techniques such as BET, SEM/EDS, TEM, XRD, FTIR, PL, and UV–vis. All the nanocomposites absorbed in the visible range of the solar spectrum with band gaps between 1.68 and 2.79 eV, and the specific surface area of the CB2 composite increased by 35.8% from that of Bi4O5I2/Bi5O7I. There was an observed massive reduction in the rate of electron and hole recombination, and the band gaps of the composites decreased. The mineralization of PNP and BB was followed by determination of the total organic carbon with reductions of 93.6 and 83.7%, respectively. The main active species were the hydroxyl radicals, while the superoxide anion radical and generated holes were minor as confirmed by radical trapping experiments. The optimum pHs for degradation of PNP and BB were 9.6 and 5.3, respectively. The enhanced performance of the catalyst was due to C-scheme heterojunction formation that reduced the electron and hole recombination rate and was attributed to strong adsorption of the pollutants on the photocatalyst active surface. The nanocomposite is apposite for solar energy-driven remediation of organic pollutants from environmental aqueous samples.

Porous TiO2 Film Immobilized with Gold Nanoparticles for Dual-Polarity SALDI MS Detection and Imaging.

Surface-assisted laser desorption/ionization (SALDI) mass spectrometry (MS) has become an attractive complementary approach to matrix-assisted laser desorption/ionization (MALDI) MS. SALDI MS has great potential for the detection of small molecules because of the absence of applied matrix. In this work, a functionalized porous TiO2 film immobilized with gold nanoparticles (AuNPs-FPTDF) was prepared to enhance SALDI MS performance. The porous TiO2 films were prepared by the facile sol-gel method and chemically functionalized for dense loading of AuNPs. The prepared AuNPs-FPTDF showed superior performance in the detection and imaging of small molecules in dual-polarity modes, with high detection sensitivity in the low pmol range, good repeatability, and low background noise compared to common organic MALDI matrixes. Its usage efficiently enhanced SALDI MS detection of various small molecules, such as amino acids and neurotransmitters, fatty acids, saccharides, alkaloids, and flavonoids, as compared with α-cyano-4-hydroxycinnamic acid, 9-aminoacridine, and the three precursor substrates of AuNPs-FPTDF. In addition, the blood glucose level in rats was successfully determined from a linearity concentration range of 0.5-9 mM, as well as other biomarkers in rat serum with SALDI MS. More importantly, the spatial distribution of metabolites from the intact flowers of the medicinal plant Catharanthus roseus was explored by using the AuNPs-FPTDF as an imprint SALDI MS substrate in dual-polarity modes. These results demonstrate wide applications and superior performances of the AuNPs-FPTDF as a multifunctional SALDI surface with enhanced detection sensitivity and imaging capabilities.