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1.
Niger J Clin Pract ; 25(9): 1484-1489, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-36149208

RESUMO

Background to Aim: To compare the effects of disinfectants on surface roughness of the conventional impression materials following chemical disinfection procedures. Materials and Methods: Equal numbers (65 for each impression material) of disc-shaped (15 × 3 mm) samples (Total n = 195) were fabricated from polyvinyl siloxane (Zhermack Elite), polyether (3M Impregum Penta Soft), and vinyl siloxane ether (Kettenbach Identium Lightbody) impression materials. Each impression material group was divided into five subgroups including one control group (n = 13). Impression material samples were immersed in CaviCide for 3 min, Zeta 7 solution for 10 min, and 5.25% sodium hypochlorite solution for 3 and 10 min. Surface roughness (Ra) was measured using a profilometer (Mitutoyo-SJ 410, Mitutoyo Corp.). The study data were analyzed statistically. Results: A statistically significant difference was found among impression materials and disinfectants in terms of surface roughness (P < 0.05). Polyvinyl siloxane material showed a lower Ra value compared to Polyether and VSE materials; while polyether material showed a significantly lower Ra value compared to VSE material. Ra values of the control group were significantly lower than the disinfectant group immersed in 5.25% NaOCl solution for 10 min. Conclusion: Among all impression materials, polyvinyl siloxane showed the least surface roughness following disinfection procedures. Impression disinfectants that are specially designed for disinfecting dental impressions resulted in less surface roughness in all impression materials. With this study, it was aimed to obtain a smooth and clear model for the production of correct and compatible prostheses in the laboratory while at the same time purifying the impressions from microorganisms.


Assuntos
Desinfetantes , Materiais para Moldagem Odontológica , Desinfecção/métodos , Éteres/química , Humanos , Teste de Materiais , Polivinil/química , Siloxanas/química , Hipoclorito de Sódio/química , Propriedades de Superfície
2.
Anal Chim Acta ; 1229: 340174, 2022 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-36156213

RESUMO

Worldwide, the valorization of biogas, landfill gas and biomethane is gaining momentum as circular economies and energy transitions are triggered. Nevertheless, to sustainably integrate those gases into today's energy mix, their quality must be controlled regarding their major, minor and trace constituents to preserve the integrity of infrastructures wherein they are burned, transported or stored. Field gas sampling is the first and most critical step in the analytical chain to characterize the composition of such gases. A large array of gas sampling techniques is available, yet choosing the most suitable technique is complex, especially when targeting trace compounds (

Assuntos
Biocombustíveis , Compostos Orgânicos Voláteis , Gases/química , Silanos , Siloxanas , Compostos de Enxofre
3.
Chem Commun (Camb) ; 58(76): 10596-10618, 2022 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-36069250

RESUMO

Multiple reviews have been written concerning conjugated macromonomers and polymers both as general descriptions and for specific applications. In most examples, conjugation occurs via electronic communication via continuous overlap of π orbitals, most often on carbon. These systems can be considered to offer traditional forms of conjugation. In this review, we attempt to survey macromonomers and polymers that offer conjugation involving novel forms of carbon and/or other elements but with conjugation achieved via other bonding formats, including many where the mechanism(s) whereby such behavior is observed remain unresolved. In particular, this review emphasizes silsesquioxane containing polymeric materials that offer properties found typically in conjugated polymers. However, conjugation in these polymers appears to occur via saturated siloxane bonds within monomeric units that make up a variety of polymer systems. Multiple photophysical analytical methods are used as a means to demonstrate conjugation in systems where traditional conjugation is not apparent.


Assuntos
Polímeros , Siloxanas , Carbono , Fenômenos Químicos , Polímeros/química
4.
BMC Oral Health ; 22(1): 379, 2022 09 05.
Artigo em Inglês | MEDLINE | ID: mdl-36064393

RESUMO

BACKGROUND: This study aimed to compare the dimensional accuracy, hydrophilicity and detail reproduction of the hybrid vinylsiloxnether with polyether and polyvinylsiloxane parent elastomers using modified digital techniques and software. This was done in an attempt to aid in solving the conflict between the different studies published by competitive manufacturers using different common manual approaches. METHODS: A polyether, polyvinylsiloxanes and vinyl polyether silicone hybrid elastomeric impression materials were used in the study. Dimensional accuracy was evaluated through taking impressions of a metallic mold with four posts representing a partially edentulous maxillary arch, that were then poured with stone. Accuracy was calculated from the mean of measurements taken between fixed points on the casts using digital single-lens reflex camera to produce high-resolution digital pictures for all the casts with magnification up to 35×. Hydrophilicity was assessed by contact angle measurements using AutoCAD software. The detail reproduction was measured under dry conditions according to ANSI/ADA Standard No. 19 and under wet conditions as per ISO 4823. A metallic mold was used with three V shaped grooves of 20, 50, and 75 µm width. Specimens were prepared and examination was made immediately after setting using digital images at a magnification of 16×. RESULTS: The hybrid impression (0.035 mm) material showed significantly higher dimensional accuracy compared to the polyether (0.051 mm) but was not as accurate as the polyvinyl siloxane impression material (0.024 mm). The contact angles of the hybrid material before and after setting was significantly lower than the parent materials. With regard to the detail reproduction, the three tested materials were able precisely to reproduce the three grooves of the mold under dry conditions. Whereas, under wet conditions, the hybrid material showed higher prevalence of well-defined reproduction of details same as polyether but higher than polyvinylsiloxane that showed prevalence of details with loss of sharpness and continuity. CONCLUSIONS: The digital technique used could be a more reliable and an easier method for assessment of impression materials properties. The hybridization of polyvinyl siloxane and polyether yielded a promising material that combines the good merits of both materials and overcomes some of their drawbacks.


Assuntos
Materiais para Moldagem Odontológica , Siloxanas , Técnica de Moldagem Odontológica , Elastômeros , Humanos , Teste de Materiais , Polivinil , Silicones , Propriedades de Superfície
5.
Artigo em Inglês | MEDLINE | ID: mdl-36078606

RESUMO

The growing global energy demand requires the continuous development and optimization of the production of alternative energy sources. According to the circular economy approach, waste conversion into biogas and biomethane represent an interesting energy source. The input into the distribution network and energy conversion systems of biomethane requires quality monitoring and the use of cleaning up systems. Therefore, there is a need to constantly invest in the development of sampling and analysis systems that save time, costs, and materials. The purpose of this study was to use activated porous carbon fiber (APCF), an extremely versatile material for sampling and analysis by thermal desorption, to show the advantages it has over the adsorbents traditionally used for siloxane monitoring. Siloxanes are among the contaminating compounds that are mainly present in biogas and biomethane, and if not removed sufficiently, they endanger the quality and use of the gas. These are highly harmful compounds since during combustion, they produce quartz particles that are abrasive to the surfaces of the materials involved in the energy production process. In addition, siloxanes directly hinder the energy properties of biomethane during combustion, due to their radical scavenger properties. In this work, the efficiency of APCF tube was evaluated by comparing it with common multilayer tube thought sampling and analyzing siloxanes in lab scale and in real scale (biogas plant). Thermal desorption analysis coupled with GC-MS for the determination of siloxanes showed that the use of APCF allows to obtain better performance. This allows to deduce that APCF is an innovative material for the establishment of a better sampling and analysis method than the current ones, enabling better results to be achieved in the process of monitoring fuel quality in biomethane production and storage facilities.


Assuntos
Biocombustíveis , Siloxanas , Biocombustíveis/análise , Fibra de Carbono , Carvão Vegetal , Porosidade , Siloxanas/análise
6.
Biomater Adv ; 137: 212848, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35929243

RESUMO

Hyperbranched polymers hold great promise in nanomedicine for their controlled chemical structures, sizes, multiple terminal groups and enhanced stability than linear amphiphilic polymer assemblies. However, the rational design of hyperbranched polymer-based nanomedicine with low toxic materials, selective cellular uptake, controlled drug release, as well as real-time drug release tracking remains challenging. In this work, a hyperbranched multifunctional prodrug HBPSi-SS-HCPT is constructed basing on the nonconventional aggregation-induced emission (AIE) featured hyperbranched polysiloxanes (HBPSi). The HBPSi is a biocompatible AIE macromolecule devoid of conjugates, showing a high quantum yield of 17.88% and low cytotoxicity. By covalently grafting the anticancer drug, 10-hydroxycamptothecin (HCPT), to the HBPSi through 3,3'-dithiodipropionic acid, HBPSi-SS-HCPT is obtained. The HBPSis demonstrate obvious AIE features and it turned to aggregation-caused quenching (ACQ) after grafting HCPT owing to the FRET behavior between HBPSi and HCPT in HBPSi-SS-HCPT. In addition to on-demand HCPT release in response to changes in environmental pH and glutathione, a series of in vitro and in vivo studies revealed that HBPSi-SS-HCPT exhibits enhanced accumulation in tumor tissues through the enhanced permeation and retention (EPR) effect and preferential cancer cell uptake by charge reversal, thus resulting in apoptotic cell death subsequently. This newly developed multifunctional HBPSi-SS-HCPT prodrug provides a biocompatible strategy for controlled drug delivery, preferential cancer cell uptake, on-demand drug release and enhanced antitumor efficacy.


Assuntos
Pró-Fármacos , Sistemas de Liberação de Medicamentos , Liberação Controlada de Fármacos , Polímeros/química , Pró-Fármacos/farmacologia , Siloxanas
7.
ACS Appl Mater Interfaces ; 14(32): 37229-37247, 2022 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-35939765

RESUMO

Combining amphiphilic fouling-release (FR) coatings with the surface-active nature of amphiphilic additives can improve the antifouling/fouling-release (AF/FR) properties needed to offer broad-spectrum resistance to marine biofoulants. This work is focused on further tuning the amphiphilic character of a previously developed amphiphilic siloxane-polyurethane (SiPU) coating by varying the amount of PDMS and PEG in the base system. Furthermore, surface-modifying amphiphilic additives (SMAAs) were incorporated into these amphiphilic FR SiPU coatings in varying amounts. ATR-FTIR, contact angle and surface energy measurements, and AFM were performed to assess changes in surface composition, wettability, and morphology. AF/FR properties were evaluated using laboratory biological assays involving Cellulophaga lytica, Navicula incerta, Ulva linza, Amphibalanus amphitrite, and Geukensia demissa. The surfaces of these coatings varied significantly upon changes in PDMS and PEG content in the coating matrix, as well as with changes in SMAA incorporation. AF/FR properties were also significantly changed, with formulations containing the highest amounts of SMAA showing very high removal properties compared to other experimental formulations, in some cases better than that of commercial standard FR coatings.


Assuntos
Incrustação Biológica , Siloxanas , Incrustação Biológica/prevenção & controle , Polímeros , Poliuretanos , Propriedades de Superfície
8.
Int J Mol Sci ; 23(16)2022 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-36012340

RESUMO

The structure, thermodynamic parameters, and the character of thermal motion in octamethylcyclotetrasiloxane (D4) were investigated using the combination of experimental (single-crystal X-ray diffraction, thermochemistry) and theoretical (density functional theory calculations, ab initio molecular dynamics and metadynamics) methods. Single crystals of D4 were grown in a glass capillary in situ and the structures of high- (238-270 K) and low-temperature (100-230 K) phases were studied in detail. In the temperature interval 230-238 K, a phase transition with rather low enthalpy (-1.04(7) kcal/mol) was detected. It was found that phase transition is accompanied by change of conformation of cyclosiloxane moiety from boat-saddle (cradle) to chair. According to PBE0/6-311G(d,p) calculation of isolated D4, such conformation changes are characterized by a low barrier (0.07 kcal/mol). The character of molecular thermal motion and the path of phase transition were established with combination of periodic DFT calculations, including molecular dynamics and metadynamics. The effect of crystal field led to an increase in the calculated phase transition barrier (4.27 kcal/mol from low- to high-temperature phase and 3.20 kcal/mol in opposite direction).


Assuntos
Raios X , Conformação Molecular , Transição de Fase , Siloxanas , Termodinâmica
9.
Langmuir ; 38(32): 9844-9852, 2022 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-35926220

RESUMO

The integration of biological components and artificial devices requires a bio-machine interface that can simultaneously trigger and monitor the activities in biosystems. Herein, we use an organically modified silicate (ormosil) composite coating containing a light-responsive nanocapsule and a fluorescent bioprobe for reactive oxygen species (ROS) to decorate ultrathin optical fibers, namely, ormosil-decorated ultrathin fibers (OD-UFs), and demonstrate that these OD-UFs can optically trigger and monitor the intracellular metabolism activities in living cells. The sizes and shapes of UF tips were finely controlled to match the dimension and mechanical properties of living cells. The increased elasticity of the ormosil coating of OD-UFs reduces possible mechanical damage during the cell membrane penetration. The light-responsive nanocapsule was physically absorbed on the surface of the ormosil coating and could release a stimulant to trigger the metabolism activities in cells upon the guided laser through OD-UFs. The fluorescent bioprobe was covalently linked with the ormosil matrix for monitoring the intracellular ROS generation, which was verified by the in vitro experiments on the microdroplets of a hydrogen peroxide solution. Finally, we found that the living cells could maintain most of their viability after being inserted with OD-UFs, and the intracellular metabolism activities were successfully triggered and monitored at the single-cell level. The OD-UF provides a new platform for the investigation of intracellular behaviors for drug stimulations and represents a new proof of concept for a bio-machine interface based on the optical and chemical activities of organic functional molecules.


Assuntos
Nanocápsulas , Espécies Reativas de Oxigênio , Silicatos/química , Siloxanas/química
10.
Sci Total Environ ; 845: 157379, 2022 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-35843336

RESUMO

Methylsiloxanes (MSs) are widely used as solvents or emollients in various personal care products (PCPs) and may pose a health risk. In this study, we assessed external and internal exposure to MSs among students at two universities in southwestern China. Samples of air, dust, and PCPs were collected to evaluate indoor non-dietary exposure to MSs via multiple pathways among the students. Indoor MS levels were approximately 1-3 orders of magnitude higher in the dormitories of female students than in either classrooms or the dormitories of male students. Lipstick contained the highest MS levels. Cyclic MS (CMS: D4-D6) levels were 1 order of magnitude higher in female students than in male students. Among the three CMSs, D5 levels were highest in the plasma of all students (1.3-15 ng/mL). In dormitories, dermal contact with PCPs was the major route of exposure to CMSs for all students. Among linear MSs (LMSs: L5-L16), dermal PCP absorption and dust ingestion were the predominant exposure routes for male and female students, respectively. Although the overall risk of exposure to D4 and D5 was below the chronic reference dose for all exposure routes and all students, the total daily doses of exposure to D4 and D5 via dermal PCP absorption approached the chronic reference dose in four female students. Therefore, the effects of MSs on female students should be further investigated in future studies.


Assuntos
Poluição do Ar em Ambientes Fechados , Cosméticos , Poluição do Ar em Ambientes Fechados/análise , China , Poeira , Exposição Ambiental/análise , Monitoramento Ambiental , Feminino , Humanos , Masculino , Medição de Risco , Siloxanas/análise , Estudantes
11.
Environ Toxicol Chem ; 41(10): 2466-2478, 2022 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-35860956

RESUMO

Herring gulls (Larus argentatus) are opportunistic feeders, resulting in contaminant exposure depending on area and habitat. We compared contaminant concentrations and dietary markers between two herring gull breeding colonies with different distances to extensive human activity and presumed contaminant exposure from the local marine diet. Furthermore, we investigated the integrity of DNA in white blood cells and sensitivity to oxidative stress. We analyzed blood from 15 herring gulls from each colony-the urban Oslofjord near the Norwegian capital Oslo in the temperate region and the remote Hornøya island in northern Norway, on the Barents Sea coast. Based on d13 C and d34 S, the dietary sources of urban gulls differed, with some individuals having a marine and others a more terrestrial dietary signal. All remote gulls had a marine dietary signal and higher relative trophic level than the urban marine feeding gulls. Concentrations (mean ± standard deviation [SD]) of most persistent organic pollutants, such as polychlorinated biphenyl ethers (PCBs) and perfluorooctane sulfonic acid (PFOS), were higher in urban marine (PCB153 17 ± 17 ng/g wet weight, PFOS 25 ± 21 ng/g wet wt) than urban terrestrial feeders (PCB153 3.7 ± 2.4 ng/g wet wt, PFOS 6.7 ± 10 ng/g wet wt). Despite feeding at a higher trophic level (d15 N), the remote gulls (PCB153 17 ± 1221 ng/g wet wt, PFOS 19 ± 1421 ng/g wet wt) were similar to the urban marine feeders. Cyclic volatile methyl siloxanes were detected in only a few gulls, except for decamethylcyclopentasiloxane in the urban colony, which was found in 12 of 13 gulls. Only hexachlorobenzene was present in higher concentrations in the remote (2.6 ± 0.42 ng/g wet wt) compared with the urban colony (0.34 ± 0.33 ng/g wet wt). Baseline and induced DNA damage (doublestreak breaks) was higher in urban than in remote gulls for both terrestrial and marine feeders. Environ Toxicol Chem 2022;41:2466-2478. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.


Assuntos
Charadriiformes , Bifenilos Policlorados , Ácidos Alcanossulfônicos , Animais , Cruzamento , Dano ao DNA , Monitoramento Ambiental/métodos , Fluorcarbonetos , Hexaclorobenzeno , Humanos , Poluentes Orgânicos Persistentes , Bifenilos Policlorados/análise , Siloxanas
12.
Biofouling ; 38(4): 384-400, 2022 04.
Artigo em Inglês | MEDLINE | ID: mdl-35655420

RESUMO

Grooming may be an effective technique to control marine biofouling without damaging the coating or discharging active ingredients into the environment. This study assessed the grooming performance of three experimental biocide-free siloxane polyurethane (SiPU) fouling-release coatings. Coatings were statically immersed in Port Canaveral, Florida, and groomed every two weeks for five months using three different brush types. The ungroomed panels became heavily fouled with biofilm, tubeworms, barnacles, and bryozoans. Two of the brushes were able to control the fouling with a coverage of <5%. The commercial silicone elastomer coating was damaged from grooming procedures, while the SiPU coatings were not. Laboratory biological assays were carried out and mirrored the grooming results. Through surface characterization techniques, it was concluded that the coatings were unaffected by the grooming procedures. This study shows that marine fouling on durable SiPU fouling-release coatings can be controlled via grooming without damage or changing the surface properties.


Assuntos
Incrustação Biológica , Thoracica , Animais , Biofilmes , Incrustação Biológica/prevenção & controle , Asseio Animal , Poliuretanos , Navios , Siloxanas , Propriedades de Superfície
13.
ACS Appl Mater Interfaces ; 14(24): 28258-28269, 2022 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-35674729

RESUMO

Flexible micro-light-emitting diodes (f-µLEDs) have been regarded as an attractive light source for the next-generation human-machine interfaces, thanks to their noticeable optoelectronic performances. However, when it comes to their practical utilizations fulfilling industrial standards, there have been unsolved reliability and durability issues of the f-µLEDs, despite previous developments in the high-performance f-µLEDs for various applications. Herein, highly robust flexible µLEDs (f-HµLEDs) with 20 × 20 arrays, which are realized by a siloxane-based organic-inorganic hybrid material (SHM), are reported. The f-HµLEDs are created by combining the f-µLED fabrication process with SHM synthesis procedures (i.e., sol-gel reaction and successive photocuring). The outstanding mechanical, thermal, and environmental stabilities of our f-HµLEDs are confirmed by a host of experimental and theoretical examinations, including a bending fatigue test (105 bending/unbending cycles), a lifetime accelerated stress test (85 °C and 85% relative humidity), and finite element method simulations. Eventually, to demonstrate the potential of our f-HµLEDs for practical applications of flexible displays and/or biomedical devices, their white light emission due to quantum dot-based color conversion of blue light emitted by GaN-based f-HµLEDs is demonstrated, and the biocompatibility of our f-HµLEDs is confirmed via cytotoxicity and cell proliferation tests with muscle, bone, and neuron cell lines. As far as we can tell, this work is the first demonstration of the flexible µLED encapsulation platform based on the SHM, which proved its mechanical, thermal, and environmental stabilities and biocompatibility, enabling us to envisage biomedical and/or flexible display applications using our f-HµLEDs.


Assuntos
Iluminação , Pontos Quânticos , Humanos , Luz , Reprodutibilidade dos Testes , Siloxanas
14.
J Am Chem Soc ; 144(27): 12280-12289, 2022 07 13.
Artigo em Inglês | MEDLINE | ID: mdl-35758403

RESUMO

To develop siloxane-containing vitrimers with fast dynamic characteristics, different mechanistic pathways have been investigated using a range of catalysts. In particular, one siloxane exchange pathway has been found to show a fast dynamic behavior in a useful temperature range (180-220 °C) for its application in vitrimers. The mechanism is found to involve 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) as an organic catalyst in the presence of hydroxyl groups. Using this new mechanistic approach, vitrimers with ultrafast stress-relaxation characteristics (relaxation times below 10 s) have been prepared with a readily available epoxy resin and siloxane-amine hardener. Subsequently, the low viscosity siloxane-containing vitrimer resin enabled the preparation of glass fiber-reinforced vitrimer composites using an industrially relevant vacuum-assisted resin infusion technique. The resulting composite was successfully thermoformed into a new shape, which makes it possible to envision a second life for such highly engineered materials.


Assuntos
Siloxanas , Viscosidade
15.
J Chromatogr A ; 1674: 463138, 2022 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-35617910

RESUMO

The present work systematically investigates the chemical microheterogeneity as part of the optimization of a single-step surface bonding chemistry of 3-mercaptopropylsilatrane (MPS) on mesoporous silica gel in comparison to the state-of-the-art silane chemistry with 3-mercaptopropyltrimethoxysilane (MPTMS). MPS functionalization turns out to be a favourable chemistry for the further use in thiol-ene click reactions such as the immobilization of chiral selectors, herein tert-butylcarbamoylquinine (tBuCQN), for the synthesis of chiral stationary phases (CSPs). MPS has higher reactivity than MPTMS and prefers the formation of trifunctional siloxane bondings unlike MPTMS which favours difunctional siloxane bonds to silica, as investigated by solid-state cross-polarization/magic angle spinning (CP/MAS) NMR (29Si and 13C nuclei). Reaction conditions (ternary mixtures of methanol, water and toluene; with and without acid; prewetting of silica; HCl pretreatment of silica) were evaluated with the aim to find conditions which promote the formation of a horizontal siloxane polymer layer on top of the silica surface. Silanization reaction times could be reduced to 2 h. The 29Si NMR signal corresponding to trifunctional siloxane bonding could be increased to 60% with no T1 signal that refers to monofunctional siloxane bonding in spite of water in the ternary reaction mixture. Furthermore, no significant disulfide bridges were formed in this approach, leading to high selector loadings. The thiol and selector coverage reached up to 4.6 and 1.4 µmol/m2, respectively. With the preferred CSP, the enantioselectivity could be increased for a chiral probe (FMOC-Phe) and the mass transfer resistance (C-term) bisected compared to the corresponding CSP prepared from benchmark MPTMS-modified silica (2.54 vs 5.72 ms). It is demonstrated that the fine-tuning of the microstructure on the silica surface can have a significant influence on enantioselectivity and mass transfer kinetics of the resultant CSPs.


Assuntos
Dióxido de Silício , Siloxanas , Compostos Bicíclicos Heterocíclicos com Pontes , Cromatografia Líquida de Alta Pressão/métodos , Cromatografia Líquida , Compostos de Organossilício , Fenilalanina/análogos & derivados , Dióxido de Silício/química , Siloxanas/química , Estereoisomerismo , Compostos de Sulfidrila/química , Água
16.
Macromol Rapid Commun ; 43(17): e2200149, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-35592913

RESUMO

The molecular weight is a key factor affecting the properties of conjugated polymers. To determine the critical molecular weights of conjugated polymers modified with siloxane side chains, poly-diketo-pyrrolopyrrole-selenophene (PTDPPSe-5Si) samples with molecular weights ranging from 20 to 350 kDa are synthesized. The critical molecular weight of the polymer is determined in the range of 60-100 kDa by testing the viscosity of the solution. When the molecular weight of the 27-60 kDa polymers is below the critical molecular weight, they exhibit a high crystallinity and low ductility. When the molecular weight of the 100 kDa polymer reaches the critical molecular weight, the crystallinity decreases, and the ductility increases. As the molecular weight increases, the polymer film also gradually changes from brittle to ductile. Furthermore, when the molecular weight of the 315 kDa polymer is much higher than the critical molecular weight, the film exhibits a significant ductility, which results in the polymer films showing no pronounced cracks after high-percentage stretching. Additionally, due to the oriented alignment of the molecular chains caused by stretching, the carrier mobility in the parallel direction becomes 2.14-fold of the initial film.


Assuntos
Polímeros , Siloxanas , Peso Molecular , Polímeros/química
17.
Toxicol In Vitro ; 82: 105379, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35561954

RESUMO

Literature shows contradictory information regarding the effect of freezing the excise skin ex vivo on the diffusion of substances into the skin. Few studies indicate that storing the human or animal skin in a frozen state decreases the barrier properties after thawing. Therefore, to understand the properties of frozen skin, we evaluated the effect of storage of ex vivo human skin (2 weeks at -20 °C) on the penetration of stratum corneum and permeation into deeper skin layers (epidermis, and dermis) as well as to the receptor fluid by octamethylcyclotetrasiloxane (D4) a representative test compound of cyclic siloxanes. The main research were preceded by checking the integrity of nonfrozen ex vivo human skin in comparison to the frozen-thawed one by using the Electrical Resistance technique (ER) and the fluorescence microscopy. Samples collected in the skin absorption experiment were analyzed by gas chromatography equipped with a flame ionization detector (GC-FID). The results of this study demonstrated that freezing of excised ex vivo human skin at -20 °C for up to 14 days does not alter the permeability of D4 in a statistically significant manner. Thus, our results confirmed the validity of using skin storage conditions for testing the penetration and permeation of xenobiotics recommended by the OECD, EMA, and WHO guidelines.


Assuntos
Siloxanas , Pele , Animais , Bioacumulação , Congelamento , Humanos , Permeabilidade , Siloxanas/metabolismo , Pele/metabolismo , Absorção Cutânea
18.
Environ Sci Process Impacts ; 24(9): 1343-1359, 2022 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-35608286

RESUMO

The adsorption of thallium (Tl) onto phyllosilicate minerals plays a critical role in the retention of Tl in soils and sediments and the potential transfer of Tl into plants and groundwater. Especially micaceous minerals are thought to strongly bind monovalent Tl(I), in analogy to their strong binding of Cs. To advance the understanding of Tl(I) adsorption onto phyllosilicate minerals, we studied the adsorption of Tl(I) onto Na- and K-saturated illite and Na-saturated smectite, two muscovites, two vermiculites and a naturally Tl-enriched soil clay mineral fraction. Macroscopic adsorption isotherms were combined with the characterization of the adsorbed Tl by X-ray absorption spectroscopy (XAS). In combination, the results suggest that the adsorption of Tl(I) onto phyllosilicate minerals can be interpreted in terms of three major uptake paths: (i) highest-affinity inner-sphere adsorption of dehydrated Tl+ on a very low number of adsorption sites at the wedge of frayed particle edges of illite and around collapsed zones in vermiculite interlayers through complexation between two siloxane cavities, (ii) intermediate-affinity inner-sphere adsorption of partially dehydrated Tl+ on the planar surfaces of illite and muscovite through complexation onto siloxane cavities, (iii) low-affinity adsorption of hydrated Tl+, especially in the hydrated interlayers of smectite and expanded vermiculite. At the frayed edges of illite particles and in the vermiculite interlayer, Tl uptake can lead to the formation of new wedge sites that enable further adsorption of dehydrated Tl+. On the soil clay fraction, a shift in Tl(I) uptake from frayed edge sites (on illite) to planar sites (on illite and muscovite) was observed with increasing Tl(I) loading. The results from this study show that the adsorption of Tl(I) onto phyllosilicate minerals follows the same trends as reported for Cs and Rb and thus suggests that concepts to describe the retention of (radio)cesium by different types of phyllosilicate minerals in soils, sediments and rocks are also applicable to Tl(I).


Assuntos
Siloxanas , Tálio , Adsorção , Silicatos de Alumínio , Césio/química , Argila , Minerais/química , Silicatos , Solo/química , Tálio/análise
19.
J Biomed Mater Res A ; 110(8): 1512-1523, 2022 08.
Artigo em Inglês | MEDLINE | ID: mdl-35366061

RESUMO

Contact lenses are one of the most successful biomaterials in history with a global market estimated to be worth over $17 billion in 2025. Silicone hydrogel contact lenses dominate the market and are complex biphasic biomaterials with several critical material properties needed for clinical use. Careful consideration of composition and chemistry is needed to identify formulations of lenses meeting all commercial standards with the potential for improved manufacturability, cost, and/or next generation use. Four silicone macromers were investigated in this work with varying symmetry of siloxane units and macromer structure, number of siloxane groups, branching, length, and concentration. Novel silicone hydrogel lenses were produced and evaluated for optical transmittance, elastic modulus, oxygen transmissibility, water content, and surface wettability. Several lenses met commercial standards and demonstrated an increase in oxygen permeability (Dk) and inverse relationship with elastic modulus and siloxane concentration, respectively. A hydrophobic/hydrophilic ratio below 1.4 was needed for a co-continuous water phase. Substitution of methoxypropyl groups for butyl groups increased hydrophobic microdomains leading to decreased optical quality and mechanical properties. Generally, fluorine-containing silicone macromers allowed for a wider range of successful compositions, and above a certain hydrophilic composition, the presence of trifluoropropyl groups resulted in improved solubility and optically clear lenses. Data also showed asymmetric siloxane macromers have potential to meet critical lens properties at lower overall siloxane content. New lens materials with wider composition ranges meeting all clinical lens properties is a significant challenge and may significantly expand the field.


Assuntos
Lentes de Contato , Silicones , Materiais Biocompatíveis/análise , Hidrogel de Polietilenoglicol-Dimetacrilato , Hidrogéis/química , Oxigênio , Silicones/química , Siloxanas , Água
20.
Molecules ; 27(7)2022 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-35408530

RESUMO

Butvar B-98 and PDMS-OH both have a demonstrable ability as consolidants for archaeological wood. This makes them both potential treatment options for the Oseberg collection, which is one of the most important archaeological finds from the Viking era. Both Butvar B-98 and PDMS-OH are soluble in organic solvents, offering a useful alternative to aqueous-based consolidants. Extensive characterisation studies were carried out on both of these polymers, with the use of analytical ultracentrifugation and viscometry, for the benefit of conservators wanting to know more about the physical properties of these materials. Short column sedimentation equilibrium analysis using SEDFIT-MSTAR revealed a weight-average molar mass (weight-average molecular weight) Mw of (54.0 ± 1.5) kDa (kg · mol-1) for Butvar B-98, while four samples of PDMS-OH siloxanes (each with a different molar mass) had an Mw of (52.5 ± 3.0) kDa, (38.8 ± 1.5) kDa, (6.2 ± 0.7) kDa and (1.6 ± 0.1) kDa. Sedimentation velocity confirmed that all polymers were heterogeneous, with a wide range of molar masses. All molecular species showed considerable conformational asymmetry from measurements of intrinsic viscosity, which would facilitate networking interactions as consolidants. It is anticipated that the accumulated data on these two consolidants will enable conservators to make a more informed decision when it comes to choosing which treatment to administer to archaeological artefacts.


Assuntos
Hidrodinâmica , Madeira , Peso Molecular , Polímeros , Resinas Sintéticas , Siloxanas , Ultracentrifugação
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