Solvent Research Articles

Hydrosilane‐Functionalized [2.2]Paracyclophane for Plasma‐Etch‐Resistant and Post‐Modifiable Poly(Para‐Xylylene)

AbstractPoly(para‐xylylene)s (PPXs), or so‐called parylenes, have become a well‐established polymer class in the conformal coating industry. Due to their transparent nature, low electrical conductivity, and high biocompatibility, they are ideal candidates for coating medical devices and other delicate electronics. However, the crosslinking of PPXs to enhance their durability is still challenging today. Expensive setups need to be used to obtain crosslinked PPXs. Furthermore, the possibility of functionalization post‐polymerization is limited. In this work, we present the synthesis of a hydrosilane functionalized [2.2]paracyclophane, which is used to obtain the corresponding hydrosilane functionalized poly(para‐xylylene) (PPX‐SiH). Through the formation of siloxane bonds during the low‐pressure chemical vapor deposition (LP‐CVD), which increases internal bonding, PPX‐SiH is obtained as a flexible and durable polymer film. The siloxane formation during the LP‐CVD is investigated through X‐ray photoelectron spectroscopy (XPS), nuclear magnetic resonance spectroscopy (NMR), and Fourier‐transform infrared spectroscopy (FTIR). Additionally, mechanistic insights into the formation of siloxane bonds are given through quantum chemical calculation. The Si‐H bonds in the polymer allow for oxidation to form bridging siloxane moieties which enhances stretchability while also increasing the resistance to organic solvents. Through the passivation of the surface during oxygen plasma treatment, PPX‐SiH becomes practically plasma‐etch‐resistant.

Organic Solvent Nanofiltration Membrane with In Situ Constructed Covalent Organic Frameworks as Separation Layer

Organic solvent nanofiltration (OSN) technology is advantageous for separating mixtures of organic solutions owing to its low energy consumption and environmental friendliness. Covalent organic frameworks (COFs) are good candidates for enhancing the efficiency of solvent transport and ensuring precise molecular sieving of OSN membranes. In this study, p-phenylenediamine (Pa) and 1,3,5-trimethoxybenzene (Tp) are used to construct, in situ, a TpPa COF skin layer via interfacial polymerization (IP) on a polyimide substrate surface. After subsequent crosslinking and activation steps, a kind of TpPa/polyimide (PI) OSN membrane is obtained. Under optimized fabrications, this OSN membrane exhibits an ethanol permeance of 58.0 LMH/MPa, a fast green FCF (FGF) rejection of 96.2%, as well as a pure n-hexane permeance of 102.0 LMH/MPa. Furthermore, the TpPa/PI OSN membrane exhibits good solvent resistance, which makes it suitable for the separation, purification, and concentration of organic solvents.

Exploring the Self-Assembly of a Fully Protected l-Dopa from Different Organic Solvents and the Relationship Between Gel and Crystal Structures

Exploring the Self-Assembly of a Fully Protected <scp>l</scp>-Dopa from Different Organic Solvents and the Relationship Between Gel and Crystal Structures

TECHNOLOGIES FOR DEPOSIT VOLUME ASSESSING IN AN OIL PIPELINE

Deposits of various compositions in the pipelines of oil and gas companies significantly worsen the conditions for transporting fluids between field facilities, their presence increases energy consumption and the possibility of accidents with environmental consequences. In sections where bullets are not using, the most effective way to remove asphalt-resin-paraffin deposits (ARPD) is to use compounds of organic solvents selected in laboratory conditions. One of the factors of their successful application is a preliminary assessment of the deposit volume in a complicated pipeline. The article examines a horizontal section of an oil pipeline with ARPD, closed at both ends, filled with oil with a residual content of associated petroleum gas after the first stage separator. Pressure reduction and the appearance of a certain volume of gas in a free state is initiated in the oil pipeline. The deposit volume is calculated on the basis of a mathematical formula during the injection of an organic solvent of the first portion with an information component.

Efficient separation of methyl ethyl ketone and water azeotrope using hydrophobic amino acid ester ionic liquids

BackgroundMethyl ethyl ketone (MEK), an essential organic solvent, is commonly produced via the n-butene method, where water emerges as the principal impurity. The conventional distillation processes, which are necessitated by the azeotropic behavior between MEK and water, result in a substantial expenditure of energy. As a result, liquid-liquid extraction represents a promising alternative for energy-efficient separation. MethodsIn this work, three hydrophobic amino acid ester ionic liquids L-phenylalanine ethyl ester bis(trifluoromethylsulfonyl) imide ([Phe][NTf2]), L-leucine ethyl ester bis(trifluoromethylsulfonyl) imide ([Leu][NTf2]) and L-valine ethyl ester bis(trifluoromethylsulfonyl) imide ([Val][NTf2]) were utilized as extractants for separation of the binary azeotrope methyl ethyl ketone and water. The effects of extraction time, extraction temperature, mass ratio of MEK-water mixture to ionic liquid and initial concentration of MEK on extraction efficiency were investigated. Significant findingsThe results demonstrate that the ionic liquid [Phe][NTf2] exhibits superior extraction ability for the separation of the azeotrope methyl ethyl ketone and water. The maximum extraction yield of 99.86 % was achieved with the optimum extraction conditions of extraction time, 10 min, extraction temperature, 293.15 K, mass ratio of mixture to ionic liquid, 1:1 and initial concentration of MEK, 20 %. In addition, the relationship between the structure of ionic liquids and their extraction performance was revealed by quantum chemical calculations of ionic liquids with MEK and water. These ionic liquids were positioned as promising environmentally friendly alternatives to traditional organic solvents for the recovery of MEK from aqueous solutions, providing valuable insights for industrial applications.

Carbon-Doped TiO2 Nanofiltration Membranes Prepared by Interfacial Reaction of Glycerol with TiCl4 Vapor

In the pursuit of developing advanced nanofiltration membranes with high permeation flux for organic solvents, a TiO2 nanofilm was synthesized via a vapor–liquid interfacial reaction on a flat-sheet α-Al2O3 ceramic support. This process involves the reaction of glycerol, an organic precursor with a structure featuring 1,2-diol and 1,3-diol groups, with TiCl4 vapor to form organometallic hybrid films. Subsequent calcination in air at 250 °C transforms these hybrid films into carbon-doped titanium oxide nanofilms. The unique structure of glycerol plays a crucial role in determining the properties of the resulting nanopores, which exhibit high solvent permeance and effective solute rejection. The synthesized carbon-doped TiO2 nanofiltration membranes demonstrated impressive performance, achieving a pure methanol permeability as high as 90.9 L·m−2·h −1·bar−1. Moreover, these membranes exhibited a rejection rate of 93.2% for Congo Red in a methanol solution, underscoring their efficacy in separating solutes from solvents. The rigidity of the nanopores within these nanofilms, when supported on ceramic materials, confers high chemical stability even in the presence of polar solvents. This robustness makes the carbon-doped TiO2 nanofilms suitable for applications in the purification and recovery of organic solvents.

One-Pot, Solvent Free Synthesis of 2,5-Furandicarboxylic Acid from Deep Eutectic Mixtures of Sugars as Mediated by Bifunctional Catalyst.

Currently one-pot conversion of sugars to 2,5-furandicarboxylic acid (FDCA) is of significant interest due to the attainability of sugars as a feedstock and the enormous potential of FDCA as a bioplastic monomer. However, it remains challenging to construct efficient catalysts for this process. In this study, Co3O4 species were anchored to a sulfonated covalent organic framework thus affording a bifunctional catalyst (Co3O4@COF-SO3H). The sulfonic acid sites dehydrate sugars to 5-hydroxymethylfurfural (HMF), which is next oxidized to FDCA as catalyzed by the Co3O4 species. Such a process was applied in the conversion of various binary and ternary deep eutectic mixtures involving choline chloride and sugars without additional solvent. The maximum FDCA yield of 84 % was obtained using glucose-fructose eutectic mixture as the substrates. Moreover, the catalyst was recyclable and stable under the applied reaction conditions. Our process eliminates the employment of organic solvents and expensive noble metal catalysts, resulting in green and economic biomass conversions.

Bioavailability and phytotoxicity of clomazone to corn depend on soil characteristics and can be estimated by in situ pore water

AbstractBACKGROUNDThe injury caused by residual herbicides in soils to subsequent crops has been frequently reported and is largely related to soil physicochemical properties. Elucidating the interactions between herbicide toxicity and soil properties could help assess its phytotoxicity based on local soil characteristics. Here, the influence of soil properties on the accumulation and toxicity of clomazone as a model compound to corn was explored to obtain a universal indicator for estimating the toxicity of herbicides against crops.RESULTSThe phytotoxicity of clomazone to corn differed in the five tested soils with the median inhibitory concentration (IC50) values, according to the added concentration, fluctuating between 2.80 and 26.97 mg/kg. The uptake of clomazone by corn was primarily affected by its sorption onto soils and showed a positive correlation with the concentration of clomazone in in situ pore water (CIPW) (R2 ≥ 0.775, P &lt; 0.001). In contrast to results derived from traditional soil clomazone concentrations (Csoil) determined through organic solvent extraction, consistent IC50 values (1.344–1.626 mg/L) were obtained based on CIPW in all five soils with a much lower coefficient of variation.CONCLUSIONSThese findings indicate that measuring the concentration of clomazone in in situ pore water provides a reliable and comparable method for evaluating its bioavailability and phytotoxicity on corn. Using CIPW rather than Csoil as a herbicide indicator is more accurate for assessing its actual phytotoxicity. These results are important for the scientific application of clomazone and the safe production of corn. © 2024 Society of Chemical Industry.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for rapid analysis of eight Gelsemium elegans Benth alkaloids in human plasma and urine

Gelsemium elegans Benth alkaloids are the main components of G. elegans and can cause acute toxicosis or even death. Although several studies have reported methods for detecting G. elegans alkaloids, a high-throughput and environmental-friendly strategy for detection of multiple G. elegans alkaloids has not been realized. In this work, a matrix-assisted laser desorption/ionization time-of-flight mass spectrometry method was developed for rapid detection of G. elegans alkaloids in human plasma and urine for diagnosis of poisoning. Multiple matrices and crystal spotting methods were evaluated to obtain stable and high peak intensities without “sweet spot”. We verified the methodology and obtained excellent results. The matrix effects with different dilutions were compared and good recoveries and a low relative standard deviation were obtained with a 40-fold dilution. This method could shorten the analysis time and greatly reduce the consumption of chemical solvents. Furthermore, it could be applied to quantitative assessment of G. elegans alkaloid poisoning incidents.

Valorization of coconut (Cocos nucifera L.) testa as a biocolourant

IntroductionCoconut testa, a by-product of the coconut processing industry, is currently underutilised. This study aimed to extract a coconut testa-based food colourant using various organic solvents and physical methods, and to utilise this colourant in food product preparation.MethodsDifferent organic solvents, along with various time and temperature combinations, were employed for colourant extraction using both a laboratory-scale water bath and ultrasonication. The colour coordinate values (CIELab) of the testa-derived colourants were measured, and the colourants were screened for various phytochemicals. The in vitro antioxidant potential of the testa colourant was assessed by quantifying total phenolics, and the phytochemical composition, including monomeric anthocyanins, was evaluated.ResultsThe study determined the optimal combinations of organic solvents, temperature and time to obtain extracts with maximum antioxidant activity and total phenolic content (TPC). Acidified ethanol-based extracts of testa colourants yielded highest polyphenol content (154.39 ± 2.63 mg GAE/g) and flavonoids content (53.65 ± 0.62 mg QE/g). Similarly, ethanol-based extractants of coconut testa produced high anthocyanin content [823.02 ± 1.81 mg Cy-3-glc equivalents (C3GE)/100 g]. Acidified (0.3 M HCl) solvents at relatively high temperature and time combinations exhibited high antioxidant potential of testa colourant, as measured by CUPRAC, FRAP, and DPPH assays. Following the foam mat drying process of the colourant, a mature coconut water-based jelly was prepared by incorporating the testa colourant extracted with acidified ethanol.DiscussionThis study highlights the biochemical and antioxidant potential of the food colorant derived from coconut testa and explores its suitability for functional food applications. Therefore, coconut testa extract serves a dual purpose: it enhances the aesthetic appeal of food as a colourant and provides significant health-promoting properties due to its high anthocyanin content. Insights from this study could help in promoting the valorization of one of the beneficial by products of coconut industry.

Preparation of DOX-TPP/HA-ss-OA Nanoparticles, Investigation of Drug Release Behavior In Vitro, and Evaluation of Anti-proliferative Activity In Vitro.

This study aimed to develop and characterize DOX-TPP/HA-ss-OA nanoparticles, utilizing the mitochondria-targeting prodrug doxorubicin-triphenylphosphine (DOXTPP) and a reduction-sensitive amphiphilic polymer, hyaluronic acid-disulfide-oleic acid (HAss- OA). The research focused on evaluating the drug release behavior of these nanoparticles under varying glutathione (GSH) concentrations and their anti-tumor activity in vitro. DOX-TPP/HA-ss-OA nanoparticles were prepared using probe ultrasound technology. The study examined the impact of different organic solvents on drug loading capacity and encapsulation efficiency to determine the optimal conditions. A single-factor experimental design was used to optimize the formulation process. Key parameters, including particle size and zeta potential, were measured to assess nanoparticle stability and performance. The dynamic dialysis method was employed to evaluate the reduction-sensitive drug release characteristics in media with different GSH concentrations. The MTT assay was used to analyze the growth-inhibitory effects of the nanoparticles on human breast cancer cells (MCF-7) and drug-resistant cells (MCF-7/ADR). The optimized preparation process for DOX-TPP/HA-ss-OA nanoparticles included a drug dosage of 2.0 mg, an oil-to-water volume ratio of 1:5, ultrasonic power of 500 W, and ultrasonic time of 15 minutes. The nanoparticles had an average particle size of 203.72 ± 2.30 nm and a zeta potential of 25.82 ± 0.58 mV, indicating favorable stability and effective drug delivery properties. The nanoparticles exhibited a slow, sustained release of DOX-TPP in pH 7.4 phosphate buffer solution (PBS) and accelerated release in high GSH concentrations, demonstrating reduction-responsive drug release. In vitro studies showed that DOX-TPP/HA-ss-OA nanoparticles significantly inhibited the proliferation of MCF-7 and MCF-7/ADR cells in a dosedependent manner, with enhanced efficacy compared to free DOX and other formulations. DOX-TPP/HA-ss-OA nanoparticles demonstrate excellent reduction sensitivity, effective tumor cell growth inhibition in vitro, and the ability to overcome drug resistance. Including particle size and zeta potential measurements supports their suitability as drug carriers, highlighting their potential for targeted cancer therapy and further development.

Microwave-Assisted Enzymatic Green Solvent Technology for the Extraction and Characterization of Sesame Seed Oil

Traditional methods of extracting oil with organic solvents raise issues related to health, safety, and the environment. Microwave-assisted enzymatic green solvent extraction (MAEGSE) technology is environment friendly because it involves less hazardous chemical synthesis, utilizes renewable feedstock, and decreases the chemical load and emissions produced by organic solvents. The solvents methanol, ethanol, and various cell wall degrading enzymes such as hemicellulose, viscozyme L, pectinase, xylanase, and cellulase were used in this study. The MAEGSE process of sesame oil was conducted, and the results indicated that, unlike the controlled group, no enzymes were used during the process. Among all the combinations a higher oil extraction efficiency was obtained with combination of pectinase and ethanol (37.27%) followed by the xylanase with ethanol (36.75%) from sesame seed without compromising the quality of oil. Among the enzymes tested, pectinase resulted in the highest oil extraction efficiency, followed by xylanase. Use of pectinase improved the oil extraction efficiency in both ethanol and methanol mediums. The outcomes suggested that the application of pectinase enzymes plays a significant role in increasing the oil yield in comparison with the control without compromising quality of oil. Oil extracted without the use of enzyme (control) had a lower free fatty acid (FFA) concentration than the oils extracted with MAEGSE. Even though the specific gravity (SG) and refractive index (RI) of extracted oils were not significantly different in the solvents, the saponification value (SV), peroxide value (PV), iodine value (IV), and free fatty acid (FFA) were found to have minor differences among the extraction techniques.

Developing Sustainable Wood Preservatives: The Antifungal Efficiency of Afzelia quanzensis Welv. and Androstachys johnsonii Prain Sawdust Extracts from Mozambique

This study aimed to both develop and assess the antifungal efficacy of extractives derived from different sets of sawdust originating from two hardwood species, namely chanfuta (Afzelia quanzensis Welv.) and mecrusse (Androstachys johnsonnii Prain). These hardwood species possess inherent characteristics of high natural durability. The primary objective was to use these extractives to impregnate perishable wood species, enhancing their durability and augmenting their commercial value. Collected wood sawdust was initially sieved to remove residues and unwanted materials and conditioned until 12% moisture content. Subsequently, the sawdust was Soxhlet-extracted using a mixture of organic solvents, including acetone, ethanol, and toluene. After evaporating the solvents, the resulting extractives were used to prepare a preservative solution with ethanol and acetone. The extractive solutions from each wood species were mixed with malt extract agar and then diluted to various concentrations: 0.125 mg/mL, 0.25 mg/mL, 0.5 mg/mL, 1.25 mg/mL, 2.0 mg/mL, and 2.5 mg/mL. For each concentration, fungal plugs from the periphery of actively growing cultures were moved to the centre of Petri dishes and placed in controlled laboratory conditions for incubation. The antifungal efficacy was assessed against specific wood-decaying fungi, including brown rot fungi (Coniophora puteana, Postia placenta, Lentinus lapideus) and white rot (Trametes versicolor). The evaluation involved daily monitoring of the linear expansion along two perpendicular radii for each fungus expressed as a percentage of the empty Petri dish area. The results indicated that the chanfuta extractives inhibited the growth of brown rot fungi at a concentration of 0.25 mg/mL and white rot fungi at 2.0 mg/mL. Similarly, the mecrusse extractives inhibit brown rot at 0.5 mg/mL and white rot at 2.0 mg/mL. The fatty acids Oleic (C18:1) present in the chanfuta extractives solution and linoleic (C18:2) in mecrusse extractives contributed to restraining the fungal growth. These results suggest that sawdust extractives from both wood species exhibit promising potential for creating environmentally friendly wood preservatives, which, with effective treatments, could extend the lifespan of perishable wood species

Diffusion of organic solvents in thermoplastic elastomers: infinite dilution experiments

Diffusion of organic solvents in thermoplastic elastomers: infinite dilution experiments

HRMAS NMR for Studying Solvent-Induced Mobility of Polymer Chains and Metallocene Migration Into Low-Density Polyethylene (LDPE).

HRMAS (high-resolution magic angle spinning) nuclear magnetic resonance (NMR) spectroscopy of low-density polyethylene (LDPE) affords 1H and 13C NMR spectra with superior resolution. For acquiring HRMAS NMR spectra, the polymer is first swollen with representative organic solvents. Then, the samples are measured with a conventional solid-state NMR spectrometer in the wideline mode or at the low spinning speed of 2 kHz. Anisotropic interactions like CSA (chemical shift anisotropy) and dipolar interactions are reduced due to the additional mobility of the polymer chains in the presence of the solvent within the polymer network. The combined effect of this mobility and MAS leads to signals with substantially reduced halfwidths as compared to classic MAS of the dry polymer. With HRMAS, all signals of the polymer become visible, and the spectra can be used for a quick and easy assessment of the polymer swelling behavior in diverse solvents. Being able to characterize polymers on the molecular level, and identifying the solvents that penetrate the polymer network best, enables the study of post-synthesis modifications of the polymers. It is demonstrated by paramagnetic HRMAS that the metallocene nickelocene (Cp2Ni) penetrates the LDPE network along with the solvent and is homogeneously dispersed in the polymer. SEM images prove that the structure of the polymer is not altered by the presence of a solvent and Cp2Ni. The impact of the paramagnetic Cp2Ni on the 1H signal halfwidth and T1 time of LDPE is studied. HRMAS allows a quick assessment of metal complexes regarding their ability to penetrate the LDPE network and therefore supports future studies of catalytic polymer degradation.

Phytochemical Screening of Seaweed Flour (Eucheuma cottonii) Using Various Organic Solvents and Its Application in Tilapia Feed (Oreochromis niloticus)

This study aims to qualitatively analyze the bioactive compounds in Eucheuma cottonii seaweed flour extract and its application in commercial feed for tilapia (Oreochromis niloticus). The methodology employed is experimental and consists of two phases. Phase 1 involves the extraction of E. cottonii flour using three different organic solvents with varying polarity (ethanol, ethyl acetate, and a combination of ethanol + ethyl acetate). The testing parameters include qualitative phytochemical tests for alkaloids, steroids/triterpenoids, saponins, flavonoids, and tannins. Phase 2 consists of the application of the extract to tilapia over a 30-day rearing period with four treatments: control/commercial feed (P0), commercial feed + ethanol extract (P1), commercial feed + ethyl acetate extract (P2), and commercial feed + combined ethanol and ethyl acetate extract (P3). The parameters tested include absolute weight, specific growth rate, survival rate, and water quality. Phytochemical and water quality data are presented in table format. Meanwhile, growth and survival data are analyzed using ANOVA, followed by Duncan’s test for significant differences. The results of the researches carried out, it can be concluded that the phytochemical analysis of E. cottonii extract in ethanol and the ethanol + ethyl acetate combination yielded similar compounds: alkaloids, steroids/triterpenoids, and flavonoids. The ethyl acetate extract contained triterpenoids and flavonoids. Both saponins and tannins returned negative results across all organic solvent treatments. All treatments with the addition of E. cottonii seaweed extract in various organic solvents demonstrated better growth in tilapia compared to the control treatment.

Cleaning of Water Surface from Oil and Oil Products in Arctic Conditions

The results of obtaining and studying the properties of the composite for elimination of oil and petroleum products on water areas at low temperatures on the basis of oligomer obtained from urea resin and treated with polymer solution in organic solvent are presented. It is concluded that the proposed composite has a high degree of purification from oil and petroleum products, which does not change when the temperature drops to -40 °С.

Paclitaxel loaded Capmul MCM and tristearin based nanostructured lipid carriers (NLCs) for glioblastoma treatment: screening of formulation components by quality by design (QbD) approach.

Paclitaxel (PTX), a naturally occurring diterpenoid isolated from Taxus brevifolia, is a first-line drug for the treatment of glioblastoma; however, it suffers from the disadvantages of poor water solubility and nonspecific biodistribution, which cause serious side effects in the human body. The marketed formulation suffers from serious side effects, such as allergic reactions, neutropenia, and neuropathy, which require safe and effective formulations of PTX. In the present study, PTX was entrapped in a solid-liquid lipid mixture with the aid of a surfactant using a modified solvent evaporation technique. Higher entrapment of the impressive stability of the formulation was achieved by employing quality design-based strategies. Optimized levels by employing a numerical optimization technique for each factor, that is, surfactant concentration (X1), lipid concentration (X2), and amount of organic solvent (X3) were 0.3%, 0.76% & 8.3 ml respectively. The resultant formulation exhibited a particle size of 121.44 nm, entrapment efficiency of 94.27%, and zeta potential of -20.21 mV with unimodal size distribution. A reduction in the % crystalline index from 48 to 3.4% ensured the amorphous form of the entrapped drug inside the formulation, which precludes the fear of leakage and instability of the formulation. Cell line studies conducted on U87MG Cell lines also suggested that the NLC of paclitaxel are more effective than those of pure PTX. In summary, PTXNLC seem to be a superior alternative carrier system for the formulation industry to obtain higher entrapment with excellent stability.

Engineering Injectable and Highly Interconnected Porous Silk Fibroin Microspheres for Tissue Regeneration.

Injectable porous microspheres represent a promising therapeutic platform for cell delivery, drug delivery, and tissue regeneration. Yet, the engineering of silk fibroin microspheres with a highly interconnected porous structure remains an unsolved challenge. In this study, a simple and efficient method is developed that does not require the use of organic solvents to prepare silk fibroin microspheres with a predictable structure. Through extensive screening, the addition of glucose is found to direct the formation of a highly interconnected porous structure from the interior to the surface of silk fibroin microspheres. Compared to silk fibroin microspheres (SF microspheres) produced through a combination of electro-spray, cryopreservation, and freeze drying, silk fibroin-glucose microspheres (SF-Glu microspheres) demonstrates enhanced capabilities in promoting cell adhesion and proliferation in vitro. Both SF-Glu and SF microspheres exhibit the capacity to maintain the sustained release kinetics of the loaded model drug. Furthermore, SF-Glu microspheres facilitate the recruitment of endogenous cells, capillary migration, and macrophage phenotype switch following subcutaneous injection in the rats. This study opens a new avenue for the construction of porous silk fibroin microspheres, which could lead to a broader range of applications in regenerative medicine.

One-Pot Divergent Synthesis of a 13-Ring Triquinone and its Facile Conversion to a [4.4.4]Tridecastarphene.

Acenes are notable for their optoelectronic properties and applications in organic electronics. Starphenes are structurally related molecules possessing three acene arms that radiate linearly from a central benzene ring (i. e., linearly annellated triphenylenes). Large starphenes have been prepared using convergent syntheses involving transition metal catalyzed cyclotrimerizations of either preformed acenes or arynes. Here, we report a one-pot divergent synthesis of a 13-ring triquinone that is readily converted to a [4.4.4]tridecastarphene derivative. The one-pot procedure involves the sequential reactions of three 1,4-anthraquinones with o-quinodimethane derivatives that are generated sequentially from a stable, trisulfone precursor. The resulting [4.4.4]tridecastarphene derivative bearing p-(t-butyl)phenyl substituents was characterized by 1H NMR, 13C NMR and UV-vis spectroscopies, as well as mass spectrometry, cyclic voltammetry and differential pulse voltammetry. Theoretical and experimental studies reveal a relatively high-lying HOMO orbital (about -4.70 to -4.86 eV) and a relatively small HOMO-LUMO gap (2.1 eV), suggesting utility as a p-type organic semiconductor. Our [4.4.4]tridecastarphene derivative photooxidizes in a CH2Cl2 solution exposed to ambient light and air with a half-life of 150 minutes at room temperature, but shows no sign of degradation after 12 months in the solid-state. Our [4.4.4]tridecastarphene derivative also shows excellent solubility in a number of organic solvents including dichloromethane, chloroform and toluene, potentially enabling printed electronic applications.