Solvent Compatibility Research Articles

Increasing Applications of Graphite Thermoplastic Electrodes with Aryl Diazonium Grafting

AbstractCarbon composite thermoplastic electrodes (TPEs) consist of graphite and thermoplastic made using an easy, solvent‐assisted fabrication. TPEs have the advantages of high conductivity, good electron transfer kinetics, low cost, reusability, and easy patterning, but have only been used with aqueous solvents due to solvent compatibility with the poly(methyl methacrylate) (PMMA) template. The limited solvent compatibility hinders the application range and surface modifications. Here, cyclic olefin copolymer (COC) TPEs in glass templates that are compatible with additional solvents are presented. TPEs are grafted with aryl diazonium salts in acetonitrile, showing covalent surface TPE modification for the first time. Further investigation is carried out with scanning electrochemical microscopy (SECM). The TPEs are post‐functionalized with a ferrocene moiety via click chemistry. The diazonium electrografting and click chemistry modifications open up future studies and broader applications of TPEs.

Spontaneous Interface Ion Exchange: Passivating Surface Defects of Perovskite Solar Cells with Enhanced Photovoltage

AbstractInterface engineering is of great concern in photovoltaic devices. For the solution‐processed perovskite solar cells, the modification of the bottom surface of the perovskite layer is a challenge due to solvent incompatibility. Herein, a Cl‐containing tin‐based electron transport layer; SnOx‐Cl, is designed to realize an in situ, spontaneous ion‐exchange reaction at the interface of SnOx‐Cl/MAPbI3. The interfacial ion rearrangement not only effectively passivates the physical contact defects, but, at the same time, the diffusion of Cl ions in the perovskite film also causes longitudinal grain growth and further reduces the grain boundary density. As a result, an efficiency of 20.32% is achieved with an extremely high open‐circuit voltage of 1.19 V. This versatile design of the underlying carrier transport layer provides a new way to improve the performance of perovskite solar cells and other optoelectronic devices.

Resolvation-Based Damage to Metal–Organic Frameworks and Approaches to Mitigation

Metal–organic framework (MOF) activation involves the removal of solvent and other guests by “activation” conditions suited to their specific solvent compatibilities and structural stabilities. When MOFs are used in liquid-phase applications, such as catalysis, they are often activated according to best practices but subsequently submerged in high-surface-tension solvents. The destructive potential of this process is demonstrated here using a range of model systems. Furthermore, a method for avoiding this damage, termed reverse solvent exchange (RSE), is outlined. RSE involves resolvation with low-surface-tension solvents followed by exchange into higher-surface-tension solvents. The efficacy of this protocol is shown for several MOFs, including the highly fragile FJI-1, for which resolvation-induced MOF collapse can be almost entirely ameliorated. This work informs best practices for MOF resolvation by ensuring that MOF function is maximized and that performance results are not convoluted by solvation-induced framework damage.

3D Micromachined Polyimide Mixing Devices for in Situ X-ray Imaging of Solution-Based Block Copolymer Phase Transitions.

Advances in modern interface- and material sciences often rely on the understanding of a system's structure-function relationship. Designing reproducible experiments that yield in situ time-resolved structural information at fast time scales is therefore of great interest, e.g., for better understanding the early stages of self-assembly or other phase transitions. However, it can be challenging to accurately control experimental conditions, especially when samples are only available in small amounts, prone to agglomeration, or if X-ray compatibility is required. We address these challenges by presenting a microfluidic chip for triggering dynamics via rapid diffusive mixing for in situ time-resolved X-ray investigations. This polyimide/Kapton-only-based device can be used to study the structural dynamics and phase transitions of a wide range of colloidal and soft matter samples down to millisecond time scales. The novel multiangle laser ablation three-dimensional (3D) microstructuring approach combines, for the first time, the highly desirable characteristics of Kapton (high X-ray stability with low background, organic solvent compatibility) with a 3D flow-focusing geometry that minimizes mixing dispersion and wall agglomeration. As a model system, to demonstrate the performance of these 3D Kapton microfluidic devices, we selected the non-solvent-induced self-assembly of biocompatible and amphiphilic diblock copolymers. We then followed their structural evolution in situ at millisecond time scales using on-the-chip time-resolved small-angle X-ray scattering under continuous-flow conditions. Combined with complementary results from 3D finite-element method computational fluid dynamics simulations, we find that the nonsolvent mixing is mostly complete within a few tens of milliseconds, which triggers initial spherical micelle formation, while structural transitions into micelle lattices and their deswelling only occur on the hundreds of milliseconds to second time scale. These results could have an important implication for the design and formulation of amphiphilic polymer nanoparticles for industrial applications and their use as drug-delivery systems in medicine.

Development of an At-Column Dilution Modulator for Flexible and Precise Control of Dilution Factors to Overcome Mobile Phase Incompatibility in Comprehensive Two-Dimensional Liquid Chromatography.

With the combination of different mechanisms, two-dimensional liquid chromatography has brought revolutionary changes compared to the traditional one-dimensional separation, which dramatically improve the peak capacity in separation and meet the ever-increasing demand for the analysis of complex samples in different research fields, such as chemistry, medicine, etc. However, the incompatibilities between two columns due to the transport of the large sample volume and the solvent effect always limit the wide use of two-dimensional liquid chromatography. In order to resolve this problem an at-column dilution (ACD) modulator was established to overcome the solvent incompatibility in the orthogonal combination within the comprehensive two-dimensional liquid chromatography. This interface is modified from normal two-dimensional interfaces by an additional transfer pump, which realize the at-column dilution without a flow split during the transportation. Moreover, with the control of the transfer flow and the second-dimensional gradient flow, it is able to precisely regulate the at-column dilution factor and conveniently optimize the separation conditions in both dimensions. In this work, a systematic research has been done between the setups with/without the at-column interface in the combination of reversed-phase liquid chromatography and hydrophilic interaction chromatography (RPLC × HILIC) and HILIC × RPLC, which proved that the at-column interface is able to resolve the solvent conflict problem very well. Furthermore, red ginseng was chosen as a real sample to investigate the applicability of the at-column dilution modulator for comprehensive two-dimensional chromatography with high orthogonality.

Compatibility of poly(dimethylsiloxane) microfluidic systems with high viscosity hydrocarbons

In this work, the compatibility of poly(dimethylsiloxane) (PDMS) with high viscosity petroleum liquids (bitumen) was evaluated to study the possibility of using PDMS microchannels in heavy oil and bitumen extraction research using solvent based methods such as Vapor Extraction. Three curing agent to base ratios (1:2, 1:10, and 1:20) were used to fabricate PDMS. Swelling ratio of these three samples in the vicinity of different organic solvents and diluted bitumen were evaluated by measuring the weight of sample every 15 min. It was found that 1:10 ratio PDMS was preferential ratio for minimizing absorption. We were particularly interested in the kinetic of swelling, deformation, and discoloration of PDMS. The hypothesis was that a PDMS microchip can still be used for experiments with heavy oil and bitumen if the experiment time is much shorter than the time it takes for PDMS discoloration, swelling, and deformation. The coating of PDMS slabs with trichloro (1 h 1 h 2 h 2 h-perfluorooctyl) silane was also tested and swelling ratios were again measured to evaluate the effect of surface coating. Swelling ratios were at the same order for uncoated PDMS which shows silane coating is not able to improve the solvent compatibility of PDMS. Moreover, solubility parameter was used to predict the swelling ratio of 1:10 PDMS sample in organic solvents. It predicts that hexane and toluene have the highest solubility that was in great agreement with experimental results. It seems that solubility parameter is a reliable factor to qualitatively predict the swelling ratio of PDMS. The effect of bitumen on transparency of PDMS was also studied using Ultraviolet–Visible spectrophotometer.

Effective extraction of flavonoids from Lycium barbarum L. fruits by deep eutectic solvents-based ultrasound-assisted extraction

The efficient extraction of natural products from biomass is deemed an essential area of interest using green technology in the pharmaceutical and biochemical industries. In recent years, deep eutectic solvents (DESs) have been paying broad interest as compatible, safe, and inexpensive solvents. In this study, we addressed, for the first time, to give a fruitful illustration to extract bioactive compounds from favourite Lycium barbarum L. fruits using DESs as green designer solvents, and displaying the tuneability of DESs to extract bioactive compounds from biomass efficiently. Among the studied DESs, the 1 : 2 M mixture of choline chloride and p-toluene sulfonic acid (DESs-6) with an ultra-sound assisted extraction (UAE) method was more efficient to get high extraction yields of flavonoids including myricetin (57.2 mg/g), morin (12.7 mg/g), and rutin (9.1 mg/g) in net DESs. The resulting extraction method in which 50 mg of sample powder was extracted by UAE for 1.5 h using DESs-6 was found to be a more efficient process than conventional extraction methods such as heating plus stirring. Operational conditions including the extractant to sample solid ratio, the effect of water content, the effect of temperature, recycling of DESs, and the effect of ultra-sound irradiation time were investigated. The proposed DESs based extraction procedure attained recovery for flavonoids were in the range 75.6%–96.9%. Therefore, p-toluenesulfonic acid-based DESs may have strong potential as promising materials for the green and efficient extraction of pharmaceutical compounds from other plants or fruits.

Synthesis of Dihydropyridine Derivatives under Eco‐friendly Approach and Investigation of Cytotoxic Activity

In an effort for development of innovative biologically active agents, a sequence of 1,4‐dihydropyridine analogues was synthesized through the green synthetic method. In addition, all compounds were evaluated for their cytotoxic activities against three human cancer cell lines and mouse melanoma and figured out the most active compounds. Besides, promoter reusability, easy handling of the chemical reagent, simple reaction process, time minimization, ethanol–water solvent compatibility, and cost reduction reagent are key tools for this fruitful path. Thus, these examinations recommended that dihydropyridine and their derivatives are motivating moieties for the discovery of new anticancer drugs.

Spectrometric Smartphone-Based System for Ibuprofen Quantification in Commercial Dosage Tablets

A rapid and portable analytical methodology has been developed for ibuprofen (IBU) quantification in commercial dosage tablets using a spectrometric smartphone-based system. The analytical methodology employs point-of-use approaches both for sample preparation and detection, demonstrating its potential utility for portable quality control of pharmaceutical products. In this work, IBU is dissolved in methanol and then treated with a Co(II) aqueous solution, forming a blue complex which is extractable by dispersive liquid-liquid microextraction. Then, the sample’s absorption spectrum is directly measured by a spectrometric smartphone-based system using cartridge made of polyoxymethylene for solvent compatibility. The main experimental factors affecting the dispersive liquid-liquid microextraction of Co-IBU complex were optimized using a multivariate analysis. Under optimized conditions, a working range between 20 and 80 μg mL−1 was obtained with a correlation coefficient of 0.996 for 5 calibration points. The limit of detection and limit of quantification obtained were 4 and 12 μg mL−1, respectively. The performance of the proposed methodology was evaluated in commercial tablet dosage forms, and the results demonstrate the ability of the method to determine IBU in samples representative of those used in real-world quality control applications. Recovery values between 97% and 105% were obtained, which are comparable to those obtained via standard titrimetric methodology.

Synthesis and evaluation of novel chiral stationary phases based on N‑cyclobutylcarbonyl chitosan derivatives

Five halo-containing chitosan 3,6‑bis(phenylcarbamate)‑2‑(cyclobutylformamide) derivatives were synthesized with well-deacetylated chitosan and halo-substituted phenyl isocyanates. The structures of the derivatives were characterized by IR, elemental analysis, and 1H NMR spectrum. After being coated on silica gel, five new CSPs were obtained and their enantioseparation abilities were evaluated, and the enantioseparation abilities were compared with that of commercial CSP of Chiralcel OD-H. The results demonstrated that all the prepared CSPs showed satisfactory enantioseparation ability. The performance of CSP 2 with 3,4‑dichloro substituent on the phenyl group was the best with 11 analytes being baseline separated and 2 analytes being partially separated among 15 tested analytes. Besides, the influence of mobile phase composition, substituent on the phenyl moieties of the chitosan derivatives, as well as structure of analytes on enantioseparation ability was also discussed. In this study, the prepared CSPs exhibited excellent tolerance to “unusual solvents”, and some of them even could work in pure tetrahydrofuran. Therefore, the CSPs bear a universal solvent compatibility in comparison with coated-type CSPs of cellulose/amylose derivatives.

Tuning Merocyanine Photoacid Structure to Enhance Solubility and Temporal Control: Application in Ring Opening Polymerization

AbstractHerein we report the development of a merocyanine‐based photoacid with improved solubility in organic media and enhanced switching kinetics that can be used to impart temporal control over ring opening polymerization. The effect of the structural modification on solubility, thermal relaxation kinetics and activation energy were evaluated using 1H NMR and pump‐probe absorption spectroscopies. Overall, the new merocyanine based photoacid provides access to a wider range of chemical and material applications with improved solvent compatibility and temporal control.

Preparation and Characterization of TiO₂-PVDF/PMMA Blend Membranes Using an Alternative Non-Toxic Solvent for UF/MF and Photocatalytic Application.

The approach of the present work is based on the use of poly (methylmethacrylate) (PMMA) polymer, which is compatible with PVDF and TiO2 nanoparticles in casting solutions, for the preparation of nano-composites membranes using a safer and more compatible solvent. TiO2 embedded poly (vinylidene fluoride) (PVDF)/PMMA photocatalytic membranes were prepared by phase inversion method. A non-solvent induced phase separation (NIPS) coupled with vapor induced phase separation (VIPS) was used to fabricate flat-sheet membranes using a dope solution consisting of PMMA, PVDF, TiO2, and triethyl phosphate (TEP) as an alternative non-toxic solvent. Membrane morphology was examined by scanning electron microscopy (SEM). Backscatter electron detector (BSD) mapping was used to monitor the inter-dispersion of TiO2 in the membrane surface and matrix. The effects of polymer concentration, evaporation time, additives and catalyst amount on the membrane morphology and properties were investigated. Tests on photocatalytic degradation of methylene blue (MB) were also carried out using the membranes entrapped with different concentrations of TiO2. The results of this study showed that nearly 99% MB removal can be easily achieved by photocatalysis using TiO2 immobilized on the membrane matrix. Moreover, it was observed that the quantity of TiO2 plays a significant role in the dye removal.

Characterization and Neutral Atom Beam Surface Modification of a Clear Castable Polyurethane for Biomicrofluidic Applications

Polyurethanes (PU) are a broad class of polymers that offer good solvent compatibility and a wide range of properties that can be used to generate microfluidic layers. Here, we report the first characterization of a commercially available Shore 80D polyurethane (Ultraclear™ 480N) for biomicrofluidic applications. Studies included comparing optical clarity with Polydimethylsiloxane (PDMS) and using high-fidelity replica molding to produce solid PU structures from the millimeter to nanometer scales. Additionally, we report the first use of NanoAccel™ treatment in Accelerated Neutral Atom Beam (ANAB) mode to permanently roughen the surface of PU and improve the adhesion of breast cancer cells (MDA-MB-231) on PU. Surface energy measurements using Owens-Wendt equations indicate an increase in polar and total surface energy due to ANAB treatment. Fourier-transform infrared (FTIR) spectroscopy in attenuated total reflectance (ATR) mode was used to demonstrate that the treatment does not introduce any new types of functional groups on the surface of Ultraclear™ PU. Finally, applicability in rapid prototyping for biomicrofluidics was demonstrated by utilizing a 3D-printing-based replica molding strategy to create PU microfluidic layers. These layers were sealed to polystyrene (PS) bases to produce PU-PS microfluidic chips. Ultraclear™ PU can serve as a clear and castable alternative to PDMS in biomicrofluidic studies.

The Impact of a Dynamic Two-Step Solution Process on Film Formation of Cs0.15 (MA0.7 FA0.3 )0.85 PbI3 Perovskite and Solar Cell Performance.

This paper provides deep understanding of the formation mechanism of perovskite film fabricated by sequential solution-based methods. It compares two sequential spin-coating methods for Cs0.15 (MA0.7 FA0.3 )0.85 PbI3 perovskite. First is the "static process," with a stoppage between the two spin-coating steps (1st PbI2 -CsI-dimethyl sulfoxide (DMSO)-dimethylformamide (DMF) and 2nd methylammonium iodide (MAI)-formamidinium iodide (FAI)-isopropyl alcohol). Second is the "dynamic process," where the 2nd precursor is dispensed while the substrate is still spinning from the 1st step. For the first time, such a dynamic process is used for Cs0.15 (MA0.7 FA0.3 )0.85 PbI3 perovskite. Characterizations reveal improved film formation with the dynamic process due to the "retainment" of DMSO-complex necessary for the intermediate phase which i) promotes intercalation between precursors and ii) slows down perovskite crystallization for full conversion. The comparison on as-deposited perovskite before annealing indicates a more ordered film using this dynamic process. This results in a thicker, more uniform film with higher degree of preferred crystal orientation and higher carrier lifetime after annealing. Therefore, dynamic-processed devices present better performance repeatability, achieving a higher average efficiency of 17.0% compared to static ones (15.0%). The new insights provided by this work are important for perovskite solar cells processed sequentially as the process has greater flexibility in resolving solvent incompatibility, allowing separate optimizations and allowing different deposition methods.

Characterization of Dye Extracts from Historical Cultural-Heritage Objects Using State-of-the-Art Comprehensive Two-Dimensional Liquid Chromatography and Mass Spectrometry with Active Modulation and Optimized Shifting Gradients.

Unbiased characterization of dyes and their degradation products in cultural-heritage objects requires an analytical method which provides universal separation power regardless of dye classes. Dyes are small molecules that vary widely in chemical structure and properties, which renders their characterization by a single method challenging. We have developed a comprehensive two-dimensional liquid chromatography method hyphenated with mass spectrometry and UV–vis detection. We use stationary-phase-assisted modulation to enhance the method in terms of detection limits and solvent compatibility and to reduce the analysis time. The PIOTR program was used to optimize an assembly of shifting second-dimension gradients, which resulted in a high degree of orthogonality (80% in terms of the asterisk concept). The resulting method is universally applicable to all classes of dyes extracted from cultural-heritage objects. Thanks to the high peak capacity and orthogonality, dye components can be separated from chemically similar impurities and degradation products, providing a detailed fingerprint of the dyes mixture in a specific sample. The method was applied to a number of challenging dye extracts from 17th- and 19th-century cultural-heritage objects.

Chloroform compatible, thiol-ene based replica molded micro chemical devices as an alternative to glass microfluidic chips.

Polymeric microfluidic chips offer a number of benefits compared to their glass equivalents, including lower material costs and ease and flexibility of fabrication. However, the main drawback of polymeric materials is often their limited resistance to (organic) solvents. Previously, thiol-ene materials were shown to be more solvent resistant than most other commonly used polymers; however, they still fall short in "harsh" chemical environments, such as when chlorinated solvents are present. Here, we show that a simple yet effective treatment of thiol-ene materials results in exceptional solvent compatibility, even for very challenging chemical environments. Our approach, based on a temperature treatment, results in a 50-fold increase in the chloroform compatibility of thiol-enes (in terms of longevity). We show that prolonged heat exposure allows for the operation of the microfluidic chips in chloroform for several days with no discernable deformation or solvent-induced swelling. The method is applicable to many different thiol-ene-based materials, including commercially available formulations, and also when using other commonly considered "harsh" solvents. To demonstrate the utility of the solvent compatible thiol-enes for applications where chloroform is frequently employed, we show the continuous and uniform production of polymeric microspheres for drug delivery purposes over a period of 8 hours. The material thus holds great promise as an alternative choice for microfluidic applications requiring harsh chemical environments, a domain so far mainly restricted to glass chips.

Deacidification of aged papers using dispersion of Ca(OH)2 nanoparticles in subcritical 1,1,1,2-tetrafluoroethane (R134a)

An effective and integrated method for deacidification has become an urgent issue in the conversation of paper-based materials with natural aging of books, archives and paper relics. In this research, an efficiency of innovative method for paper deacidification using subcritical R134a combined with pre-synthetic Ca(OH)2 nanoparticles was evaluated by pH, alkaline reserve, colorimetry and tensile strength. The physicochemical properties of the deacidifying agents and paper samples before and after deacidification were characterized by XRD, SEM and FTIR. Compared with traditional spraying method for Ca(OH)2 nanoparticles, the subcritical R134a deacidification system (due to its good solvent diffusivity and compatibility) had an obvious advantage in evaluations for all the paper samples. The innovative deacidification was expected to realize the integration of cleaning and deacidification in one working procedure.

3D Printing: The Second Dawn of Lab-On-Valve Fluidic Platforms for Automatic (Bio)Chemical Assays.

In this work, inexpensive manufacturing of unibody transparent mesofluidic platforms for pressure-driven Lab-On-a-Valve (LOV) methodologies is accomplished via rapid one-step 3D prototyping from digital models by user-friendly freeware. Multichannel architecture having 800-1800 μm cross-sectional features with unconventional 3D conduit structures and integrating optical and electrochemical detection facilities is for the first time reported. User-defined flow-programming capitalizing upon software control for automatic liquid handling is synergistically combined with additive manufacturing based on stereolithographic 3D printing so as to launch the so-called fourth generation of microflow analysis (3D-μFIA). Using an affordable consumer-grade 3D printer dedicated LOV platforms are 3D printed at will and prints are characterized in terms of solvent compatibility, optical and mechanical properties, and sorption of inorganic and organic species to prospect potentialities for the unfettered choice of chemistries. The unique versatility of the 3D-printed LOV device that is attached to a multiposition rotary valve as a central design unit is demonstrated by (i) online handling of biological materials followed by on-chip photometric detection, (ii) flow-through bioaccessibility tests in exposome studies of contaminated soils with miniaturized voltammetric detection, (iii) online phospholipid removal by TiO2-incorporated microextraction approaches using on-chip disposable sorbents, and (iv) automatic dynamic permeation tests mimicking transdermal measurements in Franz-cell configurations. A multipurpose LOV fluidic platform can be fabricated for less than 11 Euros.

Click chemistry enables quantitative chiroptical sensing of chiral compounds in protic media and complex mixtures

Click reactions have become powerful synthetic tools with unique applications in the health and materials sciences. Despite the progress with optical sensors that exploit the principles of dynamic covalent chemistry, metal coordination or supramolecular assemblies, quantitative analysis of complex mixtures remains challenging. Herein, we report the use of a readily available coumarin conjugate acceptor for chiroptical click chirality sensing of the absolute configuration, concentration and enantiomeric excess of several compound classes. This method has several attractive features, including wide scope, fast substrate fixation without by-product formation or complicate equilibria often encountered in reversible substrate binding, excellent solvent compatibility, and tolerance of air and water. The ruggedness and practicality of this approach are demonstrated by comprehensive analysis of nonracemic monoamine samples and crude asymmetric imine hydrogenation mixtures without work-up. Click chemosensing addresses increasingly important time efficiency, cost, labor and chemical sustainability aspects and streamlines asymmetric reaction development at the mg scale.

Silicon Photonic Microring Resonator Arrays for Mass Concentration Detection of Polymers in Isocratic Separations.

Molecular weight distribution (MWD) is often the most informative analytical parameter in polymer analysis, with gel permeation chromatography (GPC) being the most common approach for determining the MWD for polymer samples. Many industrially relevant polymers lack chromogenic or fluorogenic signatures, precluding use of spectroscopy-based detection. Universal detectors, such as evaporative light scattering and charged aerosol detectors, are nonlinear, limiting quantitative polymer analysis. Differential refractive index (dRI) detectors show linear mass concentration sensitivity but are limited for some analyses given that they are incompatible with gradient-based separations, have a limited dynamic range, and require extended thermal equilibration times. In this study, we investigated the utility of silicon photonic microring resonator arrays as a quantitative mass concentration detector for industrial polymer analysis. Microring resonators have optical properties that are sensitive to changes in refractive index, offer an extended dynamic range, have a broad solvent compatibility, and have a linear mass concentration detection for a range of molecular weights. Linear mass concentration detection for microrings was demonstrated through a series of isocratic GPC separations using narrow MWD polystyrene (PS) standards. This detection technology was then utilized in conjunction with conventional GPC detectors to analyze a series of broad MWD PS standards, with results in good agreement with dRI and UV/visible. These results demonstrate the potential of the microring resonator platform as a detector for industrial polymer analysis.