Solvent Research Articles

Comparison of the Impact of NaIO4-Accelerated, Cu2+/H2O2-Accelerated, and Novel Ion-Accelerated Methods of Poly(l-DOPA) Coating on Collagen-Sealed Vascular Prostheses: Strengths and Weaknesses.

Sensitive biomaterials subjected to surface modification require delicate methods to preserve their structures and key properties. These include collagen-sealed polyester vascular prostheses. For their functionalization, coating with polycatecholamines (PCAs) can be used. PCAs change some important biological properties of biomaterials, e.g., hydrophilicity, bioactivity, antibacterial activity, and drug binding. The coating process can be stimulated by oxidants, organic solvents, or process conditions. However, these factors may change the properties of the PCA layer and the matrix itself. In this work, collagen-sealed vascular grafts were functionalized with a poly(l-DOPA) (PLD) layer using novel seawater-inspired ion combination as an accelerator, compared to the sodium periodate, Cu2+/H2O2 mixture, and accelerator-free reference methods. Then, poly(l-DOPA) was used as the interface for antibiotic binding. The coated prostheses were characterized (SEM, FIB-SEM, FTIR, UV/vis), and their important functional parameters (mechanical, antioxidant, hemolytic, and prothrombotic properties, bioactivity, stability in human blood and simulated body fluid (SBF), antibiotic binding, release, and antibacterial activity) were compared. It was found that although sodium periodate increased the strength and drug-binding capacity of the prosthesis, it also increased the blood hemolysis risk. Cu2+/H2O2 destabilized the mechanical properties of the coating and the graft. The seawater-inspired ion-accelerated method was efficient, stable, and matrix- and human blood-friendly, and it stimulated hydroxyapatite formation on the prosthesis surface. The results lead to the conclusion that selection of the PCA formation accelerator should be based on a careful analysis of the biological properties of medical devices. They also suggest that the ion-accelerated method of PLD coating on medical devices may be highly effective and safer than the oxidant-accelerated coating method.

Fullertubes: A 30-Year Story of Prediction, Experimental Validation, and Applications for a Long-Missing Family of Soluble Carbon Molecules.

ConspectusDuring the last 30 years, theoretical scientists imagined segmental families of monolayer carbon tubules with fullerene-based end-caps. These fullertube molecules would possess structural features of both fullerenes (hemispherical end-caps) and tubular belts of single-walled carbon nanotubes (SWCNTs). Yet, their experimental verification remained elusive for decades. It was not until 2020-2023 that segmental families of fullertubes were finally confirmed in the lab. The shocking irony is that these fullertubes were unwittingly coproduced alongside fullerenes (e.g., C60, C70, C84) in both flame and electric arc soot since the 1990s. Yet, nobody knew these "hidden" families of fullertubes were experimentally present in their extracted soot due to their low abundance and the absence of isolation methodology.This eruption of fullertube discoveries in 2020-2023 was brought to fruition by structural data, both DFT and experimental. This "Treasure Trove" of new molecules during this four-year window occurred with only microgram quantities. Typically, milligram levels of purified samples are required for X-ray crystallography and 13C NMR structural analysis. The breakthrough for experimentally verifying the missing fullertubes was an aminopropanol reagent to selectively react with and remove spheroidal carbon (e.g., C60, C70, C84) as hydrophilic derivatives. In contrast, there was suppressed reaction with fullertubes, which remained in organic solvent. It is well established that high symmetry (3-, 5-, and 6-fold) hemispheres for C60-Ih and other fullerenes and metallofullerenes are prerequisite end-caps for fullertubes. For the case of [5,5] C130 fullertubes, this requirement results in only eight 3-, 5-, and 6-fold symmetry structural isomers possible from a total of 39,393 possible isolated pentagon rule (IPR) isomers. From this C130 list of 8 candidate isolated pentagon rule (IPR) high symmetry isomers, surprisingly only one structure matched the DFT polarizability versus chromatographic retention parameter (a new gold standard for isomer identification). The simultaneous emergence of DFT computations of other properties (e.g., total energy, HOMO-LUMO gap, UV-vis) for large carbon molecules provided support for structural determination. Experimental approaches (e.g., mass spectrometry, UV-vis, XPS, Raman, and STEM) provided additional layers of structural elucidation at the microgram level. For the first time, we developed a chemical isolation protocol that would allow the preparation and isolation of soluble pristine fullertubes in the range of C90-C200. To date, applications of SWCNTs for use in nanoscale computer applications requires purities greater than 99.999%. Although this stringent mandate has not yet been demonstrated using SWCNT samples, this high level of purity appears achievable for metallic [5,5] D5d-C120 and semiconductor [10,0] D5h-C120 [10,766] fullertubes. Moreover, commercial production of pristine fullertubes should easily be feasible by the flame method due to its continuous operation and inexpensive feedstock. For application development, theoretical and electrochemical experimental data show that fullertubes exhibit high catalytic activity in oxygen reduction reactions. In the medical sector, pristine fullertube dispersions exhibit antimicrobial effects on Mycobacterium smegmatis and M. abscessus.

All-Aqueous Soft Milli-swimmers.

Microscale swimmers are attractive for targeted drug delivery, noninvasive microsurgery and environmental remediation at different length scales, among which, Marangoni-based swimmers have garnered considerable attention due to their independence of external energy supply. However, applications of most existing chemical swimmers are limited by complex fabrication, high cost, utilization of organic (or even toxic) solvents, poor motility performance, and lack of controllability. To address these challenges, we propose an approach for all-aqueous soft milli-swimmers that utilizes biodegradable hydrogels and biocompatible fuels. This innovative method achieves swimmer body generation and fuel loading in one step by simply dripping one aqueous solution into another, saving fabrication time and minimizing fuel loss during transfer. These all-aqueous soft milli-swimmers have rove beetle-like self-propulsion, which stores low-surface-energy compounds within their body for propulsion on liquid surfaces. Isotropic and anisotropic all-aqueous soft milli-swimmers are formed with precise control over their dimension, morphology, and movement velocity. Through their motion within engineered channels, intricate labyrinths, dynamic air-liquid interfaces, and collective self-assemblies, their remarkable adaptability in complex aqueous environments is demonstrated. Furthermore, the integration of functional nanoparticles endows these all-aqueous milli-swimmers with multifunctionality, expanding their applications in cargo transportation, sensing, and environmental remediation.

Effect of Surfactants on the Permeation Rate and Selectivity of Polyamide Composite Membranes for Organic Solvent Nanofiltration

Solvent-resistant membranes are pivotal in industrial separations. This study aims to develop thin-film composite polyamide (TFC-PA) membranes with enhanced organic solvent nanofiltration (OSN) capabilities. Polyallylamine hydrochloride (PAAH) was used as the aqueous amine and isophthaloyl chloride (IPC) as the crosslinker to form the polyamide active layer by interfacial polymerization (IP) on a polyacrylonitrile (PAN) support. The impact of using anionic sodium dodecyl sulfate (SDS) and cationic cetyltrimethylammonium bromide (CTAB) to act as phase transfer agents during IP was investigated to understand their potential for facilitating the transfer of PAAH to the organic phase for reaction with IPC. The SDS and CTAB were separately dissolved into the PAAH solutions before IP to evaluate their effects on membrane properties. Extensive characterization including SEM, EDX, AFM, Water Contact Angle, ATR-FTIR, and Solid (CP-MAS) 13C-NMR revealed various chemical and structural features of the membrane. The membrane M2 (PAAH-IPC) (exhibited >98% rejection for various anionic and cationic dyes. The inclusion of SDS during interfacial polymerization led to a substantial 3-fold increase in methanol permeate flux from 31Lm-2 h-1 to 119Lm-2 h-1, at a pressure of 15bar. Conversely, the addition of CTAB resulted in membranes with higher flux but insufficient dye rejection. Moreover, after a three-week period of static aging no significant changes were detected in either permeability or solute rejection, substantiating their stability.

Halogen‐Bonded Organic Frameworks (XOFs) Based on N⋅⋅⋅Br+⋅⋅⋅N Bonds: Robust Organic Networks Constructed by Fragile Bonds

AbstractOrganic frameworks face a trade‐off between the framework stability and the bond dynamics, which necessitates the development of innovative linkages that can generate stable frameworks without hindering efficient synthesis. Although iodine(I)‐based halogen‐bonded organic frameworks (XOFs) have been developed, constructing XOFs based on bromine(I) is desirable yet challenging due to the high sensitivity of bromine(I) species. In this work, we present the inaugural construction of stable bromine(I)‐bridged two‐dimensional (2D) halogen‐bonded organic frameworks, XOF(Br)−TPy−BF4/OTf, based on sensitive [N⋅⋅⋅Br⋅⋅⋅N]+ halogen bonds. The formation of XOF(Br)−TPy−BF4/OTf was monitored by 1H NMR, XPS, IR, SEM, TEM, HR‐TEM, SEAD. Their framework structures were established by the results from PXRD, theoretical simulations and SAXS. More importantly, XOF(Br) displayed excellent chemical and thermal stabilities. They exhibited stable two‐dimensional framework structures in various organic solvents and aqueous media, even over a wide pH range (pH 3–12), while the corresponding model compounds BrPy2BF4/OTf decomposed quickly even in the presence of minimal water. Furthermore, the influence of the counterions were investigated by replacing BF4 with OTf, which improved the stability of XOF(Br). This characteristic enabled XOF(Br) to serve as an efficient oxidizing reagent in aqueous environments, in contrast with the sensitivity of BrPy2BF4/OTf, which performed well only in organic media. This study not only deepens our fundamental understanding of organic frameworks but also opens new avenues for the development and application of multifunctional XOFs.

Halogen-Bonded Organic Frameworks (XOFs) Based on N⋅⋅⋅Br+⋅⋅⋅N Bonds: Robust Organic Networks Constructed by Fragile Bonds.

Organic frameworks face a trade-off between the framework stability and the bond dynamics, which necessitates the development of innovative linkages that can generate stable frameworks without hindering efficient synthesis. Although iodine(I)-based halogen-bonded organic frameworks (XOFs) have been developed, constructing XOFs based on bromine(I) is desirable yet challenging due to the high sensitivity of bromine(I) species. In this work, we present the inaugural construction of stable bromine(I)-bridged two-dimensional (2D) halogen-bonded organic frameworks, XOF(Br)-TPy-BF4/OTf, based on sensitive [N⋅⋅⋅Br⋅⋅⋅N]+ halogen bonds. The formation of XOF(Br)-TPy-BF4/OTf was monitored by 1H NMR, XPS, IR, SEM, TEM, HR-TEM, SEAD. Their framework structures were established by the results from PXRD, theoretical simulations and SAXS. More importantly, XOF(Br) displayed excellent chemical and thermal stabilities. They exhibited stable two-dimensional framework structures in various organic solvents and aqueous media, even over a wide pH range (pH 3-12), while the corresponding model compounds BrPy2BF4/OTf decomposed quickly even in the presence of minimal water. Furthermore, the influence of the counterions were investigated by replacing BF4 with OTf, which improved the stability of XOF(Br). This characteristic enabled XOF(Br) to serve as an efficient oxidizing reagent in aqueous environments, in contrast with the sensitivity of BrPy2BF4/OTf, which performed well only in organic media. This study not only deepens our fundamental understanding of organic frameworks but also opens new avenues for the development and application of multifunctional XOFs.

Water-Based Recycling Process of FTO/SnO2 Substrate for Sustainable Perovskite Solar Cell Technology.

Fluorine-doped tin oxide (FTO) substrate is an important and expensive component in perovskite solar cells (PSCs), which accounts for up to 40% of a typical PSC raw material cost. In this study, we investigated the recyclability of SnO2/FTO in PSCs by washing the spent PSCs using different solvent such as dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetone, water, and acetone/water mixture. Characterisation of properties of the SnO2/FTO substrates recovered from the PSCshow the surface wettability of SnO2/FTO is largely unchanged with water washing while a higher hydrophobicity is obtained with organic solvent washing. Comparison of electronic properties of the SnO2/FTO substrate shows a downward shift of the conduction band by 180 meV with water washing, creating favourable energy alignment with adjacent perovskite for efficient interfacial charge injection. Consequently, PSCs using the water-based recycled SnO2/FTO substrates produced a high power conversion efficiency (PCE) of 19.33% which is comparable to the device using fresh SnO2/FTO substrate (PCE = 19.85%). Furthermore, we demonstrated that the water washing process could retain property of SnO2/FTO substrate for decent PSC performance up to four recycling cycles. This study opens new avenues towards recycling of valuable FTO substrates in PSCs for increased sustainability and cost-effectiveness.

Layer-Ordered Organooxotin Clusters for Extreme-Ultraviolet Photolithography.

Extreme-ultraviolet (EUV) photolithography, which enables the high-throughput production of well-defined patterns with critical dimensions on the scale of several nanometers, is essential for the fabrication of a highly integrated semiconductor. The full exploitation of EUV lithographic techniques necessitates the development of photoresist (PR) materials with both high EUV sensitivity and a long shelf-life. However, despite notable advances, the available library of EUV PR materials remains limited. Here we report EUV PRs capable of forming preorganized layers consisting of ladder-structured tetranuclear stannoxanes. Single-crystal X-ray structure analyses reveal a close interlayer distance of 8.5 Å through interdigitation of the pseudoaxial butyl chains. The developed EUV PR materials exhibit high solubility in organic solvents commonly used in semiconductor processing, enabling the preparation of PR solutions with superior wettability and uniform film-forming ability on Si wafer substrates. These PR solutions also demonstrate notable resistance to hydrolytic decomposition for as long as 1 month, indicating a long shelf-life. Our PR materials enabled negative-tone patterning processes that involved a solubility decrease upon irradiation. The presence of chromophoric ligands makes our PR materials compatible with conventional UV photolithography, through photochemical reactions involving carbonyl units. In addition, e-beam and EUV lithography could produce fine line patterns of our PRs, with critical dimensions of 20 and 15 nm, respectively. Our research showcases the potential of layer-ordered organooxotin clusters for EUV PR applications.

Superhydrophobic Waterborne Epoxy Composite Coating with Good Mechanical Properties, Icing Resistance, Self-Cleaning Properties, and Corrosion Resistance.

Epoxy resins with higher corrosion resistance typically employ environmentally harmful organic solvents such as xylene, while the corrosion resistance of waterborne epoxy resins, which are relatively environmentally friendly, is not as good as that of oil-based epoxy resins. In this study, by coating the surface of waterborne epoxy resin with a superhydrophobic zinc oxide coating, the corrosion resistance of waterborne epoxy resin was enhanced. During the initial immersion, its impedance value can reach 1010 Ω·cm2. The superhydrophobic nature of the coating itself also ensures the surface's resistance to immersion, delaying the intrusion of corrosive media into the coating. Furthermore, this coating exhibits good mechanical properties, self-cleaning performance, anti-icing performance, and so on. The introduction of superhydrophobic surfaces greatly optimizes the performance of traditional waterborne epoxy resin coatings, opening up directions for the metal anticorrosion field of coatings. Meanwhile, during the EIS testing of the superhydrophobic coating, we observed the occurrence of negative impedance in the results. After studying, we speculated that this phenomenon might be related to the degree of wetting of the superhydrophobic coating. Based on this conjecture, we can evaluate the basic properties of the superhydrophobic coating through this phenomenon.

Voltage-induced modulation of interfacial ionic liquids measured using surface plasmon resonant grating nanostructures.

We have used surface plasmon resonant metal gratings to induce and probe the dielectric response (i.e., electro-optic modulation) of ionic liquids (ILs) at electrode interfaces. Here, the cross-plane electric field at the electrode surface modulates the refractive index of the IL due to the Pockels effect. This is observed as a shift in the resonant angle of the grating (i.e., Δϕ), which can be related to the change in the local index of refraction of the electrolyte (i.e., Δnlocal). The reflection modulation of the IL is compared against a polar (D2O) and a non-polar solvent (benzene) to confirm the electro-optic origin of resonance shift. The electrostatic accumulation of ions from the IL induces local index changes to the gratings over the extent of electrical double layer (EDL) thickness. Finite difference time domain simulations are used to relate the observed shifts in the plasmon resonance and change in reflection to the change in the local index of refraction of the electrolyte and the thickness of the EDL. Simultaneously using the wavelength and intensity shift of the resonance enables us to determine both the effective thickness and Δn of the double layer. We believe that this technique can be used more broadly, allowing the dynamics associated with the potential-induced ordering and rearrangement of ionic species in electrode-solution interfaces.

In situ conversion of ZnO to ZIF-8 in polyimide for ultra-high permeance organic solvent nanofiltration mixed matrix membranes

Mixed matrix membranes (MMMs) incorporating ZIF-8 nanoparticles through non-solvent induced phase separation (NIPS) hold great potential in the organic solvent nanofiltration (OSN) field, but their advancement and application have been significantly hindered by ZIF-8’s instability of ZIF-8 in aqueous conditions and major interfacial incompatibilities with polymers. This study presents an approach to overcome these obstacles by initially forming crosslinked ZnO/polyimide (PI) MMMs via NIPS and crosslinking processes, followed by in-situ conversion of ZnO to ZIF-8 within the membrane structure. This method prevents direct contact of ZIF-8 with water, optimizes the interface between ZIF-8 and the polymer, and modulates the pore structure of the membranes. The resulting crosslinked ZIF-8/PI membranes exhibit an ultra-high ethanol permeance of 42.7 L m⁻2 h⁻1 bar⁻1 and a 99.5 % rejection of Rose Bengal dye, surpassing the performance of all state-of-the-art OSN MMMs to our knowledge. Additionally, these membranes also demonstrate excellent separation performance in harsh solvents such as DMF and NMP. The findings of this study not only significantly advance the development of OSN membranes but also offer insights into the optimization of membrane fabrication techniques, setting a new benchmark for the design of high-performance OSN membranes.

Shark anti-idiotypic variable new antigen receptor specific for an alpaca nanobody: exploration of a nontoxic substitute to ochratoxin A in immunoassay

Nontoxic substitutes to mycotoxins can facilitate the development of eco-friendly immunoassays. To explore a novel nontoxic substitute to ochratoxin A (OTA), this study screened shark anti-idiotypic variable new antigen receptors (VNARs) against the alpaca anti-OTA nanobody Nb28 through phage display. After four rounds of biopanning of a naïve VNAR phage display library derived from six adult Chiloscyllium plagiosum sharks, one positive clone, namely, P-3, was validated through a phage enzyme–linked immunosorbent assay (phage ELISA). The recombinant anti-idiotypic VNAR AId-V3 was obtained by prokaryotic expression, and the interactions between Nb28 and AId-V3 were investigated via computer-assisted simulation. The affinity of AId-V3 for Nb28 and its heptamer Nb28-C4bpα was measured using Biacore assay. Combining Nb28-C4bpα with AId-V3, a novel direct competitive ELISA (dcELISA) was developed for OTA analysis, with a limit of detection of 0.44ng/mL and a linear range of 1.77-32.25ng/mL. The good selectivity, reliability, and precision of dcELISA were confirmed via cross-reaction analysis and recovery experiments. Seven commercial pepper powder samples were tested using dcELISA and validated using high-performance liquid chromatography. Overall, the shark anti-idiotypic VNAR was demonstrated as a promising nontoxic substitute to OTA, and the proposed method was confirmed as a reliable tool for detecting OTA in food. Environmental ImplicationOchratoxin A (OTA) is a common mycotoxin in food and has been listed as a Group 2B human carcinogen by IARC. In traditional immunoassays, chemical synthesis of OTA artificial antigens requires abundant OTA standard and organic solvent, which threatens the operator’s health and environmental safety. This manuscript reports a novel nontoxic substitution to OTA (anti-idiotypic VNAR) that was screened with anti-OTA alpaca nanobody from the naïve phage display shark VNAR library. The nanobody and anti-idiotypic VNAR were then used to develop a novel direct competitive ELISA to detect OTA in pepper, which is economical and eco-friendly.

Utilizing Carbon Dots Derived from Waste Face Masks for Pentachlorophenol Detection.

Pentachlorophenol is a very toxic chemical that is used as a pesticide, fungicide, herbicide, wood preservative, etc., and it should be monitored in terms of human health and environmental production. Another environmental problem is the increase in the use of facemasks, especially during the COVID-19 pandemic. This study provides a value added chemicals to sustainability of recycling process. Fluorescent carbon dots (CDs) were synthesized from waste facemasks and investigated their fluorescence sensor performances. UV-Vis and fluorescence spectra of the synthesized carbon dots were recorded in different organic solvents. The sensor properties of these carbon dots against pesticides were investigated, and a 'turn-off' response was observed toward pentachlorophenol. The limit of detection was found 8.5 µM in the linear range from 43.3 µM to 375 µM. This study showed that waste plastics such as facemasks can be recycled to obtain carbon dots, which are used in different technological areas such as photocatalysis, bioimaging, etc., as well as in sensors.

Optimized Ultrasonic Extraction of Essential Oil from the Biomass of Lippia graveolens Kunth Using Deep Eutectic Solvents and Their Effect on Colletotrichum asianum

Essential oils are emerging as alternatives to conventional pest control chemicals. Lippia graveolens Kunth (Mexican oregano) is a source of essential oils and during conventional extraction, the biomass generated is discarded as waste; however, reports show that this biomass is still a rich source of essential oils. Conventional essential oil extraction causes contamination and utilizes toxic solvents. Deep eutectic solvents (DESs) offer low toxicity, biodegradability, high selectivity, and yields comparable to organic solvents. This study obtained essential oil from Lippia graveolens biomass via hydrodistillation with ultrasound-assisted DES pretreatment. This research aimed to optimize the extraction of essential oil from Lippia graveolens biomass using ultrasound-assisted DESs and assess its in vitro and in vivo inhibitory effect on C. asianum. The response variables were extraction yield and total reducing capacity. Optimal conditions were determined using a central composite rotatable design, considering solid-to-liquid ratio (0.38 g/mL), ultrasonic amplitude (45.05%), and time (7.47 min). The optimized oil, with thymol (48%) as the predominant component, exhibited more volatile compounds than conventional hydrodistillation. Fungicidal assays highlighted its potential in controlling anthracnose in papaya fruits caused by C. asianum, making ultrasound-assisted DES pretreatment a promising alternative for obtaining essential oil from botanical byproducts.

Prenylation of aromatic amino acids and plant phenolics by an aromatic prenyltransferase from Rasamsonia emersonii

Dimethylallyl tryptophan synthases (DMATSs) are aromatic prenyltransferases that catalyze the transfer of a prenyl moiety from a donor to an aromatic acceptor during the biosynthesis of microbial secondary metabolites. Due to their broad substrate scope, DMATSs are anticipated as biotechnological tools for producing bioactive prenylated aromatic compounds. Our study explored the substrate scope and product profile of a recombinant RePT, a novel DMATS from the thermophilic fungus Rasamsonia emersonii. Among a variety of aromatic substrates, RePT showed the highest substrate conversion for l-tryptophan and l-tyrosine (> 90%), yielding two mono-prenylated products in both cases. Nine phenolics from diverse phenolic subclasses were notably converted (> 10%), of which the stilbenes oxyresveratrol, piceatannol, pinostilbene, and resveratrol were the best acceptors (37–55% conversion). The position of prenylation was determined using NMR spectroscopy or annotated using MS2 fragmentation patterns, demonstrating that RePT mainly catalyzed mono-O-prenylation on the hydroxylated aromatic substrates. On l-tryptophan, a non-hydroxylated substrate, it preferentially catalyzed C7 prenylation with reverse N1 prenylation as a secondary reaction. Moreover, RePT also possessed substrate-dependent organic solvent tolerance in the presence of 20% (v/v) methanol or DMSO, where a significant conversion (> 90%) was maintained. Our study demonstrates the potential of RePT as a biocatalyst for the production of bioactive prenylated aromatic amino acids, stilbenes, and various phenolic compounds.Key points• RePT catalyzes prenylation of diverse aromatic substrates.• RePT enables O-prenylation of phenolics, especially stilbenes.• The novel RePT remains active in 20% methanol or DMSO.Graphical abstract

Lignocellulosic biomass to glycols: Simultaneous conversion of cellulose, hemicellulose and lignin using an organic solvent

This study investigates the simultaneous conversion of holocellulose and lignin fractions during the catalytic hydrogenolysis of biomass to glycols, focusing on how different organic solvents, necessary to keep the lignin soluble, impact the conversion of non-delignified and deashed biomass, as well as the ethylene glycol production and lignin behavior. Although the catalyst amounts used were low, the cellulose and hemicellulose were converted into ethylene glycol, propylene glycol, sugar alcohols, and glycerol, yielding about 40 wt%. This is slightly lower than the benchmark process (acidified water and de-ashed biomass), which had a total yield of around 50 wt%. A noticeable difference between using organic solvents and water was found in the behavior of depolymerized lignin. When using an organic solvent, up to 63 % of the lignin could be extracted from the biomass and kept soluble, compared to only 15 % when using acidified water. The molecular weight distribution of solubilized lignin was similar for all organic solvents (Mw = 833–1190 g/mol), but it was significantly different from the benchmark experiment with acidified water (Mw = 423 g/mol).

Charge Transfer and Intersystem Crossing in Compact Naphthalenediimide-Phenothiazine Triads: Synthesis and Study of the Photophysical Property with Transient Optical and Electron Paramagnetic Resonance Spectroscopic Methods.

In order to obtain a long-lived charge separation (CS) state in compact electron donor-acceptor molecular systems, we prepared a series of naphthalenediimide (NDI)-phenothiazine (PTZ) triads, with phenylene as the linker between the donor and acceptor. Conformation restriction is imposed to control the mutual orientation of the NDI and PTZ units by attaching methyl groups on the phenylene linker to tune the electronic coupling between the donor and the acceptor. Moreover, the PTZ moiety was oxidized to sulfoxide to tune the ordering of the CS state and the 3LE state (LE: locally excited state). UV-vis absorption spectra indicate electronic coupling between NDI with the phenylene linker as well as the PTZ units, manifested by the appearance of a charge-transfer (CT) absorption band, whereas this coupling is devoid in the triads with conformation restriction imposed. Fluorescence is strongly quenched in the triads compared to the reference compound, indicating electron transfer upon photoexcitation. Femtosecond transient absorption spectra indicate that the CS takes 0.8 ps, and then the 3LE state is formed by charge recombination in 83 ps. Nanosecond transient absorption (ns-TA) spectra show that the 3NDI state was observed in nonpolar solvents such as cyclohexane (triplet state lifetime: 95.7 μs), whereas the CS state was observed in more polar solvents. The CS state lifetimes are up to 1.2 μs (in toluene). Time-resolved electron paramagnetic resonance spectra of the triads in toluene consist of two types of signals: CS states (narrower signals, ∼10 mT) and 3LE states (broader signals, ∼50 to 200 mT). In the spectra of the triads containing PTZ, the CS state signals dominate, whereas for the triads containing oxidized PTZ, the 3NDI signals (zero-field splitting D ≈ 2000 MHz) prevail, both observations being in agreement with the ns-TA spectral studies. The electron spin polarization phase pattern of the 3NDI states of the triads indicates that the intersystem crossing (ISC) mechanism is spin-orbit charge-transfer ISC. Considering the 3CS state as ion pairs, the electron-exchange energy (J) is determined to be -39 to -59 MHz, and the electron spin dipolar interaction is 83-92 MHz.

Selective Liquid-Liquid Extraction of Thorium(IV) from Rare-Earth Element Mixtures.

One of the major challenges in processing rare-earth element (REE) materials arises from the large amounts of radioactive thorium (Th) that are often found within REE minerals, encouraging enhanced metal separation procedures. We report here a study aimed at developing improved systems for REE processing with the goal of efficient extraction of Th(IV) from acidic solution. A tripodal ligand, TRPN-CMPO-Ph, was prepared that utilizes carbamoylmethylphosphine oxide (CMPO) chelators tethered to a tris(3-aminopropyl)amine (TRPN) capping scaffold. The ligand and its metal complexes were characterized by using elemental analysis, NMR, Fourier transform infrared spectroscopy, mass spectrometry, and luminescence spectroscopy. Using a liquid-liquid metal extraction protocol, TRPN-CMPO-Ph selectively extracts Th(IV) at an efficiency of 79% from a mixture of Th(IV), UO22+, and all rare-earth metal cations (except promethium) dissolved in nitric acid into an organic solvent. Th(IV) extraction selectivity is maintained upon extraction from a mixture that approximates a typical monazite leach solution containing several relevant lanthanide ions, including two ions at higher concentration relative to Th(IV). Comparative studies with a tris(2-aminoethyl)amine (TREN)-capped derivative are presented and support the need for a larger TRPN capping scaffold in achieving Th(IV) extraction selectivity.

Colloidal Titanium Nitride Nanoparticles by Laser Ablation in Solvents for Plasmonic Applications

Titanium nitride (TiN) is a candidate material for several plasmonic applications, and pulsed laser ablation in liquids (PLAL) represents a rapid, scalable, and environmentally friendly approach for the large-scale production of nanomaterials with customized properties. In this work, the nanosecond PLAL process is developed, and we provide a concise understanding of the process parameters, such as the solvent and the laser fluence and pulse wavelength, to the size and structure of the produced TiN nanoparticles (NPs). TiN films of a 0.6 μm thickness developed by direct-current (DC) magnetron sputtering were used as the ablation targets. All laser process parameters lead to the fabrication of spherical NPs, while the laser pulse fluence was used to control the NPs’ size. High laser pulse fluence values result in larger TiN NPs (diameter around 42 nm for 5 mJ and 25 nm for 1 mJ), as measured from scanning electron microscopy (SEM). On the other hand, the wavelength of the laser pulse does not affect the mean size of the TiN NPs (24, 26, and 25 nm for 355, 532, and 1064 nm wavelengths, respectively). However, the wavelength plays a vital role in the quality of the produced TiN NPs. Shorter wavelengths result in NPs with fewer defects, as indicated by Raman spectra and XPS analysis. The solvent type also significantly affects the size of the NPs. In aqueous solutions, strong oxidation of the NPs is evident, while organic solvents such as acetone, carbides, and oxides cover the TiN NPs.

Photochemical Vs Thermal Acid Catalysed Cyclization of Cannabigerol (CBG): An Unexpected Selectivity

AbstractThe reactivity of Cannabigerol (CBG, 1) in organic solvents under photochemical and acid catalyzed conditions has been investigated in detail. The obtained results pointed out the presence of different reaction paths in the photochemical and the acid‐catalyzed conditions, with a remarkable selectivity toward the formation of a 2,2‐disubstituted‐chromane derivative in the first case.