Polar Solvents Research Articles

Synthesis and Structural Characterization of a Non-Heme Iron Hyponitrite Complex.

Flavodiiron NO reductases (FNORs) are important enzymes in microbial pathogenesis, as they equip microbes with resistance to the human immune defense agent nitric oxide (NO). Despite much efforts, intermediates that would provide insight into how the non-heme diiron active sites of FNORs reduce NO to N2O could not be identified. Computations predict that iron-hyponitrite complexes are the key species, leading from NO to N2O. However, the coordination chemistry of non-heme iron centers with hyponitrite is largely unknown. In this study, we report the reactivity of two non-heme iron complexes with preformed hyponitrite. In the case of [Fe(TPA)(CH3CN)2](OTf)2, cleavage of hyponitrite and formation of an Fe2(NO)2 diamond core is observed. With less Lewis-acidic [Fe2(BMPA-PhO)2(OTf)2] (2), reaction with Na2N2O2 in polar aprotic solvent leads to the formation of a red complex, 3. X-ray crystallography shows that 3 is a tetranuclear iron-hyponitrite complex, [{Fe2(BMPA-PhO)2}2(μ-N2O2)](OTf)2, with a unique hyponitrite binding mode. This species provided the unique opportunity to us to study the interaction of hyponitrite with non-heme iron centers and the reactivity of the bound hyponitrite ligand. Here, either protonation or oxidation of 3 is found to induce N2O formation, supporting the hypothesis that hyponitrite is a viable intermediate in NO reduction.

Synthesis and Structural Characterization of a Non‐Heme Iron Hyponitrite Complex

Flavodiiron NO reductases (FNORs) are important enzymes in microbial pathogenesis, as they equip microbes with resistance to the human immune defense agent nitric oxide (NO). Despite much efforts, intermediates that would provide insight into how the non‐heme diiron active sites of FNORs reduce NO to N2O could not be identified. Computations predict that iron‐hyponitrite complexes are the key species, leading from NO to N2O. However, the coordination chemistry of non‐heme iron centers with hyponitrite is largely unknown. In this study, we report the reactivity of two non‐heme iron complexes with preformed hyponitrite. In the case of [Fe(TPA)(CH3CN)2](OTf)2, cleavage of hyponitrite and formation of an Fe2(NO)2 diamond core is observed. With less Lewis‐acidic [Fe2(BMPA‐PhO)2(OTf)2] (2), reaction with Na2N2O2 in polar aprotic solvent leads to the formation of a red complex, 3. X‐ray crystallography shows that 3 is a tetranuclear iron‐hyponitrite complex, [{Fe2(BMPA‐PhO)2}2(μ‐N2O2)](OTf)2, with a unique hyponitrite binding mode. This species provided the unique opportunity to us to study the interaction of hyponitrite with non‐heme iron centers and the reactivity of the bound hyponitrite ligand. Here, either protonation or oxidation of 3 is found to induce N2O formation, supporting the hypothesis that hyponitrite is a viable intermediate in NO reduction.

Poly(ether-ether-ketone) copolymers featuring sulfonyl moieties for organic solvent nanofiltration membranes

Poly(ether-ether-ketone) (PEEK) is an attractive material for membrane fabrication due to its exceptional thermal and chemical stability. However, traditional PEEK processing necessitates the use of harsh chemicals, such as sulfuric acid because of its limited solubility in organic solvents. To overcome this limitation, copolymers offer a solution by enhancing solubility and subsequently improving membrane characteristics such as permeability and selectivity. Herein, three novel copolymers – PEEK with various contents of SO2 and CH3 – were developed and used in membranes for the separation of polar and non-polar solvents. The chemical structure of the copolymers was tailored by varying the monomer ratio between 0.25 and 0.75 for CH3 and SO2 containing monomers. Diamine–crosslinked PEEK copolymer membranes were prepared using a green solvent (TamiSolve). The effects of the polymer structure, the dope solution rheology, and membrane properties together with separation performance were studied. The resulting membranes demonstrated a permeance for acetonitrile ranging from 7.4 to 8.2 L m−2 h−1 bar−1 with molecular weight cutoffs of 839–915 g mol−1. Molecular dynamic simulations were conducted to explore the interaction between the copolymers and nine different organic solvents. Our findings underscore the significance of copolymer design in achieving tailored membrane properties for diverse separations.

Theoretical study on precise regulation of ESIPT reaction based on ICT effect of o-carborane derivatives

The unique stereocarborane fluorophore design has attracted widespread attention because of its ability to effectively enhance the performance of thin-film fluorescence sensors. This study provides a detailed theoretical investigation of the excited-state intramolecular proton transfer (ESIPT) reactions of three o-carborane derivatives, NaCBO, PaCBO and PyCBO, using density functional theory and time-dependent density functional theory. We found that as the number of benzene rings in the electron donor groups increases, the interaction between the first excited-state electron donor–acceptor fragments is enhanced, weakening the intramolecular hydrogen bonding strength, which in turn inhibits the ESIPT. Notice that the intramolecular charge transfer (ICT) is proportional to the interaction between electron donor and acceptor fragments with the analysis of electron structure. The higher the ICT level of the target system, the more unstable the keto form generated by ESIPT. Therefore, the ESIPT can be precisely manipulated by rationally adjusting the ICT effect. Furthermore, with increasing solvent polarity, the photophysical properties of the chromophores exhibit non-solvatochromism. This is attributed to the rigid o-carborane structure, which serves as a spatial scaffold to increase the adaptability of the molecule to the environment. This study is expected to provide theoretical guidance and new ideas for preparing high-performance thin-film fluorescence sensing.

Oxindolyl-Based Radicals with Tunable Mechanochromic and Thermochromic Behavior.

Organic radicals based dynamic covalent chemistry is promising in preparing stimuli-responsive chromic materials, due to their simplicity of dissociation/association, accompanied with distinct color changes during the process. However, suitable organic radicals for dynamic covalent chemistry have not been widely explored yet. Herein, a series of oxindolyl-based mono-radicals (OxRs) with different substituents were successfully synthesized and studied systematically as potential building blocks for stimuli-responsive chromic materials. These OxRs would dimerize spontaneously to form their corresponding dimers. The structures of dimers were unambiguously confirmed through low-temperature 1H NMR and single-crystal X-ray diffraction analyses. Dynamic interconversion between monomers and dimers was achieved by reversible cleavage and recovery of the σ-bond upon soft external stimuli (temperature, pressure, and solvent polarity), accompanied by significant color changes. It is interesting that the stability of the mono-radical could be tuned through changing different substituents, and consequently altering the bond dissociation energy of the dynamic covalent bond between monomers. These new OxRs characterized by appreciable properties are entitled to more opportunities in developing mechanochromic and thermochromic materials, where their responsiveness to stimuli can be readily controlled by the substituents adhered.

Oxindolyl‐based Radicals with Tunable Mechanochromic and Thermochromic Behavior

Organic radicals based dynamic covalent chemistry is promising in preparing stimuli‐responsive chromic materials, due to their simplicity of dissociation/association, accompanied with distinct color changes during the process. However, suitable organic radicals for dynamic covalent chemistry have not been widely explored yet. Herein, a series of oxindolyl‐based mono‐radicals (OxRs) with different substituents were successfully synthesized and studied systematically as potential building blocks for stimuli‐responsive chromic materials. These OxRs would dimerize spontaneously to form their corresponding dimers. The structures of dimers were unambiguously confirmed through low‐temperature 1H‐NMR and single‐crystal X‐ray diffraction analyses. Dynamic interconversion between monomers and dimers was achieved by reversible cleavage and recovery of the σ‐bond upon soft external stimuli (temperature, pressure, and solvent polarity), accompanied by significant color changes. It is interesting that the stability of the mono‐radical could be tuned through changing different substituents, and consequently altering the bond dissociation energy of the dynamic covalent bond between monomers. These new OxRs characterized by appreciable properties are entitled to more opportunities in developing mechanochromic and thermochromic materials, where their responsiveness to stimuli can be readily controlled by the substituents adhered.

Tuning the Solubility of Soluble Support Constructs in Liquid Phase Oligonucleotide Synthesis.

Solubility of the growing oligonucleotide-soluble support constructs in the liquid phase oligonucleotide synthesis (LPOS) is a critical parameter, which affects coupling efficiency, purity, and recovery of the growing oligonucleotides during the chain elongation. In the present study, oligonucleotides have been assembled on a 4-oxoheptanedioic acid (OHDA) linker-derived tetrapodal soluble support using 5'-O-(2-methoxyprop-2-yl)-protected 2'-deoxyribonucleotide phosphoroamidite building blocks with different nucleobase protecting groups [isobutyryl (Gua), 1-butylpyrrolidin-2-ylidene (Gua, Cyt), 2,4-dimethylbenzoyl (Ade, Cyt), and Bz (Thy)]. The solubility of the oligonucleotide-soluble support constructs (molecular mass varying between 3 and 10 kDa) as models of protected tetra-, octa-, dodeca-, hexadeca-, and eicosa-nucleotides was measured in different solvent systems and in potential antisolvents. By tuning the nucleobase protecting group scheme, the solubility can be improved in aprotic organic solvent systems, while the recovery of the constructs in the precipitation, used for the isolation and purification of the growing oligonucleotide intermediates in a protic antisolvent (2-propanol), remained near quantitative. The precipitation-based yield of the protected tetrapodal oligonucleotides varied from a quantitative to 90% yield. Overall yield (for di-: 95%, tri-: 79-96%, tetra-: 82-88%, and pentanucleotides: 68-75%) and purity of the LPOS were evaluated by RP HPLC and MS-spectroscopy of the released oligonucleotide aliquots. In addition, the orthogonality of the OHDA linker was applied to release authentic protected nucleotides from the soluble supports.

Binary Catalytic Hydrogen/Deuterium Exchange of Free α-Amino Acids and Derivatives.

The increasing demand for deuterium-labeled amino acids and derivatives has heightened interest in direct hydrogen/deuterium exchange reactions of free amino acids. Existing methods, including biocatalysis and metal catalysis, typically require expensive deuterium sources or excessive use of deuterium reagents and often struggle with site selectivity. In contrast, this binary catalysis system, employing benzaldehyde and Cs2CO3 in the presence of inexpensive D2O with minimal stoichiometric quantities, facilitates efficient hydrogen/deuterium exchange at the α-position of amino acids without the need for protecting groups in the polar aprotic solvent DMSO. The process is highly compatible with most natural and non-natural α-amino acids and derivatives, even those with potentially reactive functionalities. This advancement not only addresses the cost and efficiency concerns of existing methods but also significantly broadens the applicability and precision of deuterium labeling in biochemical research.

Integrated Instructions and Solvent Polarity Indicators: Reducing the Complexity of First-Time Distillation

Integrated Instructions and Solvent Polarity Indicators: Reducing the Complexity of First-Time Distillation

Ostwald ripening inhibition by a bipolar ligand achieves long-term-reaction and scalable synthesis of ultra-stable CsPbX3 perovskite quantum dots towards LEDs

All-inorganic perovskite quantum dots (PeQDs) hold immense potential for use in light-emitting diodes (LEDs) due to their excellent optoelectronic properties. However, the scalable synthesis and poor stability have severely hindered their application. Here, we solved both the two issues with “one stone”, namely a bipolar ligand 3-(N,N-dimethyloctadecylammonio) propane sulfonate (ASC18). ASC18 contains a positively charged quaternary ammonium group and a negatively charged sulfonic group, which enables for long-term reaction and gram-level synthesis of PeQDs with outstanding morphology, crystallinity, and optical properties. Density functional theory calculations and experimental studies show that these merits arise from the inhibition of Ostwald ripening by ASC18 due to their simultaneous interaction with undercoordinated Br– and Pb2+ via a bidentate binding mode. Furthermore, ASC18 capped PeQDs present significantly improved stabilities against air, UV irradiation, heat, and polar solvent. Finally, both electroluminescent LEDs and down-conversion white LEDs fabricated with our PeQDs show significant operational stability. This presents a trustworthy avenue to obtain high-quality PeQDs for their practical applications.

One-pot synthesis of 5-norbornene-2,3-dicarboxylic anhydride with high exo/endo ratio in a microreactor under high temperature and appropriate pressure

5-Norbornene-exo-2,3-dicarboxylic anhydride (exo-NDA), widely used in the synthesis of medicine and pesticide, was primarily obtained through the subsequent thermal isomerization of 5-norbornene-endo-2,3-dicarboxylic anhydride (endo-NDA) synthesized from cyclopentadiene (CPD) and maleic anhydride (MAH). Herein, density functional theory (DFT) was employed to elucidate the transition states and reaction pathways of different configurations. The endo-path exhibited a lower energy barrier, and the exo-isomer demonstrates greater structural stability. It was found that both high temperature and solvent polarity influenced the generation of NDA with different configurations. Due to considering solubility of MAH, an acetone/ethylbenzene mixed solvent was chosen for the reaction instead. According to the DFT calculations, we developed continuous-flow microreactor for high-efficiency one-pot synthesis of the isomers with exo/endo ratio of up to 1.19:1 as well as almost 100 % conversion and 98 % selectivity just in 2 min at 260 °C and 4 MPa, which CPD was generated in situ to participate in a series of Diels-Alder reactions instead of dicyclopentadiene as raw material existed at room temperature. Moreover, excessive or insufficient pressure in the reaction system should elevate byproduct formation, resulting in a decrease in reaction selectivity, as could prolonged residence time.

High quantum yield blue fluorescent molecule of hydroxybenzo[c]chromen-6-ones: Synthesis and fluorescence characteristics

Hydroxybenzo[c]chromen-6-ones had been synthesized by the reaction of hydroxy‑substituted chalcone and ethyl acetoacetate in the presence of Cs2CO3 and their optical properties were then investigated. We found it particularly that dimethylamino-substituted hydroxybenzocoumarin 4e had extremely high quantum yield blue fluorescence (λem = 487 nm, ФF = 0.83) in dichloromethane and the fluorescence red shifted with the increase of solvent polarity, which had a good solvatochromic effect on the polarity of the solvent. Additionally, DFT and TD-DFT calculations were applied to explain and verify the good fluorescence properties of hydroxybenzo[c]chromen-6-one 4e.

Regiospecific Synthesis of 1,4-Diaryl-5-cyano-1,2,3-triazoles and Their Photoconversion to 2- or 3-Cyanoindoles.

We report the synthesis of 1,4-diaryl-5-cyano-1,2,3-triazoles from azides and alkynes via two copper-mediated steps. Aryl-substituted cyanotriazoles are emissive in nonpolar solvents. When the N1-aryl group is electron-donating, the photoconversion of a cyanotriazole to a cyanoindole is efficient. Each of the seven pairs of 4- and 5-cyanotriazole isomers is photoconverted to either distinctive cyanoindoles without rearrangement or a major cyanoindole product via the presumed common intermediate azirine. The resulting cyanoindoles appear to be stronger emitters in polar solvents than the parent cyanotriazoles.

Super-Resolution Microscopic Imaging of Lipid Droplets in Living Cells via Carbonized Polymer Dot-Based Polarity-Responsive Nanoprobe.

Lipid droplets (LDs) are dynamic subcellular organelles that participate in various physiological processes, and their abnormality can also lead to various diseases. Tracing the dynamics of LDs in living cells will be valuable for understanding cell physiological states. Here, we employed a structured light illumination super-resolution imaging assisted with a carbonized polymer dot (CPD)-based fluorescence nanoprobe to track the travel paths of LDs and other organelles. The CPDs we developed are highly biocompatible with living cells and exhibit a highly sensitive response to solvent polarity, allowing for high specificity in staining LDs in living cells. Aided by these nanoprobes, we successfully observed many real-time LD-involved dynamics in living cells, such as intracellular LD interactions, communications with other organelles, and dynamic behaviors under external stimuli (oxidative stress inducer). These studies deepen our comprehension of the physiological role of LDs and drive the advancement of super-resolution fluorescent probes.

Investigating the role of solvents in modulating glass transition and dynamic mechanical characteristics of polystyrene film

This study investigates how different solvents impact the glass transition and dynamic mechanical properties of polystyrene (PS) films. Using FTIR spectroscopy, it analyzes solvent-induced variations in molecular vibrations, particularly in the phenyl ring region. Results show solvent-specific effects on the 750 cm-1 peak, associated with the "meta-substituted aromatic ring," influencing phenyl ring vibrations. DSC analysis highlights solvent effects on the glass transition temperature (Tg), revealing complexities in PS films prepared with chloroform, tetrahydrofuran (THF), and toluene. Varied Tg behavior suggests solvent-driven structural modifications and gradual solvent removal. Dynamic Mechanical Analysis (DMA) demonstrates solvent-dependent changes in storage modulus, loss modulus, and tan δ, indicating solvent polarity role in polymer chain dynamics. Toluene-induced plasticization reduces Tg and increases creep compliance, revealing PS film sensitivity to solvents. These findings stress solvent selection importance in tailoring thermal and mechanical properties of polymer films for specific applications.

Structural and spectroscopic characterization of N1,N2-diphenylacenapthylene-1,2-diimines and the influence of substituents on the viscosity of alkyl magnesium solutions

Butyl octyl magnesium solutions are important raw materials in various chemical processes but suffer from their high reactivity with even traces of water, protic solvents or oxygen and an increased viscosity in hydrocarbon solution due to the formation of polymeric structures. N1,N2-diphenylacenaphthylene-1,2-diimines (BIANs) have already been identified as potential candidates to reduce the viscosity of alkyl magnesium solutions and this study provides a systematic insight into the dependence of this ability on the position and structures of substituents on the BIAN. Besides the various BIANs, ZnCl2 complexes and hydrogenated derivatives were characterized and tested for their ability to reduce the viscosity. HPLC-high resolution mass spectrometry, MALDI-ToF mass spectrometry, but most important FTIR and NMR experiments under inert conditions have been used to shine light on the interaction of the different BIAN derivatives with alkyl magnesium solutions. Hydrogenated BIANs, especially those with bulky alkyl groups in the ortho position(s) have been identified as the most promising candidates. An additional benefit of the hydrogenated species is that in contrast to BIANs and BIAN-Zn complexes they do not undergo permanent chemical modification and can be reused after extraction.

Complexes of Copper(II) and Adenine at Various pH: Synthesis and Characterization

The coordination of Cu(II) ion with purine base is pH dependent and versatile. This study describes the synthesis, structuralcomponents and coordination behavior of Cu(II) with adenine. Three complexes of Cu(II) with adenine have been preparedat different pH in aqueous solution and ambient conditions. All synthesized complexes are polycrystalline solids of variouscolors, air-stable and partially soluble in polar solvents. The complexes were characterized by numerous analytical techniques including compositional analyses, Fourier transform infrared and UV-visible analyses, and thermal investigation. The elemental analyses of the complexes established their chemical composition as [Cu(adeninium)Cl3], [Cu(adenine)(H2O)Cl2] and [Cu(H2O)2(adeninato)2]. Analytical results suggest that the adenine nucleobase could act as a cationic (pH: 5), or a neutral (pH: 7), or an anionic (pH: 8) monodentate ligand in pH facilitated aqueous solution. In the structure, the purine moiety, chloride ion and aqua groups are situated around the copper(II) center is basically in a tetrahedral arrangements. Protonation or deprotonation of the adenine and intramolecular interligand hydrogen bond assisted the pH dependent versatile coordinating behavior of purine base. Dhaka Univ. J. Sci. 72(2): 84-90, 2024 (July)

Surface modification effects on ammonium perchlorate wettability

Solid propellants are commonly used for propulsion systems due to their high volumetric thrust and reliability. Powder bed, binder jetting manufactured propellants will enable unique geometries to be made that are necessary for designers to achieve high thrust levels. However, changes to the particulate wettability from the solvent-based manufacturing technique must be understood such that propellants with adequate mechanical properties are achieved. In this work, the wettability of ammonium perchlorate (AP) crystal surfaces is quantified with solvent and air plasma treatments. Removal of adventitious carbon from AP surface decreases the polybutadiene contact angle from 34 ± 1° to 15 ± 4°. The presence of hydrocarbons from non-polar solvents used in this study with lower vapor pressure was observed to have a similar effect as the adventitious carbon whereas higher vapor pressure solvents have minimal influence on the final wettability of AP surfaces. Polar solvents were determined to alter the surface topology by creating a more hydrophobic surface when compared to the plasma treated samples. An increase in concentration of amine surface groups overcomes the decrease in wettability from carbonaceous residue and surface morphology. The extension and implications of these findings to powder bed, binder jetting manufacturing for propellants is discussed.

Copper and ZnO Dual-Catalyzed Photo-Assisted Depolymerization of Poly(Methyl Methacrylate) without Deoxygenation

Despite significant advancements in thermal and photothermal depolymerizations, the success of these techniques relies on tedious deoxygenation procedures. Herein, we report the development of the depolymerization technique efficient without prior deoxygenation, which was enabled by copper/ligand complexes and the inclusion (0.25 wt% relative to solvent) of zinc oxide (ZnO) nanocrystals activated by UV light. This approach was tested for poly(methyl methacrylate) (PMMA) prepared by atom transfer radical polymerization (ATRP); the effects of solvent polarity and the activity of ligands were investigated. Unexpectedly, a low-activity Cu-complex with 2,2‘-bipyridine ligand, in combination with a low-polarity solvent, 1,2,4-trichlorobenzene, enabled relatively high depolymerization yields in less than 1 h at 150 °C. Higher activity ATRP complexes with tris(2-pyridylmethyl)amine (TPMA) and N,N,N‘,N‘‘,N‘‘-pentamethyldiethylenetriamine (PMDETA) ligands, were less efficient, which was associated with their thermal decomposition and/or the excessive formation of radicals and premature termination of the chain ends. The presented facile approach was designed to be used even in partially aerated reactors, opening new avenues for efficient depolymerization.

CsPbBr3@PbSO4 nanocomposites with near-unity photoluminescence and ultrastability via in-water in situ embedding synthesis strategy

Perovskite quantum dots (PQDs) are emerging as promising nanomaterials for optoelectronic applications. However, developing a cost-effective green synthesis process that simultaneously possesses satisfactory photoluminescence quantum yield (PLQY) and stability remains a severe challenge. Here, CsPbBr3@PbSO4 nanocomposites with a near-unity PLQY of 99.8 % and robust ambient stability are synthesized in situ in water via 4-Bromobenzenesulfonic acid and ditetradecylamine ligands. Notably, these nanocomposites show no decline in PLQY even after being immersed in water for over 250 days, and also exhibit superior stability against heating, ultrasonication, UV irradiation, anion exchange, and erosion by polar solvents. First-principles calculations reveal that CsPbBr3@PbSO4 nanocomposites can form a natural quantum well structure, which effectively promotes the radiative recombination of carriers in CsPbBr3 QDs. Meanwhile, the remarkable stability is attributed to the ultrahigh decomposition enthalpy of PbSO4 that serves as a strong barrier preventing the invasion of anions and polar media into the embedded CsPbBr3 QDs. Finally, besides the convenient application of green fluorescent paper, a fingerprint recognition is demonstrated by fabricating a bright-green LED integrated with the CsPbBr3@PbSO4 nanocomposites powder and a commercial UV chip. This work provides a new strategy for green synthesis and practical application of high-efficient and ultrastable PQDs.