Polar Solvents Research Articles

Colloidal Dispersions of Sterically and Electrostatically Stabilized PbS Quantum Dots: Structure Factors, Second Virial Coefficients, and Film-Forming Properties.

Electrostatically stabilized nanocrystals (NCs) and, in particular, quantum dots (QDs) hold promise for forming strongly coupled superlattices due to their compact and electronically conductive surface ligands. However, studies of the colloidal dispersion and interparticle interactions of electrostatically stabilized sub-10 nm NCs have been limited, hindering the optimization of their colloidal stability and self-assembly. In this study, we employed small-angle X-ray scattering (SAXS) experiments to investigate the interparticle interactions and arrangement of PbS QDs with thiostannate ligands (PbS-Sn2S64-) in polar solvents. The study reveals significant deviations from the ideal solution behavior in electrostatically stabilized QD dispersions. Our results demonstrate that PbS-Sn2S64- QDs exhibit long-range interactions within the solvent, in contrast to the short-range steric repulsion characteristic of PbS QDs with oleate ligands (PbS-OA). Introducing highly charged multivalent electrolytes screens electrostatic interactions between charged QDs, reducing the length scale of the repulsive interactions. Furthermore, we calculated the second virial (B2) coefficients from SAXS data, providing insights into how surface chemistry, solvent, and size influence pair potentials. Finally, we explore the influence of long-range interparticle interactions of PbS-Sn2S64- QDs on the morphology of films produced by drying or spin-coating colloidal solutions. The long-range repulsive term of PbS-Sn2S64- QDs promotes the formation of amorphous films, and screening the electrostatic repulsion by the addition of an electrolyte enables the formation of crystalline domains. These findings highlight the critical role of NC-NC interactions in tailoring the properties of functional materials made of colloidal NCs.

Sodium dodecyl sulfate‐coated silver nanoparticles accelerate antimicrobial potentials by targeting amphiphilic membranes

AbstractCompelling concerns about antimicrobial resistance and the emergence of multidrug‐resistant pathogens call for novel strategies to address these challenges. Nanoparticles show promising antimicrobial activities; however, their actions are hindered primarily by the bacterial hydrophilic–hydrophobic barrier. To overcome this, we developed a method of electrochemically anchoring sodium dodecyl sulfate (SDS) coatings onto silver nanoparticles (AgNPs), resulting in improved antimicrobial potency. We then investigated the antimicrobial mechanisms and developed therapeutic applications. We demonstrated SDS‐coated AgNPs with anomalous dispersive properties capable of dispersing in both polar and nonpolar solvents and, further, detected significantly higher bacteriostatic and bactericidal effects compared to silver ions (Ag+). Cellular assays suggested multipotent disruptions targeting the bacterial membrane, evidenced by increasing lactate dehydrogenase, protein and sugar leakage, and consistent with results from the transcriptomic analysis. Notably, the amphiphilic characteristics of the AgNPs maintained robust antibacterial activities for a year at various temperatures, indicating long‐term efficacy as a potential disinfectant. In a murine model, the AgNPs showed considerable biocompatibility and could alleviate fatal Salmonella infections. Collectively, by gaining amphiphilic properties from SDS, we offer novel AgNPs against bacterial infections combined with long‐term and cost‐effective strategies.

Shielding Fluoride Ion Basicity through Diurea Coordination for Nonaqueous Fluoride Shuttle Batteries

AbstractThe strong basicity of fluoride ions leads to detrimental nucleophilic attack on organic components in the electrolytes, such as β‐hydrogen elimination reactions with organic cations and solvents, converting “naked” F− into corrosive and unstable bifluoride (HF2−) ions. These reactions significantly constrain the choice of suitable solvents and salts to develop electro(chemical) stable fluoride ion electrolytes. In this work, we replaced the triple water ligands typically present in industrial organic fluoride salts with dual 1,3‐diphenylurea (DPU) coordination via hydrogen bonding interaction. This modification successfully suppressed the Lewis basicity of fluoride ions, providing long‐term chemical stability (over 1000 hours) across a wide range of aprotic solvents, a broadened electrochemical stability window (−2.5–0.9 V vs. Ag+/Ag) and high ionic conductivity (1.7 mS cm−1) at room temperature. Additionally, the weaker hydrogen bonding in F−‐DPU coordination, compared to the conventional boron‐based anion acceptor (AA) strategy that relies on intensive Lewis acid‐base interactions, facilitates faster (de)fluorination kinetics at the electrode. The proposed room temperature fluoride ion batteries sustain improved electrochemical performance by pairing with the Pb‐PbF2 anode and BiF3 or Ag cathode.

Structural Characterization and Hydration Dynamics of Cross-Linked Collagen and Hyaluronic Acid Scaffolds by Nuclear Magnetic Resonance.

Understanding a biomaterial's structural and hydration dynamics is essential for its development and applications in tissue regeneration. In this study, collagen-hyaluronic acid (HA) scaffolds were analyzed utilizing Nuclear Magnetic Resonance (NMR) techniques to elucidate how different cross-linking conditions influence the internal architecture and interaction with solvents in these scaffolds. The scaffolds were fabricated using 3D printing and cross-linked with 1,4-butanediol diglycidyl ether (BDDGE), a process known to impact their mechanical properties. We gained insights into the microstructural organization and hydration behavior within the scaffolds when exposed to water and ethanol by employing proton relaxation and diffusion measurements. To better understand the system's performance, static and dynamic experiments were performed. Our results indicate that the degree of cross-linking affects the scaffold's ability to retain water, with higher cross-linking leading to more rigid structures. This also altered the hydration dynamics mainly due to a difference in the diffusion of water within the scaffold. In addition, the anisotropy of the collagen fibers also decreases with the cross-linking. Ethanol, a less polar solvent, provided a contrasting environment that further revealed the structural dependencies on the cross-linking density. The study's findings contribute to a deeper understanding of how the structure and morphology affect the functionality of collagen-HA scaffolds, offering critical information for optimizing their design for specific biomedical applications, such as soft tissue regeneration. Our experiments show how NMR is a valuable tool to provide information on dynamic processes not only in collagen-HA scaffolds but also in many biocompatible polymeric samples. The outcomes of this research provide a foundation for future work aimed at tailoring scaffold properties to enhance their performance in clinical settings, ultimately advancing the field of tissue engineering.

Linear and Nonlinear Rheological Investigations of Poly(3-hexylthiophene) H-Aggregated Gel Networks.

Owing to its facile synthesis and low cost, poly(3-hexylthiophene) (P3HT) has been extensively investigated in the field of organic electronics. Well-defined packing of P3HT chains and getting controlled morphologies, which solely depend on the polarity of the solvent, remain challenging. Herein, the aggregation behaviors of P3HT in organic solvents having different solvent polarities have been investigated to achieve different orderings of P3HT chains (H-type or J-type). The aggregation in the solution phase and the subsequent structural as well as morphological behaviors of P3HT chains have been investigated by absorption, X-ray powder diffraction, and topological studies, respectively. It has been noticed from absorption studies that P3HT forms H-type aggregates in anisole, phenetole, etc., whereas it produces J-type aggregates in toluene. More surprisingly, H-type aggregations of P3HT chains at low concentrations (CP3HT = 0.001 g/cm3) eventually lead to the formation of the gel network that ceases the flow of the solvents. Contrary to expectations, J-type aggregation in toluene does not produce the gel network at the said concentration. Further, to reveal the viscoelastic and microstructural properties, P3HT gel networks have been thoroughly investigated by small-amplitude oscillatory shear (SAOS) and large-amplitude oscillatory shear (LAOS) with varying concentrations, solvents, and molecular weights of P3HT. With quantitative analysis, the nonlinear rheological characteristics of higher harmonics, strain-stiffening ratio, shear-thinning ratio, dissipation ratio, intracycle transient moduli, and derivative of transient moduli have been evaluated for P3HT networks, which significantly provide the rheological information for the understanding of conducting polymer networks.

Editorial

Homeopathy, once considered solely a well-established alternative or complementary healing discipline, has also become a focal point for a burgeoning branch of scientific exploration. Beyond its conventional healing practice, the foundations and mechanisms of potentized high dilutions are subject to scrutiny through an expanding body of scientific research. These investigations go far beyond clinical studies and include tissue and cellular models of different organisms and, more recently, ecology. In addition, in the last decades, the stated research has gone far beyond living beings since it extended to the physicochemical realm, studying the altered characteristics of fluids subjected to the homeopathic ultra-high dilution (UHD) process. Extensive scientific efforts have offered convincing evidence of the altered properties of fluids treated with the UHD methodology. These findings provide substantial support for the view that the efficacy of homeopathy is rooted in the emergent properties of polar solvents, water, in particular. More than that, the water properties we learn about from UHD solutions also occur in other treatments of water or aqueous solutions. This is why we can establish a new science of emergent properties of water. It is to substantiate and make new steps in developing this science that the November Conference in Ljubljana was dedicated to. This multi-faceted approach sheds light on the fundamental principles of the effectiveness of homeopathy as well as of many other non-chemical water treatments, opening up an entirely new horizon for the development of global health, ranging from individual living beings, including humans, through ecosystems to planet Earth as a whole. The XXXVII GIRI Meeting was held in November 9-12th, 2024 in Ljubljana, at the Town Hall, Slovenia, with the co-participation and shared organization of Bion Institute, Ljubljana, Slovenia, and World Water Lab consortium, an initiative to gather scientists interested to understand and advance the science of emergent properties of water. Research into water is different from the investigation of other substances because it so aptly reflects some as yet hidden principles and laws of nature. Many of them show to be utterly neglected or even banned from the standpoint of conventional (academic) sciences since they do not conform to their mechanistic and reductionist models. These profound features are investigated by water scientists working on all aspects of water properties, from physicochemical and biological aspects to the quantum electrodynamic field view. The initiative to gather these three institutions (GIRI – BION – WWL) allowed to discuss together and create a wide view of UHD effects on living systems. The program was organized in four Keynote talks, two round tables and 15 individual presentations selected from a careful peer-review process. One general seminar about the main topics studied in the context of the WWL activities closed the meeting. All talks focused the physicochemical aspects of UHDs, mainly the probable field effect, provoking a discussion about how good-quality basic research can improve the plausibility of clinical / agronomic use of UHD preparations, which seems to be an essential grounding for the evidence-based medicine clinical studies (including the veterinary ones) by improving its trial protocols, and for a high-tech sustainable resource of food production. Since both aspects are complementary, the need of high-level clinical studies on homeopathy and high dilutions is an urgent issue as well, as was also discussed. At the end of the conference, the Madeleine Bastide Prize was given to the best individual presentations, being the first place attributed to Prof. Fateme Mirzajani (Iran), the second place to Dr. Leonardo Faedo (Brazil - UK), and three mentions were given to Sandra Tribolo (France), Lorena Guimarães (Brazil), and Adriana Miranda (Brazil). We wish the readers an enjoyable read!

Colorimetric and fluorimtric microenvironment responsivity of oxazolidine in solvatochromic latex nanoparticles: Versatile intelligent polymeric materials with advanced applications

Oxazolidine, a new category of stimuli-chromic dyes, has displayed a wide range of responsivities, such as halochromism, solvatochromism, ionochromism, and hydrochromism. The optical properties of oxazolidine molecules can be influenced notably by the polarity of solvent, media, and polymer nanoparticles. In this study, multi-functionalized acrylic latex nanoparticles containing different polar functional groups such as amide, amine, acid, hydroxyl, epoxide, and long-chain ester were synthesized by one-pot emulsion copolymerization. Prepared latex nanoparticles have a mean particle size in the range of 45–170 nm and spherical or non-spherical (anisotropic) morphologies depending on the polarity of functional groups. To prepare multi-color photoluminescent latex nanoparticles and investigation of solvatochromism in both colloidal solution and solid phase, as prepared multi-functionalized latex nanoparticles were modified physically with an oxazolidine derivative (5 wt%). Investigation of the solvatochromism of the oxazolidine in colloidal solution and solid phase indicated that the media is the main effective parameter for solvatochromism in colloidal solution. In the case of solid-state solvatochromism, the optical properties of oxazolidine were influenced significantly by the polarity of functional groups, because the interactions of oxazolidine molecules with functional groups of latex nanoparticles is the main parameter that influenced the solvatochromism. The solvatochromic properties of oxazolidine in solid polymer powders are useful for developing multi-color photoluminescent materials with advanced applications in the dual-mode visualization of latent fingerprints (LFPs), anticounterfeiting solid inks, and organic light-emitting diodes (OLEDs). Results displayed potential applications of multi-color polymer powders for the detection of LFPs under visible light and UV-light irradiation, for printing of optical security tags, and construction of OLEDs. The presented study introduces a new category of multi-color solid photoluminescent nanomaterials with multiple applications using solvatochromic properties.

Carbon dots with high brightness and stability towards efficient Cr(Ⅵ) and l-arginine sensors

To create fluorescent sensors for Cr (VI) and l-arginine detection, blue-emitting carbon dots (CDs, named as M-CDs) were prepared via a solvothermal synthesis by using m-phenylenediamine. The introduction of sulfuric acid changed the blue-emitting of CDs into green-emitting (named as S-CDs), in which the photoluminescence (PL) peak wavelengths of samples M-CDs and S-CDs were 450 and 540 nm, while their PL efficiencies were 21.7 and 84.2 % respectively. Sulfuric acid resulted in the average fluorescent lifetime of the CDs was prolonged into 8.19 from 4.65 ns. The photo and thermal stable tests demonstrated that theses CDs revealed excellent stability. Meanwhile, CDs flexible films with bright blue- and green-emitting were prepared utilizing the favorable solubility of CDs in polar solvents. Mono-dispersed CDs as luminescent materials demonstrated it promising prospects in luminescent devices field. Furthermore, M-CDs exhibited excellent selectivity towards Cr(Ⅵ) and l-arginine. The detected limit (0.86 μM for Cr(Ⅵ) and 0.43 μM for l-arginine) was determined by assessing the response of M-CDs to various concentrations of Cr(Ⅵ) ion and l-arginine solutions. These bright CDs revealed great potential for accurate detection of Cr(Ⅵ) and l-arginine.

Phytochemical Composition and Antioxidant Properties of Canarium odontophyllum (Sarawak Olive): A Seasonal Fruit from Borneo, East Malaysia.

BackgroundCanarium species are reported rich of polyphenol, alkaloids, flavones, and saponins compounds. Canarium odontophyllum from Borneo's variety, on the other hand is remaining unclear especially on the antioxidant activity towards radicals. PurposeTo investigate phytochemical composition and antioxidant properties of C. odontophyllum. MethodsAntioxidant properties were evaluated using 2,2-diphenyl-1-picrylhydrazyl-hydrate (DPPH) assay, 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) assay, and ferric-reducing antioxidant power (FRAP) assay with different polarity of extraction solvents (methanol, acetone and hexane). The phytochemical composition was determined by Liquid Chromatography Mass Spectrometry Quadrupole Time of Flight (LCMS-QTOF). ResultsAcetone showed the highest scavenging activity in the DPPH (0.0307 mg/ml) and FRAP (3.926 mg/ml) assays, while hexane exhibited the highest activity in the ABTS assay (0.119 mg/ml). The LCMS-QTOF chromatogram identified 22 potential compounds. Among these, the major compounds oleamide (10.49%) and emmotin A (7.23%) have previously been reported to exhibit antioxidant activity. Other health-beneficial compounds were also found, such as palmitic amide (2.46%), deoxymiroestrol (6.23%), and N-Cyclohexanecarbonylpentadecylamine (48.92%), which are important in preventing metal corrosion, regulating hormones, and distinguishing between N-palmitoylethanolamine-hydrolyzing acid amidase (NPAA) and fatty acid amide hydrolase (FAAH), respectively. ConclusionThe results indicate that C. odontophyllum shows a promising potential an alternative drug in pharmaceutical developments.

Modified Microwave-assisted Solid-liquid Halex Reaction using Phosphonium Salt as Efficient and Robust Phase Transfer Catalyst

: A modified solid-liquid halex reaction was developed in the presence of a robust phase transfer catalyst under microwave conditions. A fast, mild, and practical microwave- assisted synthesis of 2,3-difluoro-5-chloropyridine 3 starting from 2,3,5- trichlorpyridine 1 and spray-dried KF in polar aprotic solvent was developed. The addition of Tetrakis (piperidino) phosphonium chloride as phase transfer catalyst A was studied under microwave irritation (450W) and increased the yield and significantly reduced the reaction time in contrast to the conventional heating procedure. The highest reaction rate was observed at 5 wt% phase transfer phosphonium salt catalyst to 2,3,5-trichloropyridine 1.

A self-assembly capsule-like solvation structure electrolyte for lithium metal batteries

The localized high-concentration electrolyte can be achieved by diluting a high-concentration electrolyte with an anti-solvent, which inherits the original solvation structural characteristics and reduces harmful interfacial reactions, resulting in an electrolyte with unique functions suitable for lithium metal batteries. Here, we design a localized high-concentration electrolyte with a capsule-like solvation structure and non-flammable properties to obtain stable-cycle and safe lithium metal batteries. The weak coordination and dipole-dipole interactions of fluorinated ether molecules promote the self-assembly of capsule-like solvated sheaths, encapsulating cations/anions and polar solvent molecules within the solvation sheath, which improves the oxidative stability of the electrolyte system and promotes the reduction of anions. A high-quality solid electrolyte layer was derived at the electrode interfaces, leading to rapid Li+ transport and dendrite-free lithium deposition. Consequently, a Coulombic efficiency of 99.7% is achieved, and the assembled Li||NCM811 battery exhibits a long cycle life of more than 400 cycles at 0.5C with a capacity retention of 83%. This work provides a promising approach for developing non-flammable electrolytes suitable for high-voltage lithium metal batteries.

Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone

Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone

Efficient Removal of Lipophilic Compounds from Sewage Sludge: Comparative Evaluation of Solvent Extraction Techniques

Municipal sewage sludge, a by-product of wastewater treatment plants, presents environmental challenges due to its complex composition. Particular concern is the lipophilic and aliphatic compounds that pose risks to the environment and human health. This study focuses on the efficient removal of those compounds from sewage sludge using several organic solvents (hexane, toluene, chloroform, dichloromethane, acetone, hexane-methanol mixture, ethanol, and methanol) and ionic liquids (ILs) like tetrakis(hydroxymethyl)phosphonium chloride and 1-ethyl-3-methylimidazolium acetate by solvent extraction techniques. To determine optimal conditions, various factors such as solvent types, contact time, and temperature were examined. The results reveal that solvent polarity significantly impacts extract composition, with non-polar solvents like hexane and toluene yielding profiles characteristic of lipid-type compounds. An in-depth analysis of contaminants present in the sewage sludge was studied by Fourier-transform infrared spectroscopy (FTIR). Additionally, nuclear magnetic resonance (NMR) was used to identify the extracted compounds, including triglycerides, aliphatic esters, aliphatic alcohols, and free carboxylic acids. NMR provides data on the composition of the sewage sludge and indicates that among all the solvents used, tetrakis(hydroxymethyl) phosphonium chloride was the most suitable solvent for removing lipophilic and aliphatic compounds. Regeneration potential and reusability of the IL were conducted and verified by NMR. The results showed that tetrakis(hydroxymethyl) phosphonium chloride ionic liquid could be used for several extraction cycles. Identifying these compounds in the extracted mixture demonstrates that it adds value and potential for various applications. Towards environmental sustainability and circular economy, this effort develops strategies for the safe management, disposal, and recyclability of sewage sludge and, the reduction in environmental and health hazards associated with organic compounds.

Excimer formation in a 2D confined space

Combination of organic dyes with 2D materials can lead to integrations forming heterostructures with tunable properties, where organic dyes, with their distinct energy levels and high absorption, can enhance the performance of 2D material-based optoelectronic devices. This manuscript focuses on the confinement-induced changes of such structures containing 4,4’-(2,6-naphthalenediyl)dipyridine dications capable to form excimer species within the 2D interlayer space of synthetic saponite. The interlayer space provides an interesting microenvironment enabling to control optical properties of the intercalated organic molecules by either varying their amount or expanding the interlayer space via swelling with aprotic solvents, resulting in stimuli-responsive materials. Utilization of spectroscopic techniques, statistical analysis, and theoretical methods revealed distinct features corresponding to the relative presence of different species with unique spatial arrangements. Depending on the occupancy of the interlayer space, the subsequent application of dimethyl sulfoxide leads to a swelling of the interlayer space, affecting the orientation and relative distribution of species. Presented study also highlights the importance of in-depth analysis of organic species in confined environments of 2D materials, contributing to the optimization and development of novel applied materials.

Self-Healing Supramolecular Flexible Network of Zn(II): Exploring Chemo-Responsiveness, Antimicrobial Efficiency, and Variable Microelectronic Device Performances.

The Zn(II)-supramolecular metallogel (i.e., Zn-Py) of 2,6-pyridinedicarboxylic acid was prepared through the addition of a metal source and 2,6-pyridinedicarboxylic acid as a low molecular weight gelator. The Zn-Py metallogel encapsulated N,N'-dimethylformamide as gel-immobilized polar aprotic solvent media. The mechanical features of the synthesized metallogel were investigated. The thixotropic behavior of the Zn-Py metallogel was also analyzed. The microscopic feature of the metallogel was imaged through FESEM and TEM studies. The EDS pattern of the metallogel ratified the role of different gel-building chemical constituents. The stimuli responsiveness of the metallogel was also tested. The metallogel-forming mechanistic protocol was visualized through FTIR and ESI mass spectroscopic analyses. The bioeffectiveness, i.e., antimicrobial potency, of Zn-Py was also studied. The antimicrobial efficiency against both Gram +ve and Gram -ve bacteria including Salmonella typhimurium (MTCC 98), Escherichia coli (MTCC 1667), Bacillus cereus (ATCC 13061), Listeria monocytogenes (MTCC 657), and Staphylococcus aureus (MTCC 96) was critically analyzed. The FESEM images of the live bacteria and damaged bacteria due to the action of the metallogel were experimentally investigated. The Zn-Py metallogel was also used to fabricate the heterojunction and Schottky-type photodetectors to show their excellent light-matter interaction and their potentiality as active material in optoelectronics. The electrical parameters of semiconductor diodes such as the p-n junction and Schottky diode fabricated by the synthesized Zn-Py metallogel were investigated. Outcomes of the experimental investigation demonstrated that the tested metallogel effectively showed p-n junction diode parameters, especially with the ideality factor (η) of 1.3 under a dark environment. This fabricated device efficiently depicted a great ON/OFF ratio of 33.4 at a reverse bias voltage of -2 V. The metal-semiconductor-metal (M-S-M) junction-type Schottky barrier diode was also fabricated using the Zn-Py metallogel where the Au/Zn-Py metallogel/Au-based device fabrication strategy was implemented.

Quantum chemical study of new oxadiazoles as efficient optical and nonlinear optical and photovoltaic materials under gas, PCM and COSMO solvent effects

The science of organic optical and nonlinear optical (NLO) materials has been captivating the scientific community owing to their extensive applications in optoelectronics, OLEDs, and telecommunications. This study presents the design and investigation of novel organic compounds of pyrene and 1,3,4-oxadiazole derivatives (1-oxza to 6-oxza), featuring various push–pull combinations. Quantum chemical calculations were employed to determine linear polarizabilities (α) and third-order NLO polarizabilities (γ). Notably, the largest average third-order NLO polarizability value was found to be 254.9 × 10−36 esu for the finely tuned push–pull system 6-oxza, which is ∼35 times greater than that of the prototype NLO molecule of p-nitroaniline (p-NA). Among the derivatives, 1-oxza exhibits the highest linear isotropic polarizability (αiso) value of 61.59 × 10−24 esu, while 5-oxza displays the highest linear anisotropic polarizability (αaniso) value of 60.09 × 10−24 esu. A notable increase of approximately ∼1 to ∼2 times in < γ > is observed for selected compounds (1-oxza, 4-oxza, 6-oxza), indicating that the Conductor-like Screening Model (COSMO) overestimates the values compared to the polarizable continuum model (PCM) and gas phases. Solvent significantly enhances third-order NLO polarizability amplitudes depending upon solvent polarity and strength of substitution groups. We calculated the frequency-dependent third-order NLO polarizability of 6-oxza at laser wavelengths ranging from 1400 to 1970 nm. The second hyperpolarizability EFISHG process (γ(−2ω; ω, ω, 0)) was calculated at a laser wavelength of 1400 nm, and the γ-amplitude was found to be 400.1 × 10−36 esu. The remarkable hyperpolarizability response in the gas phase is corroborated by TD-DFT calculations, which reveal a larger transition dipole moment of 3.062 and a lower transition energy of 3.780 eV as origin of larger hyperpolarizability for 6-oxza. A comprehensive analysis was performed based on FMOs for designed compounds to elucidate the intramolecular charge transfer (ICT) mechanisms and observed a notable reduction in energy band gap 4.89 eV for 6-oxza, which is responsible for enhanced NLO response. Additionally, DOS maps revealed the quantitative contributions of HOMOs and LUMOs for crucial electronic states related to the efficient ICT process. Additionally, we analyzed the photovoltaic properties and found that 6-oxza has the highest dye regeneration and the lowest open-circuit voltages of 1.89 eV and 2.22 eV, respectively. Our designed model compounds can put real-time such compounds under spotlight of scientific interests which seeks more efficient optical and NLO properties.

Encapsulation-induced hypsochromic shift of emission properties from a cationic Ir(III) complex in a hydrogen-bonded organic cage: A theoretical study.

Encapsulation of coordination complexes within the confined spaces of self-assembled hosts is an effective method for creating supramolecular assemblies with distinct chemical and physical properties. Recent studies with calix-resorcin[4]arene hydrogen-bonded hexameric capsules revealed that encapsulated metal complexes exhibit enhanced and blue-shifted photoluminescence compared to their unencapsulated forms. The photophysical change has been hypothetically attributed to encapsulation-induced confinement, which isolates the metal complex from the solvent, suppressing stabilization of the excited state of the guest by solvent reorganization and structural relaxation, and altering the local environment, such as solvent polarity and viscosity, around the guest. In this study, density-functional theory calculations were conducted to explore how encapsulation affects the photophysical properties of a cationic iridium complex within a hydrogen-bonded hexameric capsule. The encapsulation-induced emission shift was analyzed by separating it into three factors: suppression of solvent reorganization, suppression of structural relaxation of the complex, and electronic interactions between the complex and the capsule. The findings indicate that the photoluminescence modulation is driven by the electronic interaction between the host and guest, which affects the energy levels of the molecular orbitals involved in the T1 excited state and the suppression of excited-state structural relaxation of the Ir complex due to the presence of the host. This study advances our understanding of the photophysical dynamics of coordination complexes within the confined spaces of hexameric capsules, providing a valuable approach for tuning the excited state properties of guest molecules.

Inion Sulfocation Membranes Plasticized with Propylene Carbonate

The rapidly developing field of portable energy sources requires the search and development of effective materials for such devices. To improve the safety of the most common metal-ion batteries (lithium- and sodium-ion), instead of a liquid electrolyte, it is proposed to use a gel-polymer electrolyte with unipolar conductivity based on a Nafion-like electrolyte (Inion), plasticized with aprotic solvents. The work presents the results of a study of the thermal stability, molecular structure and supramolecular packing, as well as ionic conductivity of the Inion membrane in lithium and sodium forms, plasticized with propylene carbonate, using methods of simultaneous thermal analysis, IR spectroscopy, small-angle X-ray scattering and impedance spectroscopy.

Molecular Design of a Diketopyrrolopyrrole Conjugated Oligoelectrolyte Capable of Imaging Intracellular Vesicle Membrane Dynamics.

Conjugated oligoelectrolytes (COEs) are lipid bilayer spanning optical reporters that hold promise for delineating spatiotemporal changes in subcellular compartments. However, their ability to probe a broader range of biological processes remains restricted due to the lack of environmentally-responsive chemical functionalities. Herein, the study reports a novel COE, namely COE-KP, for monitoring spatiotemporal changes in the endolysosomal vesicles. COE-KP features a central diketopyrrolopyrrole functional group in the optically active conjugated core that confers photophysical properties suitable for bioimaging, in particular responding to the presence of hydrogen bonding functionalities within the hydrophobic domain of the lipid bilayer. COE-KP can thus discriminate cells in different growth states through two-photon fluorescence lifetime imaging microscopy (FLIM) with excitation in the NIR-II range. These changes in lifetime most reasonably reflect the degree of water permeability through the membrane and are not linked to notable differences in membrane tension or solvent polarity. Furthermore, using stimulated emission depletion (STED) nanoscopy, it is possible to directly visualize membrane-bound COEs within cellular vesicles. These results illustrate further opportunities for applying COE-based reporters for super-resolution microscopy of organelle membranes, visualization of subcellular membrane morphologies, and imaging long-term changes in membrane properties.

Simulation of Solvatochromic Phenomena in Xanthione Using Explicit Solvent Methods

Xanthione is a sulfated polycyclic aromatic hydrocarbon which exhibits unique anti-Kasha properties and substantial sensitivity to its medium. Due to this sensitivity however, this makes xanthione-based systems very difficult to simulate. Further, xanthione’s is understood to be come more photostable in the presence of a highly polar medium, however whether these photophysical properties could be taken advantage of for certain applications remains to be seen. In clarifying long-held beliefs of specific solvent effects, we apply a rigorous theoretical solvent analysis in both implicit and explicit solvent mediums to elucidate a more complete description of solvent polarity sensitivity in xanthione using both quantum chemical and molecular dynamics techniques. Not only was it found that explicit solvation methods are vital in an accurate description of the system, only a handful of explicit solvent molecules in the simulation are required to yield an appropriate electronic description. This short work is vital to devising future applications for xanthione-based and other quantum technologies, and is an important foundation stone on this journey.