Varying Chain Length Research Articles

Cation Chain Length of Nonhalogenated Ionic Liquids Matters in Enhancing SERS of Cytochrome c on Zr-Al-Co-O Nanotube Arrays.

Surface-enhanced Raman scattering (SERS) is a remarkably powerful analytical technique enabling trace-level detection of biological molecules. The interaction of a probe molecule with the SERS substrate shows important distinctions in the SERS spectra, providing inherent fingerprint information on the probe molecule. Herein, nonhalogenated phosphonium-based ionic liquids (ILs) containing cations with varying chain lengths were used as trace additives to amplify the interaction between the cytochrome c (Cyt c) and Zr-Al-Co-O (ZACO) nanotube arrays, strengthening the SERS signals. An increased enhancement factor (EF) by 2.5-41.2 times compared with the system without ILs was achieved. The improvement of the SERS sensitivity with the introduction of these ILs is strongly dependent on the cation chain length, in which the increasing magnitude of EF is more pronounced in the system with a longer alkyl chain length on the cation. Comparing the interaction forces measured by Cyt c-grafted atomic force microscopy (AFM) probes on ZACO substrates with those predicted by the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory, the van der Waals forces became increasingly dominant as the chain length of the cations increased, associated with stronger Cyt c-ZACO XDLVO interaction forces. The major contributing component, van der Waals force, stems from the longer cation chains of the IL, which act as a bridge to connect Cyt c and the ZACO substrate, promoting the anchoring of the Cyt c molecules onto the substrate, thereby benefiting SERS enhancement.

Poly(vinyl benzoate)-b-poly(diallyldimethyl ammonium TFSI)-b-poly(vinyl benzoate) Triblock Copolymer Electrolytes for Sodium Batteries

Block copolymers (BCPs) as solid electrolytes for batteries are usually designed to have an ion-solvating block for ion conduction and an ionophobic block for providing mechanical strength. Here, we show a novel solid polymer electrolyte (SPE) for sodium batteries based on a poly(vinyl benzoate)-b-poly(diallyldimethyl ammonium bis(trifluoromethanesulfonyl)imide) PVBx-b-PDADMATFSIy-b-PVBx ABA triblock copolymer. The SPE triblock copolymer comprises a polymerized ionic liquid (PIL) ion-solvating block combined with NaFSI salt as an internal block and an ionophilic PVB as an external block. Four distinct compositions with varying chain lengths of the blocks were synthesized by reversible addition−fragmentation chain-transfer (RAFT) polymerization. The neat copolymers were subsequently mixed with NaFSI in a 2:1 mol ratio of Na to ionic monomer units. Through comprehensive analysis using differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR), and nuclear magnetic resonance (NMR), it was revealed that the ion coordination within the polymer–salt mixtures undergoes changes based on the composition of the starting neat polymer. Electrochemical evaluations identified the optimal composition for practical application as PVB11.5K-b-PDADMATFSI33K-b-PVB11.5K, showing an ionic conductivity at 70 °C of 4.2 × 10−5 S cm−1. This polymer electrolyte formulation was investigated for sodium in Na|Na symmetrical cells, showing an overpotential of 200 mV at 70 °C at 0.1 mA cm−2. When applied in a sodium–air battery, the polymer electrolyte membrane achieved a discharge capacity of 1.59 mAh cm−2 at 50 °C.

Clarifying the role of carboxyl functionality in squaraines towards aggregation and self-assembly through photophysical characterization and BSA interactions

The demand for near-infrared (NIR) probes with robust and stable fluorescence signals has surged, driven by their applications in optical sensing and bioimaging. Squraine dyes as NIR fluorescent probes have gained significant traction. However, understanding their behavior in aqueous media is important for their successful application. Herein we report the synthesis and photophysical characterization of carboxy-functionalized unsymmetrical squaraine dyes capable of light absorption and emission in the near-infrared (NIR) wavelength region. Structural variations in alkyl chain length, and spacer chain length between the primary chromophore and –COOH group were systematically introduced to investigate their impact on self-assembly in aqueous media leading to dye aggregation and their differential interactions with Bovine Serum Albumin (BSA) as a model protein. In phosphate buffer (PB) the absorption intensity decreased drastically along with pronounced shoulders due to dye aggregation leading to complete fluorescence quenching. However, in the presence of BSA, the intensity of shoulder bands reduced coupled with a sharp increase in the absorption associated with monomeric dye with the increasing concentration of BSA, indicating the prevention of dye aggregation owing to dye-BSA interactions. The prevention of dye aggregation due to dye-BSA interaction also led to a tremendous increase in the fluorescence intensities as a function of the increasing BSA concentrations. Site-selective study off BSA showed that these dyes bind preferably at Site-II using hydrophilic interactions. Thus, these dyes show great potential as FRET or fluorescent on/off probes for biosensing, non-covalent labeling of proteins, and fluorescent probes for bioimaging.

High-Strength Polycrystalline Covalent Organic Framework with Abnormal Thermal Transport Insensitive to Grain Boundary.

Grain boundaries (GBs) in two-dimensional (2D) covalent organic frameworks (COFs) unavoidably form during the fabrication process, playing pivotal roles in the physical characteristics of COFs. Herein, molecular dynamics simulations were employed to elucidate the fracture failure and thermal transport mechanisms of polycrystalline COFs (p-COFs). The results revealed that the tilt angle of GBs significantly influences out-of-plane wrinkles and residual stress in monolayer p-COFs. The tensile strength of p-COFs can be enhanced and weakened with the tilt angle, which exhibits an inverse relationship with the defect density. The crack always originates from weaker heptagon rings during uniaxial tension. Notably, the thermal transport in p-COFs is insensitive to the GBs due to the variation of minor polymer chain length at defects, which is abnormal for other 2D crystalline materials. This study contributes insights into the impact of GBs in p-COFs and offers theoretical guidance for structural design and practical applications of advanced COFs.

Reverse Mapping of Coarse Grained Polyglutamine Conformations from PRIME20 Sampling.

An inverse coarse-graining protocol is presented for generating and validating atomistic structures of large (bio-) molecules from conformations obtained via a coarse-grained sampling method. Specifically, the protocol is implemented and tested based on the (coarse-grained) PRIME20 protein model (P20/SAMC), and the resulting all-atom conformations are simulated using conventional biomolecular force fields. The phase space sampling at the coarse-grained level is performed with a stochastical approximation Monte Carlo approach. The method is applied to a series of polypeptides, specifically dimers of polyglutamine with varying chain length in aqueous solution. The majority (>70 %) of the conformations obtained from the coarse-grained peptide model can successfully be mapped back to atomistic structures that remain conformationally stable during 10 ns of molecular dynamics simulations. This work can be seen as the first step towards the overarching goal of improving our understanding of protein aggregation phenomena through simulation methods.

Wave propagation in finite discrete chains unravelled by virtual measurement of dispersion properties

AbstractTravelling waves in circuit chains are studied to measure continuous dispersion. A lock‐in frequency meter (LIF) is suitable for precisely determining k for each set of waves in finite alternate LC chains, where LIF has been proven to be more accurate than the fast Fourier transform. In addition to the –k measurement, the wave impedance spectrum of the travelling wave can be measured simultaneously, for investigating the dispersion and splitting of pulse propagation. The measured dispersion is validated to be consistent with the derived theoretical equations. The result provides an independent way to precisely obtain dynamical system properties for chains composed of non‐ideal components, such as resistors for researching non‐Hermitian behaviour under dissipation. Systematical mapping of relative deviation dependence of wave dispersion measurement with LIF on different chain length and component variation is studied, indicating boundaries of 1%, 0.1%, and 0.01% precision for guidance of experiments.

Investigation of Alkane-Assisted dodecylamine on flotation desilication of magnesite Tailings: Molecular dynamics simulations and model optimization

Investigating the reverse flotation desilication process of magnesite tailings (MT) holds substantial merit in the context of magnesium metal recovery from solid waste. However, scant attention has been devoted to exploring the influence of the carbon chain length of diverse alkanes on the reverse flocfloatation desilication of MT. This research systematically delved into the selective adsorption behavior exhibited by dodecylamine (DDA) and its compound collectors on the surfaces of quartz and magnesite. As the carbon chain length of alkanes increases, the efficacy of reverse flotation desilication of MT diminishes. Under optimized conditions, the concentration of MgO in the concentrate registers a 0.93% increment, accompanied by a 2.05% reduction in SiO2 content. The optimal MgO grade attains 42.68%. The augmenting carbon chain length of alkanes leads to a decline in the dispersibility of the compound collector and a reduction in the diffusion coefficient of the monolayer film at the alkane/water interface. The compound collector, comprising n-heptane and DDA, manifests a noteworthy synergistic promotion effect on the flotation desilication of MT. This effect reduces the multilayer adsorption of DDA, promotes more hydrogen bonding formation, and favors DDA adsorption on the quartz surface over magnesite. Consequently, issues related to froth entrapment and poor selectivity are alleviated. Longer alkane chains in the compound collectors result in a stronger van der Waals force effect between the carbon chains. This effect causes DDDA to slide more easily on the quartz surface, which is not conducive to enhancing the hydrophobicity of the surface. Furthermore, alkane-induced hydrophobic flocculation increases the floccules size of quartz, enhancing the likelihood of bubble-particle adhesion. This investigation elucidates the molecular-level mechanism underlying alkane hydrophobic flocculation with varying chain lengths, contributing a theoretical foundation and technical support for the large-scale MT management and the sustainable production of magnesium metal.

Impact of Halogen Termination and Chain Length on π-Electron Conjugation and Vibrational Properties of Halogen-Terminated Polyynes.

We explored the optoelectronic and vibrational properties of a new class of halogen-terminated carbon atomic wires in the form of polyynes using UV-vis, infrared absorption, Raman spectroscopy, X-ray single-crystal diffraction, and DFT calculations. These polyynes terminate on one side with a cyanophenyl group and on the other side, with a halogen atom X (X = Cl, Br, I). We focus on the effect of different halogen terminations and increasing lengths (i.e., 4, 6, and 8 sp-carbon atoms) on the π-electron conjugation and the electronic structure of these systems. The variation in the sp-carbon chain length is more effective in tuning these features than changing the halogen end group, which instead leads to a variety of solid-state architectures. Shifts between the vibrational frequencies of samples in crystalline powders and in solution reflect intermolecular interactions. In particular, the presence of head-to-tail dimers in the crystals is responsible for the modulation of the charge density associated with the π-electron system, and this phenomenon is particularly important when strong I··· N halogen bonds occur.

Rational design of a red-emission fluorescent probe for imaging mitochondrial viscosity and fatty liver tissues

Abnormal mitochondrial viscosity is closely associated with various diseases. Thus, it is imperative to design and synthesized fluorescent probes for monitoring changes in mitochondrial viscosity. In this work, two series of fluorescence probes with triphenylamine unit and 2-hydroxyphenylbenzothiazole unit respectively were constructed. The impact of varying chain lengths on the photophysical properties of these probes was investigated. The results indicated that probe TPAC12 with dodecane group exhibited the largest fluorescence enhancement. The results of cell imaging experiments demonstrated that all these probes exhibited specific targeting towards mitochondria and were not influenced by changes in mitochondrial membrane potential. Additionally, probe TPAC12 facilitated the monitoring of viscosity alterations within mitochondria. Importantly, probe TPAC12 has been effectively utilized for the identification of both fatty liver and normal liver tissues. These results suggested that probe TPAC12 holds great potential as a valuable tool for detecting mitochondrial viscosity in biological systems.

Theoretical prediction (DFT) and experimental observation of electronic and electro-optical properties of HATn (n = 5,6,7,8) molecules for optoelectronic applications

The formation of triphenylene core-based discotic mesogens exhibiting a classical columnar phase led to several superior electronic and optoelectronic applications. The present work reports the theoretical investigation of discotic hexaalkoxytriphenylene (HATn; n = 5, 6, 7, 8) mesogens including electro-optical, electronic, and thermodynamic properties using density functional theory (DFT) as a computational quantum mechanical tool. The various physical and chemical properties of these mesogens, such as electronegativity, specific heat capacity, polarizability, absorption, and dipole moment are calculated computationally and discussed in the study. The simulation study reveals the variation in physical properties either follows the odd–even effect or changes monotonically for HATn series. Experiment has been performed for comparison with the theoretical results. The physical and chemical properties of these discotic mesogens change with alkyl chain length variation and explain the structure–property correlation in the molecules. The obtained results of the designed molecular structure held promising applications for optoelectronic devices based on discotic mesogens.

Simulating the behavior of antioxidant to explore the mechanisms of oxidative stability in Pickering emulsion

This study explores effective strategies for bolstering emulsion oxidative stability via optimized interfacial distribution of varying hydrophobicity antioxidants (gallic acid, propyl gallate, octyl gallate) in zein nanoparticle (ZP) stabilized Pickering emulsions. Experimental and simulation methods revealed that antioxidant (AO) with higher hydrophobicity or loaded into ZP demonstrated stronger hydrogen bonding and van der Waals interactions with ZP. This increased interfacial loading of antioxidants resulted in improved oxidative stability in Pickering emulsions. The flow, distribution and orientation of AO, as revealed by dissipative dynamics simulations, highlighted the role of hydrophobic interactions during initial AO migration, influenced by varied alkyl chain lengths. Subsequent interface rearrangements arose from conservative force interactions between the AO's phenol hydroxyl ends and ZP. These findings inform effective interfacial engineering to optimize antioxidant efficiency, guiding practical applications in emulsion systems for improved oxidative stability.

Transport of carboxylate salts of varying chain lengths in crosslinked polyether membranes

Carboxylate anions of various chain lengths are important molecules for many applications such as CO2 reduction, membrane-based bioreactors, etc. Also, carboxylate anions are ubiquitous in biological molecules such as amino acids, fatty acids, etc. Therefore, understanding the transport behavior of carboxylates of different chain lengths in polymer materials is important both as a fundamental phenomenon but also for designing materials for applications. Here, we characterized transport behavior by measuring the permeability (P), and total partition coefficient (K) for a series of polymer membranes for four model carboxylate salts—sodium salts of formate (NaOFm), acetate (NaOAc), propionate (NaOPr), and butanoate (NaOBu)—at varied upstream salt concentrations (0.1–1 M) or a series of polyethylene glycol diacrylate (PEGDA)-based membranes with 1) varying pre-polymerization water content; 2) varying uncharged side chain comonomer (polyethylene glycol methacrylate, PEGMA), and 3) varying charged comonomer)2-acrylamido-2-methyl-1-propanesulfonic acid, AMPS). Also, diffusivity values of the four salts through the membranes have been calculated based on the solution diffusion model equation (PK × D), experimentally obtained permeability, and total partition coefficients. For a majority of these membranes, NaOFm's permeability is much higher than the other three carboxylate salts (NaOAc, NaOPr, and NaOBu) seemingly due to the lower chain length and thereby smaller hydrated diameter. In terms of total partition coefficient, a size-based trend is not observed. For example, NaOBu's total partition coefficient (K) is generally the largest among the four, and at higher upstream salt concentrations (1 M), the values of the total partition coefficients of the four salts converge. From this we conclude that the carboxylate salt transport through these PEGDA-based non-porous dense membranes to be primarily driven by kinetics and not sorption.

Nano‐Calcium Carbonate with Core–Shell Structure was Prepared by Dopamine Chelation Using Pluronic F‐127 as Template

AbstractHerein, a new template carbonization method is used to prepare calcite‐type nano‐calcium carbonate (CaCO3) with a core–shell structure using calcium hydroxide as a solute and Pluronic F‐127 as a templating and pore‐forming agent. Dopamine hydrochloride is added to control the size of calcium hydroxide particles. The morphology, particle size, and crystal type of CaCO3 are characterized via transmission electron microscopy, X‐ray diffraction, nanoparticle size, and zeta potentiometer. The creation of core–shell calcium carbonate nanoparticles is examined in relation to reaction circumstances (i.e., additive sequence, additive amount, and additive mixing time), carbonization temperature, liquid flow rate, and templates with varying chain lengths. Furthermore, a discussion is held regarding the formation mechanism of spherical core–shell calcium carbonate that is created using the innovative template carbonization method. The results show that the order, amount, liquid flow rate, and template type of additives have a significant effect on the crystal shape of calcium carbonate nanoparticles. The mixing time of additives has a significant effect on the particle size of calcium carbonate nanoparticles. Interestingly, the thickness of the shell depends on the carbonization temperature, and too slow or too fast flow rate will lead to the formation of cyclic calcium carbonate nanoparticles.

Synthesis and application of novel Gemini esterquats in fabric softeners: Role of spacer chain length on surfactant properties

AbstractGemini surfactants are dimeric molecules having two monomeric units connected by a spacer. Gemini surfactants, owing to their molecular structure have better surfactant properties than other monomeric surfactants. Esterquat class gemini surfactants can be synthesized using a spacer containing ester linkages. In the current study, the synthesis of novel esterquat gemini surfactants was carried out with spacers of varying chain lengths and was characterized using sophisticated instrumental methods. Various surfactant properties including foaming, emulsification, CMC, surface excess, antimicrobial activity and wetting potential using contact angle were analyzed and compared with benzalkonium chloride. It was observed that the CMC as low as 24.79 × 10−3 mM of the synthesized surfactants is potentially lower than that of conventional monomeric surfactants and was found to increase with an increase in spacer chain length. Further, the applicability and evaluation of performance properties of the synthesized surfactants were studied in fabric softener formulation. The water absorbency and whiteness retention of the formulation prepared using 12‐6‐12 GS was the highest due to its better wettability amongst other synthesized surfactants owing to its higher spacer chain length. To summarize, the surface and anti‐microbial properties of the synthesized surfactants vary greatly with the alteration in spacer chain length.

Surface stress can initiate environment-assisted fracture in metals.

Controlling environmental effects in surface plasticity/fracture of metals is of interest for areas as diverse as manufacturing processes, product performance, and structural safety. The key to controlling these effects is understanding the effect of adsorbates on surface energy (γ) and surface stress (f). While γ has been well studied, the role of surface stress has received much less attention. We characterize surface stress induced in metals by adsorption of organic monolayers. Linear alkanoic acids of varying chain length (3-18) are deposited by molecular self-assembly onto one side of an aluminum cantilever, several centimeters in length. The surface stress is estimated from in situ measurement of the cantilever deflection. We find that the organic adsorbates induce large surface stress of -4 to +30N/m. Furthermore, we show that f may be tuned by varying adsorbate-molecule chain length. The stress data explain beneficial embrittlement of metal surfaces by organic adsorbates in cutting and comminution processes, and point to a critical role, hitherto ignored, for f in environment assisted cracking (EAC) phenomena. Our results suggest opportunities for utilizing controlled environment-assisted fracture as an aid-fracture as a friend-to enhance material removal processes, apart from using surface stress itself as an experimental probe to explore various manifestations of EAC.

A Comparative Biodegradation Study to Assess the Ultimate Fate of Novel Highly Functionalized Hydrofluoroether Alcohols in Wastewater Treatment Plant Microcosms and Surface Waters.

Per- and polyfluoroalkyl substances (PFAS) are a class of chemicals present in a wide range of commercial and consumer products due to their water-repellency, nonstick, or surfactant properties, resulting from their chemical and thermal stability. This stability, however, often leads to persistence in the environment when they are inevitability released. We utilized microbial microcosms from wastewater treatment plant (WWTP) sludge to determine how employing different functional groups such as heteroatom linkages, varying chain lengths, and hydrofluoroethers (HFEs) will impact the ultimate fate of these novel PFAS structures. A suite of five novel fluorosurfactant building blocks (F7C3OCHFCF2SCH2CH2OH (FESOH), F3COCHFCF2SCH2CH2OH (MeFESOH), F7C3OCHFCF2OCH2CH2OH (ProFdiEOH), F7C3OCHFCF2CH2OH (ProFEOH), and F3COCHFCF2OCH2CH2OH (MeFdiEOH)) and their select transformation products, were incubated in WWTP aerobic microcosms to determine structure-activity relationships. The HFE alcohol congeners with a thioether (FESOH and MeFESOH) were observed to transform faster than the ether congeners, while also producing second-generation HFE acid products (F7C3OCHFC(O)OH (2H-3:2 polyfluoroalkyl ether carboxylic acid [PFECA]) and F3COCHFC(O)OH (2H-1:2 PFECA). Subsequent biodegradation experiments with 2H-1:2 PFESA and 2H-1:2 PFECA displayed no further transformation over 74 days. Surface water Photofate experiments compared 2H-1:2 PFECA, and 2H-1:2 polyfluorinated ether sulfonate (PFESA) with their fully fluorinated ether acid counterparts, and demonstrated the potential for both HFE acid species to completely mineralize over extended periods of time, a fate that highlights the value of studying novel PFAS functionalization. Environ Toxicol Chem 2024;43:2297-2305. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Enzymatic synthesis of tyrosol esters in organic solvents and ionic liquids: Correlation between enzyme activity and solvent properties

Tyrosol is a principle phenolic compound present in olive oil and wine with great pharmacological potentials due to its strong antioxidant property. Its application can be highly extended by increasing its lipophilicity through esterification. In this study, tyrosol esters were synthesized by enzymatic transesterification of tyrosol with vinyl esters, with a commercial lipase from Novozymes (Novozym 435, Candida antarctica lipase B (CALB) immobilized on macroporous acrylic resin beads) as the catalyst, both in organic solvents and in ionic liquids. Methyl tert-butyl ether (MTBE) was the best solvent, offering complete conversions towards the synthesis of tyrosol esters with varying chain lengths (C2-C18) within 1 h. Taking the enzymatic transesterification between tyrosol and vinyl acetate as the model reaction, 18 organic solvents and 24 ionic liquids were screened, and their solvent properties (i.e. hydrophobicity, polarity, viscosity, water activity, and partition coefficients of substrate and product) were correlated to the enzyme activity. Upon enzyme screening, four new lipases were found to be highly efficient, relative to the best-performed Novozym 435 and Lipozyme TLIM (Thermomyces lanuginosus lipase (TLL) immobilized on silica gel), in tyrosol ester synthesis. This work provides enzymatic methods of esterifying tyrosol that are much more efficient than those reported in literature, and will shed light on re-consideration of the roles of solvents in nonaqueous enzymology.

Alternative Methods for Biodiesel Cetane Number Valuation: A Technical Note.

Biodiesel is an environmentally beneficial and clean energy source that may replace fossil fuels, which are detrimental to the environment and cannot be replenished. Therefore, the physicochemical parameters of biodiesel must be determined in order to verify its quality. The cetane number is a crucial dimensionless fuel property that gauges the fuel ignition quality in power diesel engines. A higher cetane number results in a shorter ignition delay time, and vice versa. Biodiesel's cetane number may fluctuate due to a variety of fatty acid compositions, including variations in carbon chain length and the degree of unsaturation. The cetane number generally increases with increasing saturation and chain length, while it decreases as chain length is reduced and degrees of unsaturation and branching increase. This is the main reason for why alkanes possess a higher cetane number than alkenes and aromatics. The standard protocols for evaluating the cetane number of biodiesel are ASTM D613 and ISO 5165 test techniques using a monocylindrical cetane engine. However, adhering to these conventional procedures is quite challenging and time-consuming, and the cetane number test result may also be affected by the presence of certain gases and fumes. As a result, many researchers are bothered with cetane number valuation, and occasionally they skip it due to a lack of other options. Consequently, the aim of this paper is to present a set of more straightforward and relevant alternative techniques that can be applied to predict the cetane number of biodiesel when engine-based measurement is not practical. The three techniques with their designed pictographic outlooks conferred in this article include color indicator titration, aniline point, and fatty acid composition-based methods. The reported values of these procedures meet the minimum cut point of the biodiesel cetane number required by ASTM D6751 (≥47) and exhibit minimal variation from the typical standard methods. Nevertheless, the above-mentioned techniques are not applicable to other alternative biofuels except biodiesel products because they have a direct implication on the characteristics of the fatty acid profiles of different oil precursors, such as carbon chain length, degree of saturation or unsaturation, and aromaticity, which make up monoalkyl esters.

On the thermodynamics of aggregation toward phosphorescent metallomesogens: From electronic tuning to supramolecular design

AbstractTwo series with three Pt(II) complexes each (PtLPh‐n, PtLFpy‐n) bearing asymmetric tetradentate ligands as dianionic luminophores with variable alkyl chain lengths were synthesized. Hence, each ligand series is distinguished by one of its cyclometallating rings (phenyl vs. 2,6‐difluoropyrid‐3‐yl). Steady‐state and time‐resolved photoluminescence spectroscopic studies in diluted solutions at room temperature and in glassy matrices at 77 K show that the emissive state is mainly centered on the invariantly electron‐rich cyclometalated side while the second ring regulates the admixture of ligand‐centered and metal‐to‐ligand charge‐transfer character. Hence, the radiative rates can be controlled, as indicated by quantum‐mechanical calculations, which also explain the temperature‐dependent trend in the phosphorescence rate constants. Studies in condensed phases (single‐crystal X‐ray diffractometry, polarized optical microscopy, differential scanning calorimetry, steady‐state and time‐resolved photoluminescence micro(spectro)scopy) showed the development of a smectic A mesophase for the fluorinated species bearing the two longest alkyl chains. Nuclear magnetic resonance‐based studies on the thermodynamics of aggregation in solution confirm the marked enthalpic stabilization of aggregates mediated by the polar 2,6‐difluoropyrid‐3‐yl moiety (and to a lesser extent by dispersive forces between the alkyl chains). On the other hand, the negative entropy of aggregation is dominated by the restriction of degrees of freedom involving the peripheral alkyl moieties upon stacking, which becomes increasingly relevant for longer chains. All these factors control Pt···Pt coupling, a crucial interaction for the design of photofunctional mesogens based on Pt(II) complexes.

Nanoparticles of Push-Pull Triphenylamine-Based Molecules for Light-Controlled Stimulation of Neuronal Activity.

Organic semiconductor materials with a unique set of properties are very attractive for interfacing biological objects and can be used for noninvasive therapy or detection of biological signals. Here, we describe the synthesis and investigation of a novel series of organic push-pull conjugated molecules with the star-shaped architecture, consisting of triphenylamine as a branching electron donor core linked through the thiophene π-spacer to electron-withdrawing alkyl-dicyanovinyl groups. The molecules could form stable aqueous dispersions of nanoparticles (NPs) without the addition of any surfactants or amphiphilic polymer matrixes with the average size distribution varying from 40 to 120 nm and absorption spectra very similar to those of human eye retina pigments such as rods and green cones. Variation of the terminal alkyl chain length of the molecules forming NPs from 1 to 12 carbon atoms was found to be an efficient tool to modulate their lipophilic and biological properties. Possibilities of using the NPs as light nanoactuators in biological systems or as artificial pigments for therapy of degenerative retinal diseases were studied both on the model planar bilayer lipid membranes and on the rat cortical neurons. In the planar bilayer system, the photodynamic activity of these NPs led to photoinactivation of ion channels formed by pentadecapeptide gramicidin A. Treatment of rat cortical neurons with the NPs caused depolarization of cell membranes upon light irradiation, which could also be due to the photodynamic activity of the NPs. The results of the work gave more insight into the mechanisms of light-controlled stimulation of neuronal activity and for the first time showed that fine-tuning of the lipophilic affinity of NPs based on organic conjugated molecules is of high importance for creating a bioelectronic interface for biomedical applications.