Linear Alkyl Chains Research Articles

Development of ferroelectricity in the smectic phases of 4-cyanoresorcinol derived achiral bent-core liquid crystals with long terminal alkyl chains

Bent-core molecules can form numerous polar and symmetry broken liquid crystalline phases with fascinating properties. Here we report the characteristics of a previously unknown polar synclinic smectic phase, $\mathrm{Sm}{C}_{\mathrm{S}}{P}_{\mathrm{X}}$, found in the phase sequence of an achiral bent-core material with a 4-cyanoresorcinol bisbenzoate core, terminated by long linear alkyl chains ($n=18$) on both ends. This phase exists over a narrow range of temperatures and is sandwiched in between the random polar synclinic smectic phase ($\mathrm{Sm}{C}_{\mathrm{S}}{P}_{\mathrm{R}}$) and polar synclinic ferroelectric ($\mathrm{Sm}{C}_{\mathrm{S}}{P}_{\mathrm{F}}$) phase with ${\mathbit{P}}_{S}\ensuremath{\sim}250\phantom{\rule{0.16em}{0ex}}\mathrm{nC}/\mathrm{c}{\mathrm{m}}^{2}$. In a planar-aligned cell it exhibits only chirality flipping on application of a conventional ac field but it also exhibits optical switching by rotation of the molecular directors on the tilt cone subjected to a modified sequence of bipolar pulses. This changeover is discussed in terms of the model given by Nakata et al. [Phys. Rev. Lett. 96, 067802 (2006)], involving a competition between the two forms of switching: the rotation around the long molecular axis and the switching through rotation of the molecular directors on the tilt cone. The model is modified to take account of the azimuthal pretilt and the molecular tilt angles. In addition to it, characteristics of $\mathrm{Sm}{C}_{\mathrm{S}}{P}_{\mathrm{R}}$ are also discussed.

Aggregation Behavior of Non‐ionic Twinned Amphiphiles and Their Application as Biomedical Nanocarriers

A new class of twinned amphiphiles was developed by conjugating a pair of hydrophilic head groups from mPEG chains (Mn : 350 or 1000) and a pair of hydrophobic segments from linear alkyl chains (C11 or C18 ) through a novel spacer synthesized from glycerol and p-hydroxybenzoic acid. The aggregation phenomena of the amphiphiles were proven by DLS and fluorescence experiments, whereas size and morphology of the aggregates were evaluated by cryo-TEM. The measurements proved the formation of globular, thread-like or rod-like micelles as well as planar double-layer assemblies, depending on the amphiphile's molecular structure. The applicability of these non-ionic amphiphilic systems as nanocarriers for hydrophobic guest molecules was demonstrated by encapsulating a hydrophobic dye, Nile Red, and a hydrophobic drug, Nimodipine. The transport capacity results for both Nimodipine and Nile Red prove them as a promising candidate for drug delivery.

Photochemical Synthesis of Oligomeric Amphiphiles from Alkyl Oxoacids in Aqueous Environments.

The aqueous phase photochemistry of a series of amphiphilic α-keto acids with differing linear alkyl chain lengths was investigated, demonstrating the ability of sunlight-initiated reactions to build molecular complexity under environmentally relevant conditions. We show that the photochemical reaction mechanisms for α-keto acids in aqueous solution are robust and generalizable across alkyl chain lengths. The organic radicals generated during photolysis are indiscriminate, leading to a large mixture of photoproducts that are observed using high-resolution electrospray ionization mass spectrometry, but these products are identifiable following literature photochemical mechanisms. The alkyl oxoacids under study here can undergo a Norrish Type II reaction to generate pyruvic acid, increasing the diversity of observed photoproducts. The major products of this photochemistry are covalently bonded dimers and trimers of the starting oxoacids, many of which are multi-tailed lipids. The properties of these oligomers are discussed, including their spontaneous self-assembly into aggregates.

Cyclic alkyl chains promote the polymer self-assembly and packing orders for solar cells

The micro-structure ordering of the π–conjugated polymer film self-assembling from solution governs its electrical characteristics and performances for organic electronics. The side chains appended on the conjugated backbone could impact the self-assembling characteristics of the polymer, which show us how to design novel substituents to optimize the polymer arrangement and packing in its solid state. Here, cyclic alkyl chains are proven to be excellent ones for designing of narrow bandgap polymers, the design feature of which with preferential conformations can promote the polymer self-assembly and result in higher degree of lamellar order as well as tighter lamellar packing in the active layer, comparing with linear alkyl chains. The linear ones have poorer ordering in the polymer:fullerene blends as well as in the single crystals of the monomers. The well-organized polymer micro-structures facilitate polymer:fullerene phase separation together with balanced hole/electron transporting, and ultimately, improve the power conversion efficiency impressively compared to linear chains.

Intramolecular Benzoin Reaction Catalyzed by Benzaldehyde Lyase from Pseudomonas Fluorescens Biovar I.

Intramolecular benzoin reactions catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I (BAL) are reported. The structure of the substrates envisaged for this reaction consists of two benzaldehyde derivatives linked by an alkyl chain. The structural requirements needed to achieve the intramolecular carbon-carbon bond reaction catalyzed by BAL were established. Thus, a linker consisting of a linear alkyl chain of three carbon atoms connected through ether-type bonds to the 2 and 2' positions of two benzaldehyde moieties, which could be substituted with either Cl, Br, or OCH3 at either the 3 and 3' or 5 and 5' positions, were suitable substrates for BAL. Reactions with 61-84 % yields of the intramolecular product and ee values between 64 and 98 %, were achieved.

Morphology Control in Films of Isoindigo Polymers by Side-Chain and Molecular Weight Effects.

The performance of devices relying on organic electronic materials, such as organic field-effect transistors (OFET) and organic photovoltaics (OPV), is strongly correlated to the morphology of the conjugated material in thin films. For instance, several factors such as polymer solubility, weak intermolecular forces between polymers and fullerene derivatives, and film drying time impact phase separation in the active layer of a bulk heterojunction OPV device. In an effort to probe the influence of polymer assembly on morphology of polymer thin films and phase separation with fullerene derivatives, five terthiophene-alt-isoindigo copolymers were synthesized with alkyl side-chains of varying lengths and branching on the terthiophene unit. These P[T3(R)-iI] polymers were designed to have similar optoelectronic properties but different solubilities in o-dichlorobenzene and were predicted to have different tendencies for crystallization. All polymers with linear alkyl chains exhibit similar thin film morphologies as investigated by grazing-incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM). The main differences in electronic and morphological properties arise when P[T3(R)-iI] is substituted with branched 2-ethylhexyl (2EH) side-chains. The bulky 2EH substituents lead to a blue-shifted absorption, a lower ionization potential, and reduced ordering in polymer thin films. The five P[T3-iI] derivatives span hole mobilities from 1.5 × 10-3 to 2.8 × 10-2 cm2 V-1 s-1 in OFET devices. In OPV devices, the 2EH-substituted polymers yield open-circuit voltages of 0.88 V in BHJ devices yet low short-circuit currents of 0.8 mA cm-2, which is explained by the large phase separation observed by AFM in blends of P[T3(2EH)-iI] with PC71BM. In these P[T3(R)-iI] systems, the propensity for the polymers to self-assemble prior to aggregation of PC71BM molecules was key to achieving fine phase separation and increased short-circuit currents, eventually resulting in power conversion efficiencies of 5% in devices processed using a single solvent.

3-(Phenyl-4-oxy)-5-phenyl-4,5-dihydro-(1H)-pyrazole: A fascinating molecular framework to study the enantioseparation ability of the amylose (3,5-dimethylphenylcarbamate) chiral stationary phase. Part II. Solvophobic effects in enantiorecognition process

The enantiomers of five chiral compounds incorporating the 3-(phenyl-4-oxy)-5-phenyl-4,5-dihydro-(1H)-pyrazole scaffold and differing only in the linear alkyl chain (varying in length from 1 to 5 carbon atoms) linked to the oxygen atom were directly separated on the amylose (3,5-dimethylphenylcarbamate) based Chiralpak AD-3 chiral stationary phase. The effects of the mobile phase composition, the structure of the analytes and temperature on the retention and enantioselectivity were investigated. It was found that the enantiomeric separations were in all cases enthalpy-driven and disfavored by entropic term. U-shape curves obtained by plotting the chromatographic data versus the alcoholic percentage in n-pentane-methanol and n-hexane-ethanol mobile phases highlighted that, at higher alcohol concentrations, solvophobic interactions were operative in the retention mechanism. The unusual trend of such curves was linked to the nature of alkyl chain of the pyrazolines and it was indicative of the solvophobic contribution to the achievement of a high degree of enantioseparation.

Ionic complexes of poly(γ-glutamic acid) with alkyltrimethylphosphonium surfactants

A series of ionic complexes with a comb-like architecture and a nearly stoichiometric composition were prepared from bacterial poly(γ,dl-glutamic acid) (PGGA) and alkyltrimethyl phosphonium bromides (nATMP·Br) bearing long linear alkyl chains with even numbers of carbon atoms (n) ranging from 12 to 22. The nATMP·PGGA complexes were non-water soluble but readily soluble in organic solvents, and they displayed a high thermal stability. Combined DSC and XRD studies revealed that these complexes adopted an amphiphilic layered structure with the polypeptide chain and the alkyl chain separated in two differentiated phases with a nanoperiodicity that increased steadily with the length of the alkyl chain. The paraffinic phase was found to be partially crystallized in an extent that decreased with n, so that complexes with n = 12 and 14 did not show any sign of crystallinity whereas those with n from 16 to 22 showed crystalline melting in the ∼30–70 °C range. The structural transitions taking place by temperature effects were characterized by simultaneous SAXS/WAXS using synchrotron radiation at real time. In all cases, a shortening of the layer periodicity occurred upon heating with recovering of the initial structure after cooling. nATMP·PGGA with n ≤ 16 showed strong antimicrobial activity against both E. coli and S. aureus, a property that could be related to the weak dissociation of the complexes happening upon incubation in water. The structure and properties of these complexes where comparatively discussed taking as reference their analog complexes made from PGGA and alkyltrimethylammonium bromides already studied by us.

Understanding weakly coordinating anions: tetrakis(pentafluorophenyl)borate paired with inorganic and organic cations.

Efficient design of ionic compounds requires a systematic understanding of cation-anion interactions. Weakening of electrostatic attraction is essential to increase the liquid range of the ionic compound and decrease its melting point. Here, we report simulations of the closest-approach cation-anion distances in a variety of ion pairs containing the tetrakis(pentafluorophenyl)borate (TFPB-) anion. Small alkali cations (Li+, Na+) penetrate the TFPB- core, whereas K+ and larger organic cations do not. In the latter case, the shortest possible distance from the cations to the boron atom of TFPB- ranges from 0.50nm to 0.63nm. TFPB- was shown to be substantially rigid, providing a steric hindrance to thermodynamically efficient cation-anion coordination. Our results prove that TFPB- is more efficient for electrostatic charge confinement than the tetraoctylammonium cation, whereas the perfluorophenyl group is more efficient than linear alkyl chains. These simulations will motivate development of TFPB--based ionic liquids with low phase transition points. Graphical Abstract Ionic configuration of the equilibrated "TFPB + K"system.

TRANSPORT PROPERTIES FOR 1-ETHYL-3-METHYLIMIDAZOLIUM n-ALKYL SULFATES: POSSIBLE EVIDENCE OF GROTTHUSS MECHANISM

The objective of this work was to study the effect of the temperature and the lengthening of the linear alkyl chain of the anion in the transport physical properties of the pure ionic liquids 1-ethyl-3-methyl imidazolium n-alkyl sulphate (being n=0, 1, 2, 4, 6 and 8). Density, viscosity and electrical conductivities were measured at atmospheric pressure in a wide temperature range. In the bibliography, data existed for these magnitudes for all ionic liquids studied but none of these had information about the electrical conductivity of 1-ethyl-3-methyl imidazolium n-alkyl sulfate whith n=0, 4, 6 and 8. The experimental results show clearly 1-ethyl-3-methyl imidazolium hydrogen sulphate cannot be considered part of the 1-ethyl-3-methyl imidazolium n-alkyl sulphate family because of its hydrogen bonding ability. Results of density and viscosity behave as expected. However, in the case of the electrical conductivity due to the lack of alkyl chain in the hydrogen sulfate we expected to get extreme values but in practise, we obtained intermediate values between 1-ethyl-3-methyl imidazolium butyl sulphate and 1-ethyl-3-methyl imidazolium hexyl sulphate. This suggests that a Grotthus mechanism exists as result of a protonic current in addition to ionic conductivity, being Waldeńs plot consistent with this idea.

Synthesis and properties of dicarbazolyltriphenylethylene-substituted fluorene derivatives exhibiting aggregation-induced emission enhancement

Abstract Two novel dicarbazolyltriphenylethylene-substituted fluorene derivatives DctF and Dct 2 F were synthesized by the Wittig-Horner and Suzuki coupling reactions. It was reasoned that introducing linear alkyl chains into the fluorene structure could facilitate the deposition of high-quality films by an economical and simple process. The thin solid films of DctF and Dct 2 F show strongly enhanced emissions in comparison to their dilute solutions, which indicate the aggregation-induced emission enhancement (AIEE). Their decomposition temperatures (T d) exceed 400°C and the glass transition temperature (T g) of DctF is 105°C. The maximum fluorescence emission wavelengths are in the region of 458–469 nm.

Degradation of organic pollutants in near-neutral pH solution by Fe-C micro-electrolysis system

The degradation of organic pollutants in the simulated and realistic wastewaters was investigated by Fe-C micro-electrolysis system. Effects of initial pH, Fe/C mass ratio, gas bubbling type (air or N2) and the type of anions on degradation and mineralization of Sunset Yellow (SY) were studied. The degradation and mineralization efficiencies of 500mg·L−1 SY were approximately 99.0% and 77.5% after 90min treatment, when the initial pH, Fe/C ratio and air bubbling flow rate were 6.0, 1:1 and 45L·h−1, respectively. Besides, the type of anions had a significant influence on the Fe-C micro-electrolysis process. The results of kinetics study indicated that Fe-C micro-electrolysis process followed second-order-kinetics well. The degradation pathway and mechanism for SY were proposed based on FTIR and LC–MS analyses of treated wastewater. Additionally, the Fe-C micro-electrolysis process could dispose linear alkyl chain and benzene ring compounds efficiently under the optimal conditions, and the mineralization efficiencies were in the range of 94–96% and approximately 80%, respectively. The degradation feasibility of a realistic wastewater by the Fe-C micro-electrolysis system was investigated with landfill leachate. In conclusion, Fe-C micro-electrolysis system is an effective and promising technology for organic wastewater treatment in near-neutral pH condition.

Specific Conformational Change in Giant DNA Caused by Anticancer Tetrazolato-Bridged Dinuclear Platinum(II) Complexes: Middle-Length Alkyl Substituents Exhibit Minimum Effect.

Derivatives of the highly antitumor-active compound [{cis-Pt(NH3)2}2(μ-OH)(μ-tetrazolato-N2,N3)]2+ (5-H-Y), which is a tetrazolato-bridged dinuclear platinum(II) complex, were prepared by substituting a linear alkyl chain moiety at C5 of the tetrazolate ring. The general formula for the derivatives is [{cis-Pt(NH3)2}2(μ-OH)(μ-5-R-tetrazolato-N2,N3)]2+, where R is (CH2)nCH3 and n = 0 to 8 (complexes 1-9). The cytotoxicity of complexes 1-4 in NCI-H460 human non-small-cell lung cancer cells decreased with increasing alkyl chain length, and those of complexes 5-9 increased with increasing alkyl chain length. That is, the in vitro cytotoxicity of complexes 1-9 was found to have a U-shaped association with alkyl chain length. This U-shaped association is attributable to the degree of intracellular accumulation. Although circular dichroism spectroscopic measurement indicated that complexes 1-9 induced comparable conformational changes in the secondary structure of DNA, the tetrazolato-bridged complexes induced different degrees of DNA compaction as revealed by a single DNA measurement with fluorescence microsopy, which also had a U-shaped association with alkyl chain length that matched the association observed for cytotoxicity. Complexes 7-9, which had alkyl chains long enough to confer surfactant-like properties to the complex, induced DNA compaction 20 or 1000 times more efficiently than 5-H-Y or spermidine. A single DNA measurement with transmission electron microscopy revealed that complex 8 formed large spherical self-assembled structures that induced DNA compaction with extremely high efficiency. This result suggests that these structures may play a role in the DNA compaction that was induced by the complexes with the longer alkyl chains. The derivatization with a linear alkyl chain produced a series of complexes with unique cellular accumulation and DNA conformational change profiles and a potentially useful means of developing next-generation platinum-based anticancer drugs. In addition, the markedly high ability of these complexes to induce DNA compaction and their high intracellular accumulation emphasized the difference in mechanism of action from platinum-based anticancer drugs.

Charge mobility enhancement for diketopyrrolopyrrole-based conjugated polymers by partial replacement of branching alkyl chains with linear ones

Side-chain engineering of three new conjugated D–A terpolymers by varying the number of branching and linear alkyl chains is presented for OFET studies.

Effects of Fatty Acid Addition to Oil-in-water Emulsions Stabilized with Sucrose Fatty Acid Ester.

Adding fatty acids to an oil-in-water (O/W) emulsion changes the stability of the emulsion. In this study, we prepared a series of O/W emulsions consisting of oil (triolein/fatty acid mixture), water and a range of surfactants (sucrose fatty acid esters) with varying hydrophilic-lipophilic balance (HLB) in order to determine the effects of alkyl chain length and the degree of unsaturation of the fatty acid molecules on the stability of the emulsions. As a result, sucrose fatty acid esters with HLB = 5-7 were suitable for obtaining O/W emulsions. In addition, the creaming phenomenon was inhibited for 30 days or more when fatty acids having a linear saturated alkyl chain with 14 or more carbon atoms were added. These findings are useful for designing stable O/W emulsions for food and cosmetic products.

Which Molecular Features Affect the Intrinsic Hepatic Clearance Rate of Ionizable Organic Chemicals in Fish?

Greater knowledge of biotransformation rates for ionizable organic compounds (IOCs) in fish is required to properly assess the bioaccumulation potential of many environmentally relevant contaminants. In this study, we measured in vitro hepatic clearance rates for 50 IOCs using a pooled batch of liver S9 fractions isolated from rainbow trout (Oncorhynchus mykiss). The IOCs included four types of strongly ionized acids (carboxylates, phenolates, sulfonates, and sulfates), three types of strongly ionized bases (primary, secondary, tertiary amines), and a pair of quaternary ammonium compounds (QACs). Included in this test set were several surfactants and a series of beta-blockers. For linear alkyl chain IOC analogues, biotransformation enzymes appeared to act directly on the charged terminal group, with the highest clearance rates for tertiary amines and sulfates and no clearance of QACs. Clearance rates for C12-IOCs were higher than those for C8-IOC analogues. Several analogue series with multiple alkyl chains, branched alkyl chains, aromatic rings, and nonaromatic rings were evaluated. The likelihood of multiple reaction pathways made it difficult to relate all differences in clearance to specific molecular features the tested IOCs. Future analysis of primary metabolites in the S9 assay is recommended to further elucidate biotransformation pathways for IOCs in fish.

New N,N-dimethylcarbamate inhibitors of acetylcholinesterase: design synthesis and biological evaluation

A series of N,N-dimethylcarbamates containing a N,N-dibenzylamino moiety was synthesized and tested to evaluate their ability to inhibit Acetylcholinesterase (AChE). The most active compounds 4 and 8, showed 85 and 69% of inhibition at 50 μM, respectively. Furthermore, some basic SAR rules were outlined: an alkyl linker of six methylene units is the best spacer between the carbamoyl and dibenzylamino moieties; electron-withdrawal substituents on aromatics rings of the dibenzylamino group reduce the inhibitory power. Compound 4 produces a slow onset inhibition of AChE and this is not due to the carbamoylation of the enzyme, as demonstrated by the time-dependent inhibition assay of AChE with compound 4 and by MALDI-TOF MS analysis of trypsinized AChE inhibited by compound 4. Instead, compound 4 could act as a slow-binding inhibitor of AChE, probably because of its high conformational freedom due to the linear alkyl chain.

High-resolution separation performance of poly(caprolactone)diol for challenging isomers of xylenes, phenols and anilines by capillary gas chromatography

Efficient separation of xylenes, phenols and anilines is a big issue in chemical and petroleum industries. This work presents the first example of employing poly (caprolactone) diol (PCL-Diol) as stationary phase for high-resolution gas chromatographic (GC) separations of these tough isomer mixtures. It showed medium polarity and stronger H-bonding basicity than H-bonding acidity. Impressively, PCL-Diol column exhibited extremely high resolving capability for the isomer mixtures of xylenes, cresols/xylenols, and toluidines/xylidines with good peak shapes. Moreover, it exhibited preferential retention for analytes of a linear alkyl chain, suggesting its shape fitting selectivity for specific analytes. In addition, its separation performance has good repeatability with RSD values on retention times below 0.01% for run to run (n=6), 0.67–0.80% for day to day (n=4) and 3.2–4.4% for column to column (n=4) repeatability, respectively. Furthermore, it was applied for the determination of isomer impurities in real samples, showing good potential for practical use. This work demonstrates the advantageous high-resolution separation performance for challenging isomers and shows its promising future of PCL-Diol-based materials in separation science.

Understanding the Structural Basis of ALDH-2 Inhibition by Molecular Docking.

The ALDH-2 enzyme has been identified as an important therapeutic target for the development of new drugs for the treatment of cocaine addiction. Several studies involving the synthesis, the design and pharmacological evaluation of daidzin (isoflavonoid inhibitor of ALDH-2) analogs were conducted. In this study, we used two in silico approaches effective to understand the mechanism of inhibition of ALDH-2 enzyme, the molecular docking and constructing a pharmacophore model, and we established a correlation between the inhibitory profiles of daidzin and its analog for ALDH-2 and their interaction profiles to understand the structural basis for their inhibitory activities. Docking is efficient and opportune tool to guide the design of new inhibitors of ALDH-2. From the results of the molecular docking studies performed herein and their relationships with the inhibitory profiles of some daidzin analogs described previously in the literature, pharmacophore groups associated with ALDH-2 enzyme recognition were identified. Summarizing our findings, the presence of a linear alkyl chain with a terminal hydrogen bond acceptor group in position 7 is important for the interaction with the Gln-289 residue. Additionally, the presence of a group that is capable of performing hydrogen bonding interactions as either a donor or acceptor in the 4' position is important for the interaction with the Glu-268 residue; this group is the primary pharmacophore that should be attached to the scaffold of the aromatic nucleus of an ideal inhibitor of ALDH-2. The structure inhibitory activity relationships among daidzin analogs were established using a molecular docking tool, thus identifying the structural reasons for the inhibition of the ALDH-2 enzyme. We defined the key pharmacophore groups required for enzyme inhibition and the maintenance of interactions with the amino acids Gln-289 and Glu-268, which are related to the potency of the ALDH-2 inhibitors. This study is highly relevant for the design of new ALDH-2 inhibitors using different medicinal chemistry tools to develop novel therapies for controlling cocaine addiction.

Norbornene Dialkyl Ester가 첨가된 Isoprene Rubber의 가공성 및 물성에 관한 연구

In this study, we applied six different norbornene dialkyl esters as a plasticizer to an isoprene rubber (IR) and evaluated replaceability of DEHP which is an endocrine disruptor. IR test sheets were prepared by blending IR, norbornene dialkyl ester, vulcanizing agent, etc. and processing properties of the IR were evaluated by measuring Toque, scorch time, cure time and mooney viscosity. Mechanical properties of IR test sheet including hardness, tensile strength, 100% modulus and elonga- tion were also measured and the physical properties of norbornene dialkyl ester applied as a plasticizer were compared to those using DEHN. Both the maximum and minimum toque for the norbornene dialkyl ester as a plasticizer were similar to those of using DEHP. In addition, the scorch and cure time of the former were slightly longer than those of the latter. The mooney viscosity for the case of DEHN was slightly lower than that of the latter. DEHN was also superior to DEHP in terms of processing. The hardness and thermal properties of all IR test sheets were measured to be similar to each other. The linear alkyl chain of norbornene compounds also exhibited good tensile characteristics.