How to broaden the light reflection band in cholesteric liquid crystals? A new approach based on polymorphism

Cholesteric liquid crystals (CLCs) may selectively reflect light when the helicoidal pitch is of the order of the wavelength of the incident beam propagating along the helix axis. The reflection bandwidth is dependent on the birefringence and is limited to a few tens of nanometers, which is insufficient for applications such as white-on-black reflective displays. Recent studies have shown that CLC polymer networks with a pitch gradient induce a broadening of the reflection bandwidth over several hundreds of nanometers. Most related processes rely on photocrosslinking reactions with a UV-gradient in a mixture made of chiral and achiral monomers with different UV-reactivities. Here a new experimental route exploiting the polymorphism of the mixture is presented. The basic concept lies in a thermally-induced pitch variation simultaneously carried out with the UV-crosslinking reaction. The optical behaviour is investigated in parallel with the cross-sectional microstructure as observed by transmission electron microscopy.     

A new synthetic approach based on (−)-menthone for chiral liquid crystals

Starting from (?)-menthone, a new chiral building block useful for liquid crystal preparation was synthesized. This chiral moiety was attached to selected phenols under mild conditions by esterification. Rigid cores of tolanebenzoates and phenylbenzoates were prepared using the palladium cross-coupling reaction or by traditional liquid crystal synthesis methods. This convergent approach ended with a second esterification or palladium cross-coupling reaction to furnish new liquid crystal materials with smectic A, smectic C* and N* phases, as well as blue phases (BP). Thermal behavior, and the effect of chiral moiety branches and molecular packing in the smectic phases, have been investigated using differential scanning calorimetry, optical microscopy and X-ray diffraction.     

On the existence of the thermomechanical terms of Akopyan and Zel’dovich in cholesteric liquid crystals

We revisit a theoretical paper of Akopyan and Zel’dovich about the thermomechanical coupling terms in nematic liquid crystals. We show that the expressions of these terms given by these authors must be corrected to satisfy the Onsager reciprocity relations, a point already stressed by Pleiner and Brand in 1987. We then extend this calculation to the cholesteric phase and show that there are no additional terms in the uniaxial approximation of this phase. Finally, we give the correspondence between the Akopyan and Zel’dovich terms and those calculated by Pleiner and Brand in 1996 by making a different choice for the forces and the fluxes in the theory.     

A new spectrum technique based on direct detection of light intensity absorbed

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A new approach to the synthesis of α-chlorocycloalkanones

α-Chlorocycloalkanones(Ⅳ) were synthesized from cycloalkanones via potassiumα-oxocycloalkylsulfonates(Ⅱ).A two-step mechanism was proposed to explain the formation ofⅣfromⅡ.     

Dispersive liquid–liquid microextraction based on ionic liquid in combination with high-performance liquid chromatography for the determination of bisphenol A in water

A method termed dispersive liquid–liquid microextraction (DLLME) coupled with high-performance liquid chromatography-variable wavelength detection (HPLC-VWD) was developed. DLLME-HPLC-VWD is a method for determination of bisphenol A (BPA) in water samples. In this microextraction method, several parameters such as extraction solvent volume, sample volume, disperser solvent, ionic strength, pH, and disperser volume were optimised with the aid of interactive orthogonal array and a mixed level experiment design. First, an orthogonal array design was used to screen the significant variables for the optimisation. Second, the significant factors were optimised by using a mixed level experiment. Under the optimised extraction conditions (extraction solvent: ionic liquid [C₆MIM][PF₆], 60 µL; dispersive solvent: methanol, 0.4 mL; and pH = 4.0), the performance of the established method was evaluated. The response linearity of the method was observed in a range of 0.002–1.0 mg L^?1 (three orders of magnitude) with correlation coefficient (R ²) of 0.9999. The repeatability of this method was 4.2–5.3% for three different BPA levels and the enrichment factors were above 180. The extraction recovery was about 50% for the three different concentrations with 3.4–6.4% of RSD. Limit of detection of the method was 0.40 µg L^?1 at a signal-to-noise ratio of 3. In addition, the relative recovery of sample of Songhua River, tap water and barrel-drain water at different spiked concentration levels was ranged 95.8–103.0%, 92.6–98.6% and 87.2–95.3%, respectively. Compared with other extraction technologies, there have been the following advantages of quick, easy operation, and time-saving for the present method.     

A new approach to the spectral analysis of liquid membrane oscillators by Gábor transformation

Liquid membrane oscillators very frequently have an irregular oscillatory behavior. Fourier transformation cannot be used for these nonstationary oscillations to establish their power spectra. This important point seems to be overlooked in the field of chemical oscillators. A new approach is presented here based on Gábor transformation allowing one to obtain power spectra of any kind of oscillations that can be met experimentally. The proposed Gábor analysis is applied to a liquid membrane oscillator containing a cationic surfactant. It was found that the power spectra are strongly influenced by the presence of various added substances.     

Liquid crystals 100 years later. What are the new concepts used in the design of molecular,macromolecular and supramolecular liquid crystals?

A brief discussion of selected synthetic strategies pursued in the field of molecular, macromolecular and supramolecular liquid crystals is made by reviewing some tandem historical events of the past 100 years of activity in this field. This survey will try to suggest the rational for the discovery, evolution and investigation of some of these new concepts. Also a brief and speculative forecast of the future of this field will be presented.     

A new approach to δ-lactones,related to the Prelog-Djerassi lactone.

The reductive rearrangement of 2-ethoxy-5-(2-alkenyl)-2H-tetrahydropyrane systems, in the presence of AlBu¹₃, was used as the key-step in the synthesis of Prelog-Djerassi related lactones.     

A novel vertical alignment technology for nematic liquid crystals based on electrostatic self‐assembled method

A novel vertical alignment film for nematic liquid crystals is reported based on electrostatic self‐assembly of alkyl sulfonic salts in aqueous solution. A series of self‐assembled films with different alkyl chain lengths were prepared and used as alignment films. It was revealed that only when the number of carbon atoms in the alkyl chain approaches 11 or larger, could the self‐assembled film induce vertical alignment of liquid crystals. We also found that the homeotropic alignment of liquid crystals was related to the surface roughness of self‐assembled films. In addition, this vertical alignment film showed good electro‐optical characteristics and excellent thermal stability.     

A visual approach to stationary phase selectivity classification based on the Snyder–Dolan Hydrophobic-Subtraction Model

A novel type of stationary phase selectivity classification “triangle” has been developed based on the Snyder–Dolan (S–D) Hydrophobic-Subtraction Model, wherein the apices of a set of four triangles represent the relative contributions of steric hindrance (χ_S), hydrogen-bonding acidity (χ_A), hydrogen-bonding basicity (χ_B), cation-exchange capacity (χ_C) to selectivity. We found that “effective selectivity” of a stationary phase is mathematically given by the ratio of system dependent interaction coefficients but not their absolute values. Thus by normalizing the S*, A, B and C terms of the S–D model by H, we were able to obtain four parameters which fully define the chromatographic selectivity of the stationary phases. By examining the parameters in groups of three, we can represent all the result in a set of four “selectivity triangles”. The distinctive feature of this approach compared to the S–D phase classification scheme is that it allows the visualization of column selectivity by plotting three-dimensional data in a two-dimensional space. Moreover, it very clearly shows that the RPLC columns thus far characterized cover only a small fraction of separation selectivity space leaving a great deal of room for researchers to develop novel RPC materials. Various applications of these “selectivity triangles” will be discussed in this paper.     

How to achieve self-assembly in polar solvents based on specific interactions? Some general guidelines

In general, self-assembly in polar solutions requires a combination of several non-covalent interactions within one binding motif. Besides the combination of H-bonds and hydrophobic or aromatic stacking interactions, in the last few years H-bonded ion pairs have been proven useful in this context. Also the molecular rigidity and the extent of intra- versus intermolecular interactions within the monomer play an important role in determining the self-assembling properties of a given monomer. We present some general guidelines and illustrative examples of various approaches that have been pursued in the literature before finally concentrating on a case study from our own work, the dimerization of a guanidiniocarbonyl pyrrole carboxylate zwitterion. This zwitterion forms stable dimers with K > 10(9) M(-1) in DMSO and >10(2) M(-1) even in water and can not only be used to study the importance of various non-covalent interactions for self-assembly in polar solvents but also to construct large nanostructures.     

A new approach to untargeted integration of high resolution liquid chromatography–mass spectrometry data

Because of its high sensitivity and specificity, hyphenated mass spectrometry has become the predominant method to detect and quantify metabolites present in bio-samples relevant for all sorts of life science studies being executed. In contrast to targeted methods that are dedicated to specific features, global profiling acquisition methods allow new unspecific metabolites to be analyzed. The challenge with these so-called untargeted methods is the proper and automated extraction and integration of features that could be of relevance. We propose a new algorithm that enables untargeted integration of samples that are measured with high resolution liquid chromatography–mass spectrometry (LC–MS). In contrast to other approaches limited user interaction is needed allowing also less experienced users to integrate their data. The large amount of single features that are found within a sample is combined to a smaller list of, compound-related, grouped feature-sets representative for that sample. These feature-sets allow for easier interpretation and identification and as important, easier matching over samples. We show that the automatic obtained integration results for a set of known target metabolites match those generated with vendor software but that at least 10 times more feature-sets are extracted as well. We demonstrate our approach using high resolution LC–MS data acquired for 128 samples on a lipidomics platform. The data was also processed in a targeted manner (with a combination of automatic and manual integration) using vendor software for a set of 174 targets. As our untargeted extraction procedure is run per sample and per mass trace the implementation of it is scalable. Because of the generic approach, we envision that this data extraction lipids method will be used in a targeted as well as untargeted analysis of many different kinds of TOF-MS data, even CE- and GC–MS data or MRM. The Matlab package is available for download on request and efforts are directed toward a user-friendly Windows executable.     

A new concept of hollow fiber liquid–liquid–liquid microextraction compatible with gas chromatography based on two immiscible organic solvents

A new concept of liquid–liquid–liquid microextraction (LLLME) was introduced based on applying two immiscible organic solvents in lumen and wall pores of hollow fiber (HF). With this methodology, analytes of interest can be extracted from aqueous sample, into a thin layer of organic solvent (dodecane) sustained in the pores of a porous hollow fiber, and further into a μL volume of organic acceptor (acetonitrile or methanol) located inside the lumen of the hollow fiber. Some chlorophenols (CPs) were selected as model compounds for developing and evaluating of the method performance. The analysis was performed by gas chromatography–electron capture detection (GC–ECD) without derivatization. The factors affecting the HF-LLLME of target compounds were investigated and the optimal extraction conditions were established. Under the optimum conditions, preconcentration factors in a range of 208–895 were obtained. The performance of the proposed method was studied in terms of linear dynamic ranges (LDRs from 0.02 to 100 ng mL⁻¹), linearity (R² ≥ 0.995), precision (RSD % ≤ 8.1) and limits of detection (LODs in the range of 0.006–0.2 ng mL⁻¹). In addition to preconcentration, HF-LLLME also served as a technique for sample clean-up.     

Prediction of the auto-ignition temperature of binary liquid mixtures based on the quantitative structure–property relationship approach

Journal of Thermal Analysis and Calorimetry - The auto-ignition temperature (AIT) is one of the most important parameters in flammability risk assessment and management in the chemical process....     

A new approach to the study of ion transport processes by an in situ radiotracer method based on measuring intensity changes and energy spectrum alterations of β-radiation

A new approach for the study of ion transport by an in situ radiotracer method is presented. The method is based upon the measurement of the intensity and energy spectrum change of -radiation during the penetration of labeled species. The applicability of the radiotracer technique is detailed through the measurement of the transport of labeled chloride ions into a PERMAPLEX-A20 anion exchanger membrane. The proposed method is applicable to in situ monitoring of the motion of ions in the membrane (or adsorbent).     

Theory on the molecular characteristic contour(Ⅰ)——A new approach to defining molecular characteristic contour

Based on the classical turning point of electron movement in a molecule, a model for defining the molecular characteristic boundary contour is advanced. By using an accurate ab initio MELD program and an auxiliary program, some electron parameters in a molecule, such as the potential felt by an electron, have been evaluated. According to our model and definition, the molecular characteristic contour of the equilibrium geometry configuration is drawn and a vivid intuitive picture for describing the forming or breaking of a chemical bond is displayed.     

A new POM-templated metal–organic complex based on the flexible bis-pyridyl-bis-amide ligand

A new POM-templated metal?Corganic complex [Cu₄(L)₇(H₂O)₁₂(SiMo₁₂O₄₀)₂]·7H₂O [L?=?N,N??-bis(3-pyridinecarboxamide)-1,6-hexane], has been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction analysis. The results reveal that the complex is a 2D metal?Corganic coordination framework of [Cu₄(L)₇(H₂O)₁₂] _n ⁸ⁿ⁺ cations containing decanuclear cycles with dimensions of ca. 17.55?×?57.42 ?, in which the SiMo₁₂O₄₀ ^4? anions act as non-coordinated anionic templates. The electrochemical properties of a bulk-modified carbon paste electrode of the complex have been investigated, and the results indicate that the complex-modified CPE has good electrocatalytic activity toward the reduction of nitrite in aqueous 1?M H₂SO₄ solution.     

Synthesis and characterisation of photopolymerisable liquid crystals based on the π-extended fluorene core and their corresponding non-reactive analogues

We have synthesised a series of new reactive mesogens with photopolymerisable di-acrylates and their corresponding non-reactive analogues based on the π-conjugated aromatic core, fluorene (F)-di-[thiophene (T)-benzene (B)], using the Stille and Suzuki coupling reaction. The effect of lateral alkyl chains on the 9-position of the central fluorene moiety as well as α, ω- side alkyl chains attached to the π-conjugated aromatic core on the mesomorphism was investigated by utilising differential scanning calorimetry (DSC) and polarising optical microscopy (POM). A wide angle X-ray scattering (WAXS) study at the various temperatures was also carried out to reveal phase structures. Photopolymerisable di-acrylates connected directly to the rigid aromatic core showed higher phase transition temperatures, probably due to the induced dipole moment in comparison with those of a non-reactive methyl–ether counterpart.