Effect of spacer length on mesomorphic behaviours of chiral liquid crystal compounds containing (-)-menthyl

ABSTRACT

A homologous series of new chiral liquid crystal compounds, MnBEB (n = 4–10), was prepared by covalently linking a chiral (–)-menthyl with biphenyl-benzoate via a dicarboxylic spacer of varying length and parity. A combination of analysis methods, such as FT-IR, ¹H NMR spectra, differential scanning calorimetry (DSC), polarised optical microscopy (POM) and X-ray diffraction was carried out to systematically investigate their phase structures and phase transition behaviours. The length and parity of the flexible spacers has a profound influence on the T_m and T_c and a modest odd-even effect is observed for the chiral liquid crystal compounds MnBEB. Only compound M4BEB developed an N* phase with selectively reflection on heating and a blue phase on cooling process. In addition, increasing the length of the flexible spacers tends to narrow the temperature range of the N* phase and widen the smectic phase, moreover, the pitch becomes longer with the spacer increases.     

Compton Spectrum Due to L-Shell Electrons

Compton spectrum due to L-shell electrons of thorium has been measured by the coincidence technique, using 279 keV incident gamma photons. The influence of L-shell electron momenta on the distribution of the scattered photons has been studied with reference to the Compton profile due to free electrons and compared with the exact and impulse hydrogenic theoretical models. Significant deviations are found between experimental and theoretical Compton spectra.     

Important unanswered questions—1970

This paper was given as the opening address at the 1970 Albany International Conference on Radiation Effects in Semiconductors, and it attempts to establish a general overview of the field by concentrating on recent research developments and important unanswered questions. The continuing importance of impurity-defect interactions, of microscopic defect identification, and of the necessity for more theoretical calculations are emphasized. The rapid development of the field of ion implantation and its close relationship with radiation effects studies are pointed out. It is predicted that research in compound semiconductors will increase rapidly with close beneficial interaction with ion implantation studies.     

不同光场二阶相干度的实验研究

基于Hanbury Brown-Twiss(HBT)实验,我们借助于两个单光子计数模块,一个50/50分束器和一个快速计数卡(FastCom-P7888)研究了不同光场的二阶相干度。我们首先制备了脉冲相干光,连续相干光以及单原子发出的单光子源,并测量这几种不同光场的二阶相干度g(2)(τ)。我们通过测量俘获在磁光阱(MOT)和远失谐偶极阱(FORT)中的单原子在近共振连续激光激发下所辐射的荧光的二阶相干度,分别得到了g(2)(τ=0)=0.08和g(2)(τ=0)=0.09,借助于实验中产生的脉冲光与单原子,接下来我们将进行触发式单光子源的实验研究。     

The gas phase oxidation of HCOOH by Cl and NH2 radicals. Proton coupled electron transfer versus hydrogen atom transfer*

ABSTRACT

The reaction of formic acid (HCOOH) with chlorine atom and amidogen radical (NH₂) have been investigated using high level theoretical methods such BH&HLYP, MP2, QCISD, and CCSD(T) with the 6–311?+?G(2df,2p), aug-cc-pVTZ, aug-cc-pVQZ and extrapolation to CBS basis sets. The abstraction of the acidic and formyl hydrogen atoms of the acid by the two radicals has been considered, and the different reactions proceed either by a proton coupled electron transfer (pcet) and hydrogen atom transfer (hat) mechanisms. Our calculated rate constant at 298?K for the reaction with Cl is 1.14?×?10^?13?cm³?molecule^?1?s^?1 in good agreement with the experimental value 1.8?±?0.12/2.0?×?10^?13?cm³?molecule^?1?s^?1 and the reaction proceeds exclusively by abstraction of the formyl hydrogen atom, via hat mechanism, producing HOCO+ClH. The calculated rate constant, at 298?K, for the reaction with NH₂ is 1.71?×?10^?15?cm³?molecule^?1?s^?1, and the reaction goes through the abstraction of the acidic hydrogen atom, via a pcet mechanism, leading to the formation of HCOO+NH₃.     

An optimized method for the determination of volatile and semi-volatile aldehydes and ketones in ambient particulate matter

A method has been developed to measure aldehydes and ketones associated with atmospheric particles. Carbonyl compounds from particulate material collected on Teflon-coated glass-fiber filters were simultaneously extracted and derivatized with an appropriate 2,4-dinitrophenylhydrazine (2,4-DNPH) solution. The efficiency of this procedure utilizing various 2,4-DNPH concentrations and solvent compositions was studied for 13 carbonyl compounds of atmospheric importance. These include formaldehyde, acetaldehyde, acetone, dicarbonyls such as glyoxal and methylglyoxal, and biogenic carbonyls such as pinonaldehyde and nopinone. An extraction solution containing 3 × 10^?2 M 2,4-DNPH, in 60% acetonitrile/40% water, and pH 3 was most efficient in extracting and derivatizing these aldehydes and ketones (83-100% recovery). Improved sample enrichment and 2,4-DNPH purification methods were developed that afforded detection limits of 0.009-5.6 ng m^?3. The relative standard deviation for replicate analyses were 1.9-10.1%. Carbonyl compounds in ambient particulate samples were quantified during a recent field study. Median values for nine carbonyl species ranged from 0.01-33.9 ng m^?3 during the study.     

An improved Sampling Strategy for the Measurement of VOCs in Air,Based on Cooled Sampling and Analysis by Thermodesorption-GC-MS/FID

Abstract

Reliable and comprehensive sampling methods are required to obtain accurate data for VOC concentrations in air samples. The major drawback of the adsorption tube sampling method, widely employed in environmental studies, is the fact that C₂ compounds are usually not trapped quantitatively.

The focus of this work was thus to improve sampling based on adsorption tubes packed with Molsieve and Carbosieve. To improve the sampling efficiency for the C₂ compounds, a cooling device, based on Peltier cooling was constructed, which could be operated at a temperature down to ?30°C.

Experiments under laboratory and field conditions were carried out to study the influence of the sampling temperatuie on the recovery of ethane and ethene as the most volatile VOCs. The results clearly demonstrate the need for a cooled sampling device for the analysis of C₂ compounds in air. Under the investigated conditions, the recoveries with ambient temperature sampling were only in the range of 38–46% for ethane and 33–59% for ethene respectively, in comparison to the cooled sampling device. These findings are only valid for the described conditions and can change significantly with temperature and concentration. A generalisation of the recovery is thus very difficult to give.

The use of the sampling device for a field study is reported, where samples were collected simultaneously at three different altitudes in a diurnal profile on the slope of the Schulterberg mountain in Tyrol (Austria).     

Issue Information

Three‐dimensional direct numerical simulation results of flow past a circular cylinder are influenced by numerical aspects, for example the spanwise domain length and the lateral boundary condition adopted for the simulation. It is found that inappropriate numerical set‐up, which restricts the development of intrinsic wake structure, leads to an over‐prediction of the onset point of the secondary wake instability (Re_cr). A best practice of the numerical set‐up is presented for the accurate prediction of Re_cr by direct numerical simulation while minimizing the computational cost. The cylinder span length should be chosen on the basis of the intrinsic wavelength of the wake structure to be simulated, whereas a long span length is not necessary. For the wake transitions above Re_cr, because the wake structures no longer follow particular wavelengths but become disordered and chaotic, a span length of more than 10 cylinder diameters (approximately three times the intrinsic wavelength) is recommended for the simulations to obtain wake structures and hydrodynamic forces that are not strongly restricted by the numerical set‐up. The performances of the periodic and symmetry lateral boundary conditions are compared and discussed. The symmetry boundary condition is recommended for predicting Re_cr, while the periodic boundary condition is recommended for simulating the wake structures above Re_cr. The general conclusions drawn through a circular cylinder are expected to be applicable to other bluff body configurations. Copyright © 2017 John Wiley & Sons, Ltd.     

Effects of graft length and density of well‐defined graft polymers on the thermoresponsive behavior and self‐assembly morphology

A series of well‐defined thermoresponsive graft polymers with different lengths and graft densities, poly(glycidyl methacrylate)‐graft‐poly(N‐isopropylacrylate) (PGMA‐g‐PNIPAM), were successfully prepared by combination of controlled/living free radical polymerization and click chemistry. Effects of grafting length and density on the thermoresponsive behavior, aggregating mean diameter, and self‐assembly morphology are systematically investigated. The thermosensitive characteristics of graft polymers in aqueous solution prove that the length and graft density had positive co‐relationship with the lower critical solution temperature value and mean diameter of micelles as well as the size distribution, while the effect of graft length of polymers is more significant than that of density. Transmission electron microscopy analysis shows that the conformations of PGMA₄₅‐g‐PNIPAM₂₀ and PGMA₄₅‐g‐PNIPAM₄₆ with longer length and bigger grafting density in aqueous solutions are spherical nanoparticles with the increasing trend of the diameters, while that of PGMA₄₅‐g‐PNIPAM_{(73, 50%)} shows a spherical‐like morphology, which indicates that the graft length and density have a significant effect on the mean diameter of micelle but not on the self‐assembly morphology. These results reveal that to obtain desired thermoresponsive behavior and self‐assembly morphology of functional polymers, it is essential to design and fabricate the structure of graft polymers with proper length and graft density. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2442–2453