用静态和动态辐射等离子流处理基板上的液晶取向

在本文,我们介绍关于液晶取向的新成果,基板用阳极分层推进器(anode layer s thruster,ALT)产生的加速氩等离子体"层(sheet)"作倾斜处理.由有机的(聚合物)和无机的(玻璃,类金刚石(DLC),二氧化硅等)原材料做成的基板,用等离子体流在静态和动态(垂直于等离子体层方向单向变化)方式下进行处理.对于正性液晶(△ε＞0),在两种方式下观察到两种取向模式易取向轴限制在入射等离子层平面内(模式1)或垂直于这个平面(模式2).在第1种取向模式中,液晶的预倾角不等于零,并且随着等离子体束入射角和辐射量而变化,其均匀性在动态辐射中更好.随着辐射的增强,会发生模式1到模式2的转变.应用于垂面取向液晶显示器(VA LCD)的负性液晶混合物(△ε＜0),只有第1种模式(在整个基板上一致取向)被观察到,在辐射量低或高(正性液晶出现第2种取向模式时的相对高的辐射量)时都能出现.预倾角可高达30°,由等离子束的辐射量和入射角来控制.第2种模式在高辐射下出现,并且只在静态方式下,位于等离子层中心的、比较密集的区域,而第1种取向模式在其外围.模式1和模式2由狭窄的过渡区分开,该区呈现多畴液晶取向(二重简并).这些畴的易取向轴相对于模式1中取向方向大约偏转±45°.对于负性液晶,由模式1到二重简并到模式2转变的取向方式,与早期真空镀膜产生的取向非常相似.对于正性和负性两种液晶,我们实现了动态辐射下在15×15cm2基板上的均匀取向.     

Chromatographic separation and multicollection-ICPMS analysis of iron. Investigating mass-dependent and -independent isotope effects

A procedure was developed that allows precise determination of Fe isotopic composition. Purification of Fe was achieved by ion chromatography on AG1-X8 strongly basic anion-exchange resin. No isotopic fractionation is associated with column chemistry within 0.02 per thousand /amu at 2sigma. The isotopic composition was measured with a Micromass IsoProbe multicollection inductively coupled plasma hexapole mass spectrometer. The Fe isotopic composition of the Orgueil CI1 carbonaceous chondrite, which best approximates the solar composition, is indistinguishable from that of IRMM-014 (-0.005 +/- 0.017 per thousand /amu). The IRMM-014 reference material is therefore used for normalization of the isotopic ratios. The protocol for analyzing mass-dependent variations is validated by measuring geostandards (IF-G, DTS-2, BCR-2, AGV-2) and heavily fractionated Fe left after vacuum evaporation of molten wüstite (FeO) and solar (MgO-Al(2)O(3)-SiO(2)-CaO-FeO in chondritic proportions) compositions. It is shown that the isotopic composition of Fe during evaporation of FeO follows a Rayleigh distillation with a fractionation factor alpha equal to (m(1)/m(2)()1/2), where m(1) and m(2) are the masses of the considered isotopes. This agrees with earlier measurements and theoretical expectations. The isotopic composition of Fe left after vacuum evaporation of solar composition also follows a Rayleigh distillation but with a fractionation factor (1.013 22 +/- 0.000 67 for the (56)Fe/(54)Fe ratio) that is lower than the square root of the masses (1.018 35). The protocol for analyzing mass-independent variations is validated by measuring terrestrial rocks that are not expected to show departure from mass-dependent fractionation. After internal normalization of the (57)Fe/(54)Fe ratio, the isotopic composition of Fe can be measured accurately with precisions of 0.2epsilon and 0.5epsilon at 2sigma for (56)Fe/(54)Fe and (58)Fe/(54)Fe ratios, respectively (epsilon refers to relative variations in parts per 10 000). For (58)Fe, this precision is an order of magnitude better than what had been achieved before. The method is applied to rocks that could potentially exhibit mass-independent effects, meteorites and Archaean terrestrial samples. The isotopic composition of a 3.8-Ga-old banded iron formation from Isua (IF-G, Greenland), and quartz-pyroxene rocks from Akilia and Innersuartuut (GR91-26 and SM/GR/171770, Greenland) are normal within uncertainties. Similarly, the Orgueil (CI1), Allende (CV3.2), Eagle Station (ESPAL), Brenham (MGPAL), and Old Woman (IIAB) meteorites do not show any mass-independent effect.     

Investigation of Nitramine‐Based Amorphous Energetics

To date, the use of high explosives (HEs) has been largely limited to their crystalline forms. The glassy forms of these materials have not received much attention. While the highest density and stability of HEs is only attainable in the crystalline state, the unique properties exhibited by glasses may offer significant practical advantages. In this work, the production and properties of glassy molecular dispersions based on CL‐20 with HMX and polyvinyl acetate additives were investigated. The glassy form was achieved by rapid precipitation of the composite ingredients using spray drying. The role of the additives on glass formation was examined. Characterization revealed multiple novel properties in comparison to the traditional crystalline HE‐based compositions. Differential scanning calorimetry (DSC) analysis showed that in the glassy state the materials have a higher configurational enthalpy, by as much as 42 J g⁻¹. Thermomechanical analysis (TMA) results indicate that the glassy materials undergo a glass transition at around 50 °C, during which a transformation from a rigid to a liquid‐like state occurs. The glasses showed a tendency to crystallize, as was observed with TMA and DSC analysis. It was observed that the stability of the amorphous phase with respect to crystallization improved with increasing pellet density. These findings serve to highlight the unique opportunity presented by glassy energetics to achieve improvements beyond those attainable with traditional crystalline materials.     

Electrocatalytic tandem Knoevenagel-Michael reaction of 3-methyl-2-pyrazolin-5-ones, aryl aldehydes and cyano-functionalized C-H acids: Facile and convenient multicomponent way to substituted 3-(5-hydroxy-3-methylpyrazol-4-yl)-3-arylpropionitriles

Electrochemically induced catalytic tandem Knoevenagel-Michael reaction of 3-methyl-2-pyrazolin-5-ones, aryl aldehydes and malononitrile or alkyl cyanoacetates in alcohols in an undivided cell in the presence of sodium bromide as an electrolyte results in the formation of substituted 3-(5-hydroxy-3-methylpyrazol-4-yl)-3-arylpropionitriles in 75-97% yields. The developed efficient electrocatalytic approach to the corresponding 3-(5-hydroxy-3-methylpyrazol-4-yl)-3-arylpropionitriles is beneficial from the viewpoint of diversity-oriented large-scale processes and represents novel, facile and environmentally benign synthetic concept for multicomponent reactions strategy.     

Design of High-Relaxivity Polyelectrolyte Nanocapsules Based on Citrate Complexes of Gadolinium(III) of Unusual Composition

Through nuclear magnetic relaxation and pH-metry, the details of the complexation of gadolinium(III) ions with citric acid (H₄L) in water and aqueous solutions of cationic polyelectrolytes are established. It is shown that the presence of poly(ethylene imine) (PEI) in solution affects magnetic relaxation behavior of gadolinium(III) complexes with citric acid (Cit) to a greater extent than polydiallyldimethylammonium chloride (PDDC). A large increase in relaxivity (up to 50 mM⁻¹s⁻¹) in the broad pH range (4–8) is revealed for the gadolinium(III)–citric acid–PEI system, which is particularly strong in the case of PEI with the molecular weight of 25 and 60 kDa. In weakly acidic medium (pH 3–7), the presence of PEI results in the formation of two tris-ligand associates [Gd(H₂L)₃]³⁻ and [Gd(H₂L)₂(HL)]⁴⁻, which do not exist in aqueous medium. In weakly alkaline medium (pH 7–10), formation of ternary complexes Gd(III)–Cit–PEI with the Gd(III)–to–Cit ratio of 1:2 is evidenced. Using transmission electron microscopy (TEM) and dynamic light scattering techniques (DLS), the formation of the particles with the size of 50–100 nm possessing narrow molecular-mass distribution (PDI 0.08) is determined in the solution containing associate of PEI with tris-ligand complex [Gd(H₂L)₂(HL)]⁴⁻.     

Phase Stability and Ionic Conductivity of Solid Solutions with NASICON Structure

Formation of heterovalent Zr-substituted solid solutions (up to 7 mol%) for Yb³⁺ in Na₆Yb₃(PO₄)₅ and LiNa₅Yb₃(PO₄)₅ complex phosphates was studied by ceramic technique at 950°C. Obtained samples were investigated with X-ray powder diffraction, infrared, and impedance spectroscopy. Zr-substituted (7 mol%) Na₆Yb₃(PO₄)₅ has ionic conductivity of 1.6·10⁻² S/cm at 300°C and 4.8·10⁻⁵ S/cm at room temperature. An updated version of phase diagram for ScPO₄–Na₃PO₄–Li₃PO₄ quasi-ternary system was provided.     

Population Analysis of Diospyros lotus in the Northwestern Caucasus Based on Leaf Morphology and Multilocus DNA Markers

Diospyros lotus is the one of the most frost-tolerant species in the Diospyros genera, used as a rootstock for colder regions. Natural populations of D. lotus have a fragmented character of distribution in the Northwestern Caucasus, one of the coldest regions of Diospyros cultivation. To predict the behavior of D. lotus populations in an extreme environment, it is necessary to investigate the intraspecific genetic diversity and phenotypic variability of populations in the colder regions. In this study, we analyzed five geographically distant populations of D. lotus according to 33 morphological leaf traits, and the most informative traits were established, namely, leaf length, leaf width, leaf index (leaf to length ratio) and the length of the fourth veins. Additionally, we evaluated the intraspecific genetic diversity of D. lotus using ISSR and SCoT markers and proposed a new parameter for the evaluation of genetic polymorphism among populations, in order to eliminate the effect of sample number. This new parameter is the relative genetic polymorphism, which is the ratio of polymorphism to the number of samples. Based on morphological and genetic data, the northernmost population from Shkhafit was phenotypically and genetically distant from the other populations. The correspondence between several morphological traits (leaf width, leaf length and first to fifth right vein angles) and several marker bands (SCoT5, SCoT7, SCoT30: 800–1500 bp; ISSR13, ISSR14, ISSR880: 500–1000 bp) were observed for the Shkhafit population. Unique SCoT and ISSR fragments can be used as markers for breeding purposes. The results provide a better understanding of adaptive mechanisms in D. lotus in extreme environments and will be important for the further expansion of the cultivation area for persimmon in colder regions.     

Inhibitory Response to CK II Inhibitor Silmitasertib and CDKs Inhibitor Dinaciclib Is Related to Genetic Differences in Pancreatic Ductal Adenocarcinoma Cell Lines

Casein kinase II (CK2) and cyclin-dependent kinases (CDKs) frequently interact within multiple pathways in pancreatic ductal adenocarcinoma (PDAC). Application of CK2- and CDK-inhibitors have been considered as a therapeutic option, but are currently not part of routine chemotherapy regimens. We investigated ten PDAC cell lines exposed to increasing concentrations of silmitasertib and dinaciclib. Cell proliferation, metabolic activity, biomass, and apoptosis/necrosis were evaluated, and bioinformatic clustering was used to classify cell lines into sensitive groups based on their response to inhibitors. Furthermore, whole exome sequencing (WES) and RNA sequencing (RNA-Seq) was conducted to assess recurrent mutations and the expression profile of inhibitor targets and genes frequently mutated in PDAC, respectively. Dinaciclib and silmitasertib demonstrated pronounced and limited cell line specific effects in cell death induction, respectively. WES revealed no genomic variants causing changes in the primary structure of the corresponding inhibitor target proteins. RNA-Seq demonstrated that the expression of all inhibitor target genes was higher in the PDAC cell lines compared to non-neoplastic pancreatic tissue. The observed differences in PDAC cell line sensitivity to silmitasertib or dinaciclib did not depend on target gene expression or the identified gene variants. For the PDAC hotspot genes kirsten rat sarcoma virus (KRAS) and tumor protein p53 (TP53), three and eight variants were identified, respectively. In conclusion, both inhibitors demonstrated in vitro efficacy on the PDAC cell lines. However, aberrations and expression of inhibitor target genes did not appear to affect the efficacy of the corresponding inhibitors. In addition, specific aberrations in TP53 and KRAS affected the efficacy of both inhibitors.