Accelerating the development of phase-change random access memory with in-fab plasma profiling time-of-flight mass spectrometry

We demonstrate the potential of using plasma profiling time-of-flight mass spectrometry (PP-TOFMS) to accelerate process developments for phase-change random access memory (PCRAM) applications, which require advanced materials with composition-driven properties. We assess the performances of PP-TOFMS for the chemical depth-profiling of GeSbTe phase change materials, first after deposition steps to investigate the top surface layer and the incorporation of silicon into the amorphous matrix, then after the thermal annealing step to refine in situ capping strategies, and finally in close loop with etching process steps. Comparison of reference-free semiquantitative PP-TOFMS analysis based on ion beam ratio with Rutherford backscattering spectrometry shows remarkable agreement (~10% relative). PP-TOFMS proves to be a fast screening tool, which allows process monitoring and selection of samples that indeed need more complex analysis.     

In Silico Analysis and In Vitro Characterization of the Bioactive Profile of Three Novel Peptides Identified from 19 kDa α-Zein Sequences of Maize

In this study, we characterized three novel peptides derived from the 19 kDa α-zein, and determined their bioactive profile in vitro and developed a structural model in silico. The peptides, 19ZP1, 19ZP2 and 19ZP3, formed α-helical structures and had positive and negative electrostatic potential surfaces (range of −1 to +1). According to the in silico algorithms, the peptides displayed low probabilities for cytotoxicity (≤0.05%), cell penetration (10–33%) and antioxidant activities (9–12.5%). Instead, they displayed a 40% probability for angiotensin-converting enzyme (ACE) inhibitory activity. For in vitro characterization, peptides were synthesized by solid phase synthesis and tested accordingly. We assumed α-helical structures for 19ZP1 and 19ZP2 under hydrophobic conditions. The peptides displayed antioxidant activity and ACE-inhibitory activity, with 19ZP1 being the most active. Our results highlight that the 19 kDa α-zein sequences could be explored as a source of bioactive peptides, and indicate that in silico approaches are useful to predict peptide bioactivities, but more structural analysis is necessary to obtain more accurate data.     

CpTiCl2-Catalyzed Cross-Coupling between Internal Alkynes and Ketones: A Novel Concept in the Synthesis of Halogenated,Conjugated Dienes

A novel concept for the synthesis of halogenated, conjugated dienes is disclosed: the CpTiCl₂-catalyzed coupling of keto-alkynes, in the presence of Me₃SiBr/Et₃N ⋅ HBr. This reaction provided five-, six-, and seven-membered carbocycles, nitrogenated heterocycles, as well as six-membered oxygenated heterocycles leading to a brominated conjugate diene. These products showed high reactivity in the Diels–Alder, Suzuki, and Sonogashira reactions, giving complex chemical structures in only three steps from the corresponding acyclic keto-alkyne. Hopefully, this strategy will pave the way towards the synthesis of bioactive natural products and new materials.     

Self-degassing SARA ATRP mediated by Na2S2O4 with no external additives

The supplemental activator and reducing agent (SARA) atom transfer radical polymerization (ATRP) mediated by Na₂S₂O₄ in the presence of air, without external deoxygenation or additional oxygen scavengers, is reported for several vinyl monomers: methyl acrylate (MA), n-butyl acrylate (n-BA), methyl methacrylate (MMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), poly(ethylene glycol) methyl ether acrylate (OEOA), and styrene (Sty). The polymerizations can be conducted in aqueous medium or using organic/water mixtures as solvent, with low concentration of copper, near room temperature. In the absence of any external deoxygenation, several well-defined homopolymers and block copolymers were obtained (Ð < 1.3). The evolution of the oxygen concentration during the polymerizations was monitored with an optical oxygen sensor. The consumption of oxygen prior polymerization in ethanol/water mixtures was attributed to the combined presence of Na₂S₂O₄ and alkyl halide initiator, which led to a lower initiation efficiency (I_eff). This could be overcome by decreasing the headspace volume of the reaction. The system reported exhibited the potential to be scalable, which is very relevant from an industrial standpoint. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 145–153     

Four N7‐alkoxybenzyl‐substituted 4,5,6,7‐tetrahydro‐1H‐pyrazolo[3,4‐b]pyridine‐5‐spiro‐1′‐cyclohexane‐2′,6′‐diones: hydrogen‐bonded supramolecular structures in zero,one, two or three dimensions

3‐tert‐Butyl‐7‐(4‐methoxybenzyl)‐4′,4′‐dimethyl‐1‐phenyl‐4,5,6,7‐tetrahydro‐1H‐pyrazolo[3,4‐b]pyridine‐5‐spiro‐1′‐cyclohexane‐2′,6′‐dione, C₃₁H₃₇N₃O₃, (I), 3‐tert‐butyl‐7‐(2,3‐dimethoxybenzyl)‐4′,4′‐dimethyl‐1‐phenyl‐4,5,6,7‐tetrahydro‐1H‐pyrazolo[3,4‐b]pyridine‐5‐spiro‐1′‐cyclohexane‐2′,6′‐dione, C₃₂H₃₉N₃O₄, (II), 3‐tert‐butyl‐4′,4′‐dimethyl‐7‐(3,4‐methylenedioxybenzyl)‐1‐phenyl‐4,5,6,7‐tetrahydro‐1H‐pyrazolo[3,4‐b]pyridine‐5‐spiro‐1′‐cyclohexane‐2′,6′‐dione, C₃₁H₃₅N₃O₄, (III), and 3‐tert‐butyl‐4′,4′‐dimethyl‐1‐phenyl‐7‐(3,4,5‐trimethoxybenzyl)‐4,5,6,7‐tetrahydro‐1H‐pyrazolo[3,4‐b]pyridine‐5‐spiro‐1′‐cyclohexane‐2′,6′‐dione ethanol 0.67‐solvate, C₃₃H₄₁N₃O₅·0.67C₂H₆O, (IV), all contain reduced pyridine rings having half‐chair conformations. The molecules of (I) and (II) are linked into centrosymmetric dimers and simple chains, respectively, by C—H...O hydrogen bonds, augmented only in (I) by a C—H...π hydrogen bond. The molecules of (III) are linked by a combination of C—H...O and C—H...π hydrogen bonds into a chain of edge‐fused centrosymmetric rings, further linked by weak hydrogen bonds into supramolecular arrays in two or three dimensions. The heterocyclic molecules in (IV) are linked by two independent C—H...O hydrogen bonds into sheets, from which the partial‐occupancy ethanol molecules are pendent. The significance of this study lies in its finding of a very wide range of supramolecular aggregation modes dependent on rather modest changes in the peripheral substituents remote from the main hydrogen‐bond acceptor sites.     

Monitoring of the Sol-Gel Synthesis of Organic-inorganic Hybrids by FTIR Transmission,FTIR/ATR,NIR and Raman Spectroscopy

Summary: The sol-gel synthesis of organic-inorganic hybrids based on triethoxysilane- terminated poly(ethylene oxide) and tetraethylorthosilicate was monitored in-situ using three spectroscopic methods (FTIR/ATR, Raman, NIR). These spectroscopic methods allow in-situ monitoring of the evolution of hybrid materials starting from the modification of the polymer and the early steps of hydrolysis up to the network formation. By application of ²⁹Si solid-state NMR spectroscopy the assignment and quantification of the Raman bands to different end groups and different cross-linking states was made. The sol-gel reaction was also followed by in-line NIR spectroscopy. A multivariate data analysis was accomplished to obtain a conversion-time curve. Furthermore, we investigated spin-coated films on wafers using FTIR transmission spectroscopy.     

Effects of the simultaneous presence of nitro and amine substituents in cubane and some azacubanes

We have carried out an ab initio self-consistent-field molecular orbital study of the structures and bond orders (as measures of relative bond strengths) of nitro and aminonitro derivatives of cubane and some azacubanes. The NO₂ group is found to have, in general, a conformation-dependent effect on relative bond strengths. When the plane of the nitro group is perpendicular to that of an endocyclic bond, that bond is weakened. An aza nitrogen adjacent to C-NO₂, however, eliminates the bond-weakening due to a perpendicular nitro group, except when a C-NH₂ is also adjacent to the C-NO₂. The NH₂ group has a direction-specific bond-weakening effect on one [and only one] endocyclic bond; the particular bond undergoing this weakening is determined by the orientation of the amine nitrogen lone pair. The influences of the NO₂ and NH₂ are essentially independent; when these substituents are on adjacent carbons the effects are reinforcing. Thus, the combination of a perpendicular NO₂ and an NH₂ on adjacent carbons in cubane and azacubanes produces a marked bond weakening. Our findings suggest that strained cage systems that have alternating aza nitrogens and C-NO₂ groups should be further investigated as potential high-energy systems.     

Altered Volcanic Tuffs from Los Frailes Caldera. A Study of Their Pozzolanic Properties

This work presents the results of the study of the physical, chemical, mineralogical and pozzolanic properties of the altered volcanic tuffs (AVT) that lie in the Los Frailes caldera, south of the Iberian Peninsula, and demonstrates their qualities as pozzolans for the manufacturing of mortars and pozzolanic cements of high mechanical strength. The main objective of this research is to show to what extent the AVTs can replace portland cement (PC) in mortars, with standardised proportions of 75:25% and 70:30% (PC-AVT). To achieve these objectives, three AVT samples were studied by a petrographic analysis of thin section (PATS), DRX, FRX and MEB. The pozzolanic properties were determined by three methods: electrical conductivity (ECT), chemical pozzolanicity tests (CPT) at 8 and 15 days and mechanical strength tests (MS) of the specimens at 2, 7, 28 and 90 days. Studies of a PATS, DRX, FRX and MEB showed that the AVT samples’ constitutions are complex where smectite (montmorillonite), mordenite, quartz, halloysite, illite, kaolinite, volcanic glass and lithic fragments coexist. The results of the ECT and CPT tests confirmed the pozzolanic properties of the samples analysed and proved an increase in mechanical strength from 2 to 90 days of testing.     

The Identification of New Triterpenoids in Eucalyptus globulus Wood

Eight polyhydroxy triterpenoid acids, hederagenin, (4α)-23-hydroxybetulinic acid, maslinic acid, corosolic acid, arjunolic acid, asiatic acid, caulophyllogenin, and madecassic acid, with 2, 3, and 4 hydroxyl substituents, were identified and quantified in the dichloromethane extract of Eucalyptus globulus wood by comparing their GC-retention time and mass spectra with standards. Two other triterpenoid acids were tentatively identified by analyzing their mass spectra, as (2α)-2-hydroxybetulinic acid and (2α,4α)-2,23-dihydroxybetulinic acid, with 2 and 3 hydroxyl substituents. Two MS detectors were used, a quadrupole ion trap (QIT) and a quadrupole mass filter (QMF). The EI fragmentation pattern of the trimethylsilylated polyhydroxy structures of these triterpenoid acids is characterized by the sequential loss of the trimethylsilylated hydroxyl groups, most of them by the retro-Diels-Alder (rDA) opening of the C ring with a π-bond at C12-C13. The rDA C-ring opening produces ions at m/z 320 (or 318) and m/z 278 (or 277, 276, 366). Sequential losses of the hydroxyl groups produce ions with m/z from [M - 90] to [M - 90*y], where y is the number of hydroxyl substituents present (from 2 to 4). Moreover, specific cleavage in ring E was observed, passing from m/z 203 to m/z 133 and conducting other major fragments such as m/z 189.     

Synthesis of trans-Mono(silyl)palladium(II) Bromide Complexes

The stoichiometric reaction of cis-[Pd(ITMe)₂(SiR₃)₂], where (SiR₃ = SiMe₃ and SiMe₂Ph and ITMe = 1,3,4,5-tetramethylimidazol-2-ylidene) with allyl bromide affords the corresponding allylsilanes along with complexes of the type trans-[Pd(ITMe)₂(SiR₃)(Br)]. The structure of trans-[Pd(ITMe)₂(SiMe₂Ph)Br] 2b has been determined in the solid state and displays a slightly distorted square-planar geometry with the two N-heterocyclic carbene ligands in a trans-configuration.