Highly dispersed clay-polyolefin nanocomposites free of compatibilizers, via the in situ polymerization of alpha-olefins by clay-supported catalysts

In situ polymerization by certain transition metal catalysts supported on and activated by acid-treated montmorillonite produces well-dispersed clay-polyolefin nanocomposites, without requiring either organic surfactants to be present in the clay phase or modification of the polyolefin structure.     

Determination of boron and other elements in volcanic rocks by prompt gamma-ray analysis: An application to magma genesis in Kyushu island,SW-Japan

Neutron induced prompt gamma-ray activation analysis (PGAA) is applied for determining boron contents in volcanic rocks, which is an important element in the discussion of material circulation in volcanic arc systems. To evaluate the recycling of oceanic crust in Kyushu, we analyzed boron and other trace element contents in basaltic rocks from the area. The basalts from volcanic front have high B/Nb (2.9–3.7), B/Zr (0.1–0.2) and B/Sm (2.8–6.0) ratios, whereas those ratios in the basalts from backarc are extremely low (<0.5; <0.1; 0.5–1.7), respectively. This indicates that the recycling of subducted oceanic crust to the arc crust is limited in the volcanic front.     

NMR studies on effects of temperature, pressure, and fluorination on structures and dynamics of alcohols in liquid and supercritical states

We measured 1H NMR chemical shifts (delta H) and 1H and 2H NMR spin-lattice relaxation times (1H- and 2H-T1) of methanol, ethanol, 2-propanol, 2,2,2-trifluoroethanol, and 1,1,1,3,3,3-hexafluoro-2-propanol in the temperature range from 298 to 673 K at reduced pressures ( Pr = P/ Pc) of 1.22 and 3.14. The delta H values showed that the degree (X HB) of hydrogen bonding decreased in the order of methanol > ethanol >2-propanol > H2O, and that the hydrogen bonding was much affected by fluorination, because of the intramolecular H-F interactions in supercritical (sc) states. Moreover, 1H- T 1 measurements revealed that the relaxation processes of OH groups in nonfluoroalcohols are controlled by dipole-dipole (DD) and spin-rotation (SR) mechanisms below and above the critical temperature (Tc), while the cross-correlation effects connected with intramolecular DD interactions between a carbon atom and an adjacent proton played an important role for hydrocarbon groups (CHn, n = 1-3) under sc conditions. This interpretation was also supported by two other results. The first is that the intramolecular H-F interactions strongly inhibit the internal rotation of CH and CH2 groups of sc fluoroalcohols, and the second is that the molecular reorientational correlation times (tauc(D)) obtained from 2H- T 1 values of deuterated hydrocarbon groups (CDn ) at temperatures above T c have significantly less temperature dependence than those of OD groups. Actually, the apparent activation energy (DeltaEa) for molecular reorientational motions in sc alcohols was smaller compared with liquid alcohols, being about 1 order of magnitude.     

Evaluation of interaction forces between profilin and designed peptide probes by atomic force microscopy

We evaluated the binding affinity of peptide probes for profilin (protein) using force curve measurement techniques and atomic force microscopy (AFM). The peptide probes designed and synthesized for this investigation were H-A3GP5GP5GP5G-OH (1), H-A3GP5G-OH (2), H-A3G7-OH (3), and H-A3G-OH (4). Each peptide probe was immobilized on a cantilever tip, and the interaction force to profilin, immobilized on a mica substrate, was examined by force curve measurements. The retraction forces obtained showed a sequence-dependent affinity of the peptide probe for profilin. The retraction force for peptide probe 1 was the largest of the four probes examined, and it confirmed that peptide probe 1 has high affinity for profilin. The single molecular retraction force between peptide probe 1 and profilin was estimated to be 96 pN, as determined by Gaussian fitting to the histogram of the retraction forces.     

Regulation of pattern dimension as a function of vacuum pressure: alkyl monolayer lithography

Photopatterning of a hexadecyl (HD) monolayer has been demonstrated using vacuum ultraviolet (VUV; lambda = 172 nm) light under controlled vacuum pressure with the objective of minimizing the pattern dimension. X-ray photoelectron spectroscopy (XPS) and lateral force microscopy (LFM) studies reveal that photodegradation of the HD monolayer not only is limited to the regions exposed to VUV but also spreads under the masked regions. The strong oxidants generated by VUV irradiation to atmospheric oxygen and water vapor diffuse toward the masked regions through the nanoscopic channels and photodissociate the monolayer under the masked area, near the photomask apertures, resulting in broadening of the photopattern. Such broadening decreases with decreased vacuum pressure inside the VUV chamber, associated with a decrease of oxidant concentration and reduction of their diffusion. Gold nanoparticles (AuNPs) were immobilized on the VUV patterned features to probe the dimension of the chemically active pattern. Field emission electron microscopy reveals the construction of 565 nm wide pattern features at a vacuum pressure of 10 Pa. This pattern widens to 1,030 nm at 10 (4) Pa using the same size apertures (500 nm) as printed on the photomask. This study provides insight for fabricating submicron patterns with high reproducibility and its exploitation for different applications, which includes the patterning of nanoparticles, biopolymers, and other nano-objects at submicron dimensions.     

Enantioselective C--C bond formation to sulfonylimines through use of the 2-pyridinesulfonyl group as a novel stereocontroller

Enantioselective C--C bond formation to 2-pyridinesulfonylimines afforded products with good enantioselectivity. Dynamic induction of chirality on the sulfur by coordination of a chiral Lewis acid to the pyridine nitrogen and one of the prochiral sulfonyl oxygens induces enantioselectivity. Since the 2-pyridinesulfonyl group can easily be removed after the reaction, it acts not only as an activating group but also as an efficient stereocontroller.     

Rapid multivariate analysis of 3D ToF‐SIMS data: graphical processor units (GPUs) and low‐discrepancy subsampling for large‐scale principal component analysis

Principal component analysis (PCA) and other multivariate analysis methods have been used increasingly to analyse and understand depth‐profiles in XPS, AES and SIMS. For large images or three‐dimensional (3D) imaging depth‐profiles, PCA has been difficult to apply until now simply because of the size of the matrices of data involved. In a recent paper, we described two algorithms, random vector 1 (RV1) and random vector 2 (RV2), that improve the speed of PCA and allow datasets of unlimited size, respectively. In this paper, we now apply the RV2 algorithm to perform PCA on full 3D time‐of‐flight SIMS data for the first time without subsampling. The dataset we process in this way is a 128 × 128 pixel depth‐profile of 120 layers, each voxel having a 70 439 value mass spectrum associated with it. This forms over a terabyte of data when uncompressed and took 27 h to process using the RV2 algorithm using a conventional windows desktop personal computer (PC). While full PCA (e.g. using RV2) is to be preferred for final reports or publications, a much more rapid method is needed during analysis sessions to inform decisions on the next analytical step. We have therefore implemented the RV1 algorithm on a PC having a graphical processor unit (GPU) card containing 2880 individual processor cores. This increases the speed of calculation by a factor of around 4.1 compared with what is possible using a fast commercially available desktop PC having central processing units alone, and full PCA is performed in less than 7 s. The size of the dataset that can be processed in this way is limited by the size of the memory on the GPU card. This is typically sufficient for two‐dimensional images but not 3D depth‐profiles without sampling. We have therefore examined efficient sampling schemes that allow a good approximate solution to the PCA problem for large 3D datasets. We find that low‐discrepancy series such as Sobol series sampling gives more rapid convergence than random sampling, and we recommend such methods for routine use. Using the GPU and low‐discrepancy series together, we anticipate that any time‐of‐flight SIMS dataset, of whatever size, can be efficiently and accurately processed into PCA components in a maximum of around 10 s using a commercial PC with a widely available GPU card, although the longer RV2 approach is still to be preferred for the presentation of final results, such as in published papers. Copyright © 2016 The Authors Surface and Interface Analysis Published by John Wiley & Sons Ltd     

Effects of magnesium salts and amines on the stereoselectivity in the imine aldol reaction

In the imine aldol reactions of 1 with aromatic aldehydes using magnesium salts in the presence of amines, the threo/erythro ratios of products increased in the order Mg(ClO4)2>MgI2>MgBr2>MgCl2>Mg(OTf)2 and N,N,N',N'-tetramethylethylenediamine (TMEDA)>Et3N. This increase in the threo/erythro ratios of products was estimated to be caused by a retro-imine aldol reaction under thermodynamic control.