Statistics in the computer age: personal reflections

It is a trivial observation that the computers have changed the way statistics is practiced. But has it also changed the theory of statistics and the way we teach it? I think yes—even if the changes appear to be surprisingly small in some contexts. This is an attempt to give a more detailed answer, based on experiences from my own corner of the world from 1964 till now.     

The Formation of Porous Membranes by Filtration of Aerosol Nanoparticles

Flame-generated aerosol particles of Al₂O₃ were deposited by gas filtration on two types of porous and ceramic tubes of -Al₂O₃ with mean pore diameters of 450 and 2700nm, respectively. The particles were aggregates with average mobility diameters in the range of 30–100nm and primary particle diameters of 4–8nm. The particles are characterized by differential mobility analysis, transmission electron microscopy, and by their specific surface area. The deposited membranes are characterized by gas permeability measurements, scanning electron microscopy, and by their pore size distribution from nitrogen capillary condensation. The particles form a distinct, homogeneous membrane layer with a porosity of 90% on top of the substrate surface and only penetrate slightly into the substrate structure. The mean pore sizes of the deposited membranes determined by nitrogen condensation agree approximately with those determined by gas permeation and the specific surface area. The mean pore diameter varies in the range of 30–70nm. The gas permeability of the deposited membranes is related to the specific surface area but influenced by the high porosity. The mean pore size and the permeability of the membranes are almost independent of the substrate structure.The development of a membrane with uniform properties is preceded by a short initial period in which the deposited particles, with an equivalent membrane thickness of roughly 2m, have a significantly lower permeability than the ultimately developed uniform membrane layer. This effect is particularly significant for the aerosol particles with the lowest mean size, probably due to particles deposited in the pore mouths of the substrate.The particles and the deposited membranes are X-ray amorphous but retain their specific surface area on heating to even high temperatures. When the membranes are heated to 1473K for 10h, X-ray diffraction shows a mixture of - and -alumina, accompanied by a partial disintegration of the membrane and a considerable loss of surface area.     

On the scope of Pd-catalyzed carboamination reactions—synthesis of 2,4-disubstituted pyrrolidines and 2-substituted piperidines and morpholines

The scope of the palladium-catalyzed carboamination reaction for the synthesis of 2-substituted pyrrolidines, piperidines, and morpholines was investigated. Formation of a 2,4-disubstituted pyrrolidine proceeded in high yield but with a diastereoisomeric ratio of only 2:5, favoring the cis-isomer. The diastereoselectivity is hence significantly smaller than that observed previously in the formation of 2,3- and 2,5-disubstituted pyrrolidines. The yields of substituted piperidines and morpholines were lowered by competing Heck arylation reactions. Both the N-substituent and the choice of phosphine ligand for the palladium-catalyzed reaction were determining for the outcome.     

Metal-free synthesis of aryl esters from carboxylic acids and diaryliodonium salts

An efficient arylation of carboxylic acids with diaryliodonium salts has been developed, giving aryl esters in high yields within short reaction times for both aromatic and aliphatic substrates. The transition-metal-free conditions are compatible with a range of functional groups, and good chemoselectivity is observed with unsymmetric diaryliodonium salts. Furthermore, steric hindrance in the ortho positions is well tolerated both in the carboxylic acid and in the diaryliodonium salt, yielding aryl esters that cannot be obtained via other esterification protocols.     

Surface-modified lead–zirconium-titanate system for solution-processed ferroelectric-gate thin-film transistors

We propose the use of a La₂O₃ (LO) film as the capping layer for improvement of a semiconductor/insulator interface in a solution-processed indium–tin–oxide (ITO) ferroelectric-gate thin-film transistor (FGT) device. It is demonstrated that the LO layer acts as a good barrier film not only for preventing the interdiffusion between the ITO semiconductor and lead–zirconium-titanate (PZT) insulator layers, but also for stabilizing the PZT surface structure. The fabricated FGT device exhibited high I _on/I _off, large M _w, high μ _FE and improved retention time of about 10⁹, 3.5 V, 7.94 cm²?V^?1?s^?1 and 1 day, respectively, which are comparable to or better than those obtained with FGTs fabricated by means of conventional vacuum processes. We also point out that the key origin of the interface improvement is likely due to the incorporation of La into the PZT system, forming a La surface-modified PZT system which is more stable than the pure PZT in terms of Pb volatility and formation of oxygen vacancies.     

A tetrathiafulvalene–perylene diimide conjugate prepared via click chemistry

A new tetrathiafulvalene (TTF)–perylene diimide (PDI) conjugate is prepared from an azide-functionalized TTF and an acetylenic PDI employing a Cu(I)-catalyzed Huisgen-Meldal-Sharpless reaction (‘click chemistry’). Thus, the TTF donor and PDI acceptor units are linked together by a 1,2,3-triazole unit. The molecules are found to assemble on a mica surface, forming fibrilar structures.     

Synthesis and characteristics of a nonaggregating tris(tetrathiafulvaleno)dodecadehydro[18]annulene

A new tris(tetrathiafulvaleno)dodecadehydro[18]annulene with six peripheral n-hexyl substituents was prepared by oxidative Glaser-Hay cyclization of a corresponding diethynylated tetrathiafulvalene (TTF) precursor. The electronic properties of the neutral and oxidized species were studied by both UV/Vis absorption spectroscopy and electrochemistry. From these studies, it transpires that the strongly violet-colored macrocycle does not aggregate in solution to any significant degree, which was confirmed by (1)H NMR spectroscopy. This reluctance towards aggregation contrasts that observed for related TTF-annulenes containing other peripheral substitutents. Oxidation of the TTF-annulene occurs in two three-electron steps as inferred from both the peak amplitudes and the spectroelectrochemical study. We find that the tris(TTF)-fused dehydro[18]annulene is more difficult to oxidize (by +0.20 V) than the silyl-protected diethynylated mono-TTF precursor. In contrast, the first vertical ionization energy calculated at the B3 LYP/6-311+G(2d,p) level for the parent tris(TTF)-fused dehydro[18]annulene devoid of peripheral hexyl substituents is in fact lower (by 0.44 eV). Moreover, the surface morphology of 1 d drop-cast on a mica substrate was investigated by atomic force microscopy (AFM). Crystalline domains with slightly different orientations were observed. The thickness of individual layers seen in the crystalline domains and the thickness of a monolayer obtained from a very dilute solution were determined to 1.8-1.9 nm. This thickness corresponds to the diameter of the macrocycle and the layers seen in the film are apparently formed when the molecules stack in the horizontal direction relative to the substrate.     

Harnessing Quinone Methides: Total Synthesis of (±)‐Vaticanol A

Although quinone methides are often postulated as intermediates in the biosynthesis of many polyphenolic natural products, deploying their power in a laboratory setting to achieve similar bond constructions has sometimes proven challenging. Herein, a total synthesis of the resveratrol trimer vaticanol A has been achieved through three instances of quinone methide chemistry. These operations, one of which succeeded only under very specific conditions, expediently generated its [7,5]‐carbocyclic core, afforded a unique sequence for dihydrobenzofuran formation, and concurrently generated, in addition to the target molecule, a series of diastereomers reflective of many other isolates.