Ring transformation and cyclization reactions of 1,1-dioxo-1,2-thiazines – syntheses of pyridines and benzo[c]thiazines with new substitution pattern

In presence of ammonia/ammonium acetate the 3,5-dimethyl-2-phenyl-1,1-dioxo-1,2-thiazine-4-carbaldehyde ( 1 ) reacts with ethyl cyanoacetate to the ethyl 2-cyano-4-[1-methyl-2-methylthio-2-(N-phenylsulfamoyl)vinyl)-hexa-2,4-dienoate] ( 3 ) and the Knoevenagel condensation product 4-(2-ethoxycarbonyl-2-cyanovinyl)-3,5-dimethyl-6-methylthio-1,1-dioxo-2-phenyl-2H-1,2-thiazine ( 2 a). The 4-(2,2-dicyanovinyl)-3,5-dimethyl-6-methylthio-1,1-dioxo-2-phenyl-2H-1,2-thiazine ( 2b ) is obtained from 1 and malononitril. The masked 1,5-dicarbonyl compound 2a undergoes ring transformation to the 3-cyano-1,6-dimethyl-5-[1-methylthio-2-(N-phenylsulfamoyl)vinyl]pyridin-2-one ( 5 ) with methylamine. With ethanolic ethoxide the condensation products 2a,b afford the 7-amino-6-ethoxycarbonyl-4-methylthio-2,2-dioxo-1-phenyl-benzo[c]1,2-thiazine ( 6a ), respectively the corresponding 6-cyano derivative 6b , while 3 cyclizises to furnish ethyl 2-amino-6-methyl-5-[1-methyl-2-methylthio-2-(N-phenyl-sulfamoyl)vinyl]nicotinate ( 4 ).     

Zirkonium-katalysierte Oxidation von primären aromatischen Aminen zu Nitroverbindungen mit tert-Butylhydroperoxid

Zirconium-catalysed Oxidation of Primary Aromatic Amines to Nitro Compounds Using tert-Butylhydroperoxide A broad range of primary aromatic amines ( 1a–x ) with electron donating and accepting substituents are oxidized in good to excellent yields to the nitro compounds 3a–x using tert-butylhydroperoxide as the oxidant and Zr(OtBu)₄ as the catalyst. The corresponding nitroso compounds 2m, 2n, 2s and 2u can be isolated in the conversion of electron-rich anilines 1m, 1n, 1s and 1u . The aminopyridines 5a–d are also converted to the corresponding nitropyridines 6a–d , but in lower yields (41–47%).     

Prediction of oil and oleic acid concentrations in individual corn (Zea mays L.) kernels using near-infrared reflectance hyperspectral imaging and multivariate analysis

Due to their heterogeneous structure and variability in form, individual corn (Zea mays L.) kernels present an optical challenge for nondestructive spectroscopic determination of their chemical composition. Increasing demand in agricultural science for knowledge of specific traits in kernels is driving the need to find high-throughput methods of examination. In this study macroscopic near-infrared (NIR) reflectance hyperspectral imaging was used to measure small sets of kernels in the spectroscopic range of 950 nm to 1700 nm. Image analysis and principal component analysis (PCA) were used to determine kernel germ from endosperm regions as well as to define individual kernels as objects out of sets of kernels. Partial least squares (PLS) analysis was used to predict oil or oleic acid concentrations derived from germ or full kernel spectra. The relative precision of the minimum cross-validated root mean square error (RMSECV) and root mean square error of prediction (RMSEP) for oil and oleic acid concentration were compared for two sets of two hundred kernels. An optimal statistical prediction method was determined using a limited set of wavelengths selected by a genetic algorithm. Given these parameters, oil content was predicted with an RMSEP of 0.7% and oleic acid content with an RMSEP of 14% for a given corn kernel.     

Scratch resistant optical coatings on polymers by magnetron-plasma-enhanced chemical vapor deposition

The magnetron-plasma-enhanced chemical vapor deposition (magPECVD) provides silicon-organic thin films for optical, electrically insulating or diffusion barrier coating applications. With process pressures of ≤ 1 Pa this technology is well adapted to the sputtering process of optical interference coatings and also facilitates an inline-process implementation. This paper describes the deposition process for scratch resistant coatings on polycarbonate (PC) and allyl diglycol carbonate substrates. Based on the optical, chemical and mechanical characterization of single magPECVD thin films of varied chemical composition, several types of layer stacks (e.g. of gradient or alternating hardness distribution) were deposited with varied total thickness on PC substrates. Abrasion test results indicate two main effects: the resistance against scratches of high load abrasion (50 N) mainly depends on the total coating thickness. The durability against scratches of low load abrasion (5 N) shows a clear advantage for the multilayer design in contrast to homogeneous single layers even of higher thickness. Finally a 5-layer antireflective system was reactively sputtered onto the magPECVD coating and successfully passed adhesion and environmental tests.     

Flexible organic transistors and circuits with extreme bending stability

Flexible electronic circuits are an essential prerequisite for the development of rollable displays, conformable sensors, biodegradable electronics and other applications with unconventional form factors. The smallest radius into which a circuit can be bent is typically several millimetres, limited by strain-induced damage to the active circuit elements. Bending-induced damage can be avoided by placing the circuit elements on rigid islands connected by stretchable wires, but the presence of rigid areas within the substrate plane limits the bending radius. Here we demonstrate organic transistors and complementary circuits that continue to operate without degradation while being folded into a radius of 100 μm. This enormous flexibility and bending stability is enabled by a very thin plastic substrate (12.5 μm), an atomically smooth planarization coating and a hybrid encapsulation stack that places the transistors in the neutral strain position. We demonstrate a potential application as a catheter with a sheet of transistors and sensors wrapped around it that enables the spatially resolved measurement of physical or chemical properties inside long, narrow tubes.     

Teaching children about bicycle safety: An evaluation of the New Jersey Bike School program

There are multiple health and environmental benefits associated with increasing bicycling among children. However, the use of bicycles is also associated with severe injuries and fatalities. In order to reduce bicycle crashes, a bicycling education program was implemented in selected New Jersey schools and summer camps as part of the New Jersey Safe Routes to School Program. Using a convenience sample of participants to the program, an opportunistic study was designed to evaluate the effectiveness of two bicycle education programs, the first a more-structured program delivered in a school setting, with no on-road component, and the other a less structured program delivered in a summer camp setting that included an on-road component. Tests administered before and after training were designed to assess knowledge acquired during the training. Questions assessed children's existing knowledge of helmet use and other equipment, bicycle safety, as well as their ability to discriminate hazards and understand rules of the road. Participating children (n = 699) also completed a travel survey that assessed their bicycling behavior and their perception of safety issues. Response to individual questions, overall pre- and post-training test scores, and changes in test scores were compared using comparison of proportion, t-tests, and ordinary least-squares (OLS) regression. Improvements between the pre-training and post-training test are apparent from the frequency distribution of test results and from t-tests. Both summer camps and school-based programs recorded similar improvements in test results. Children who bicycled with their parents scored higher on the pre-training test but did not improve as much on the post-training test. Without evaluating long-term changes in behavior, it is difficult to ascertain how successful the program is on eventual behavioral and safety outcomes.     

Analysis of computed tomographic imaging spectrometers. I. Spatial and spectral resolution

Computed tomographic imaging spectrometers measure the spectrally resolved image of an object scene in an entirely different manner from traditional whisk-broom or push-broom systems, and thus their noise behavior and data artifacts are unfamiliar. We review computed tomographic imaging spectrometry (CTIS) measurement systems and analyze their performance, with the aim of providing a vocabulary for discussing resolution in CTIS instruments, by illustrating the artifacts present in their reconstructed data and contributing a rule-of-thumb measure of their spectral resolution. We also show how the data reconstruction speed can be improved, at no cost in reconstruction quality, by ignoring redundant projections within the measured raw images.     

Novel near-infrared sampling apparatus for single kernel analysis of oil content in maize

A method of rapid, nondestructive chemical and physical analysis of individual maize (Zea mays L.) kernels is needed for the development of high value food, feed, and fuel traits. Near-infrared (NIR) spectroscopy offers a robust nondestructive method of trait determination. However, traditional NIR bulk sampling techniques cannot be applied successfully to individual kernels. Obtaining optimized single kernel NIR spectra for applied chemometric predictive analysis requires a novel sampling technique that can account for the heterogeneous forms, morphologies, and opacities exhibited in individual maize kernels. In this study such a novel technique is described and compared to less effective means of single kernel NIR analysis. Results of the application of a partial least squares (PLS) derived model for predictive determination of percent oil content per individual kernel are shown.     

Smoothed particle hydrodynamics simulation of shear-induced powder migration in injection moulding

We present the application of the smoothed particle hydrodynamics (SPH) discretization scheme to Phillips' model for shear-induced particle migration in concentrated suspensions. This model provides an evolution equation for the scalar mean volume fraction of idealized spherical solid particles of equal diameter which is discretized by the SPH formalism. In order to obtain a discrete evolution equation with exact conservation properties we treat in fact the occupied volume of the solid particles as the degree of freedom for the fluid particles. We present simulation results in two- and three-dimensional channel flow. The two-dimensional results serve as a verification by a comparison to analytic solutions. The three-dimensional results are used for a comparison with experimental measurements obtained from computer tomography of injection moulded ceramic microparts. We observe the best agreement of measurements with snapshots of the transient simulation for a ratio D(c)/D(η)=0.1 of the two model parameters.