Base free lithium-organoaluminate and the gallium congener: potential precursors to heterometallic assemblies

The first examples of base free lithium-organoaluminate and the corresponding gallium compound [LM(Me)OLi]3 (M = Al (3), Ga (4); L = HC{C(Me)N-2,6-iPr2C6H3}2) have been prepared by the reaction of Li[N(SiMe3)2] with the corresponding metal hydroxides LM(Me)OH (M = Al (1), Ga(2)); the oxygen atom in the M-O-Li fragment exists as oxide ion and is involved in the central Li3O3 six-membered ring formation.     

Structures of micelles formed by synthetic alkyl glycosides with unsaturated alkyl chains

Three new alkyl glycosides with similar molecular structures (oleyl and oleoyl alkyl chains and various head groups: disaccharide, trisaccharide and disaccharide with an additional amidoethoxy spacer) were synthesized and their supramolecular structure in aqueous solution was investigated. Small angle neutron scattering, surface tension measurement and the contact preparation method were applied to get molecular structure-property relationships. Although the chemical structures differ only in small details, their CMC values, lyotropic phase behaviour, surface area per surfactant molecule in the micelle and at the liquid-air interface, and the size and shape of the micelles are very different. We have found three different types of aggregates: spherical, cylindrical and polymer-like micelles in dilute solutions.     

Low-Carbohydrate,High-Protein,and Gluten-Free Bread Supplemented with Poppy Seed Flour: Physicochemical,Sensory, and Spectroscopic Properties

Background: This study aimed to determine the effect of poppy seed flour (PF) on the physicochemical and spectroscopic properties of low-carbohydrate, high-protein, and gluten-free bread. Methods: The changes at the molecular level were assessed in bread using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). Bread prepared with buckwheat, flaxseed, and pea protein was enriched with PF at a concentration of 5–15%. Results: The results showed that the pasting parameters of dough supplemented with PF were significantly decreased compared to the control sample. The obtained bread samples were characterized by good quality and had 14.6% of carbohydrate, 16.3% of protein, 10.2% of fiber, and 4.0% of fat, with a caloric value of 177 kcal/100 g. The addition of PF had little influence on crumb mechanical properties. The ATR-FTIR analyses revealed spectral changes in the region related to protein and carbohydrate structures, as well as changes in band intensity characteristic of α-1,4-glycoside and α-1,6-glycoside bonds. The analyses showed that the main starch skeleton remained clearly visible. Conclusions: PF up to 10% can be potentially applied as a functional ingredient in the production of bread based on buckwheat and linseed flour. Such low-carbohydrate bread can be particularly useful to diabetics.     

A proposed method for calculating the melting point of a pure substance

A method is proposed for calculating the melting temperature (T ₀) of a pure substance by combining cryoscopic measurements of melting temperature (T _m ) of various impure samples with differential calorimetric values of temperature differencesT ₀-T _m for the same samples. The proposed expression is: $$T_0 = \frac{{\mathop \Sigma \limits_1^n T_m }}{n} + \frac{{\mathop \Sigma \limits_1^n (T_0 - T_m )}}{n}$$ where the right-side term denotes the average value of a sufficiently high number of experiments (n). The value ofT ₀ determined in such a way, may be much more reliable than that obtained by using graphical methods or preparing an extremely pure sample.     

Introducing a Hydrogen‐Bond Donor into a Weakly Nucleophilic Brønsted Base: Alkali Metal Hexamethyldisilazides (MHMDS,M=Li,Na, K,Rb and Cs) with Ammonia

Alkali metal 1,1,1,3,3,3‐hexamethyldisilazide (MHMDSs) are one of the most utilised weakly nucleophilic Brønsted bases in synthetic chemistry and especially in natural product synthesis. Like lithium organics, they aggregate depending on the employed donor solvents. Thus, they show different reactivity and selectivity as a function of their aggregation and solvation state. To date, monomeric LiHMDS with monodentate donor bases was only characterised in solution. Since the first preparation of LiHMDS in 1959 by Wannagat and Niederprüm, all efforts to crystallise monomeric LiHMDS in the absence of chelating ligands failed. Herein, we present ammonia adducts of LiHMDS, NaHMDS, KHMDS, RbHMDS and CsHMDS with unprecedented aggregation motifs: 1) The hitherto missing monomeric key compound in the LiHMDS aggregation architectures. Monomeric crystal structures of trisolvated LiHMDS ( 1 ) and NaHMDS ( 2 ), showing unique intermolecular hydrogen bonds, 2) the unprecedented tetrasolvated KHMDS ( 3 ) and RbHMDS ( 4 ) dimers and 3) the disolvated CsHMDS ( 5 ) dimer with very close intermolecular Si?CH₃???Cs s‐block “agostic” interactions have been prepared and characterised by single‐crystal X‐ray structure analysis.     

Efficient experimental design tools for exploring large simulation models

Simulation experiments are typically faster, cheaper and more flexible than physical experiments. They are especially useful for pilot studies of complicated systems where little prior knowledge of the system behavior exists. One key characteristic of simulation experiments is the large number of factors and interactions between factors that impact decision makers. Traditional simulation approaches offer little help in analyzing large numbers of factors and interactions, which makes interpretation and application of results very difficult and often incorrect. In this paper we implement and demonstrate efficient design of experiments techniques to analyze large, complex simulation models. Looking specifically within the domain of organizational performance, we illustrate how our approach can be used to analyze even immense results spaces, driven by myriad factors with sometimes unknown interactions, and pursue optimal settings for different performance measures. This allows analysts to rapidly identify the most important, results-influencing factors within simulation models, employ an experimental design to fully explore the simulation space efficiently, and enhance system design through simulation. This dramatically increases the breadth and depth of insights available through analysis of simulation data, reduces the time required to analyze simulation-driven studies, and extends the state of the art in computational and mathematical organization theory.     

Efficient synthesis of gamma-alkylidenetetronic esters by sequential Lewis acid catalyzed

A new approach for the synthesis of gamma-alkylidenetetronic acids and esters is reported which involves Me3SiOTf-catalyzed, regio- and stereoselective cyclization of 4-alkoxy-1,3-bis(trimethylsilyloxy)-1,3-butadienes with oxalyl chloride. The alpha-hydroxy group of the butenolides is efficiently functionalized by palladium-catalyzed cross-coupling reactions via the corresponding enol triflates.