Structural Changes of Cellulose Crystallites Induced by Mercerisation in Different Solvent Systems; Determined by Powder X-ray Diffraction Method

The completeness of mercerisation can be evaluated by investigating the changes in the crystalline regions of cellulose from cellulose I (C-I) to cellulose II (C-II) by the X-ray powder diffraction method. Mercerisation experiments in four different solution systems: ethanol/water, acetone, DMSO and xylene, are reported. Also the effect of some additives, external pressure, treatment time and alkalisation temperature were studied. In two-phase solvent systems, structural changes of cellulose crystallites depended primarily on the distribution and solubility of sodium hydroxide in the solvent phases. The sodium hydroxide concentration in the hydrophilic phase must exceed 7–8 w/w-% before complete crystal change from C-I to C-II can occur. The precipitation of sodium hydroxide due to high concentration prevents the successful use of one-phase ethanol/water system in slurry process. On the contrary, the 2-propanol/water/sodium hydroxide system separates into two layers; to the water-rich lower layer and the 2-propanol-rich upper layer, where the sodium hydroxide remains mainly in the water-rich lower layer. This prevents the precipitation of sodium hydroxide and promotes the alkalisation of cellulose. Ammonium chloride and ammonium hydroxide clearly had a positive effect by promoting the crystal changes, however, the urea concentration used in this study was obviously too small. In the advantageous two-phase 2-propanol/water systems, the alkalisation time was only 15 min when the treatment temperature was kept between 0 and 10 °C. Reduced external pressure was found to have a small but still detectable positive effect on cellulose alkalisation while over-pressure prevented crystal changes.     

Optimal orthogonalization processes

Two optimal orthogonalization processes are devised toorthogonalize,possibly approximately,the columns of a very large and possiblysparse matrix A∈C^n×k.Algorithmically the aim is,at each step,to optimallydecrease nonorthogonality of all the columns of A.One process relies on using translated small rank corrections.Another is a polynomial orthogonalization process forperforming the L?wdin orthogonalization.The steps rely on using iterative methods combined,preferably,with preconditioning which can have a dramatic effect on how fast thenonorthogonality decreases.The speed of orthogonalization depends on howbunched the singular values of A are,modulo the number of steps taken.These methods put the steps of the Gram-Schmidt orthogonalizationprocess into perspective regardingtheir(lack of)optimality.The constructions are entirely operatortheoretic and can be extended to infinite dimensional Hilbert spaces.     

Regiospecific synthesis,structure and electron ionization mass spectra of 1,3‐thiazolidin‐4‐ones containing the acridine skeleton

The synthesis of regioisomeric 3‐alkyl(aryl)‐2‐(acridin‐9′‐yl)imino‐1,3‐thiazolidin‐4‐ones ( 8b‐i ) and 2‐alkyl(aryl)imino‐3‐(acridin‐9′‐yl)‐1,3‐thiazolidin‐4‐ones ( 11a‐i ) was performed by the reaction of 3‐(acridin‐9‐yl)‐1‐alkyl(aryl)thioureas 5a‐i with methyl bromoacetate and bromoacetyl bromide, respectively, via the corresponding isothiourea hydrobromides with excellent regioselectivity. The structure, NMR spectra and mass spectrometric behavior of the resulting compounds are discussed.     

A dissociative fluorescence enhancement technique for one-step time-resolved immunoassays

The limitation of current dissociative fluorescence enhancement techniques is that the lanthanide chelate structures used as molecular probes are not stable enough in one-step assays with high concentrations of complexones or metal ions in the reaction mixture since these substances interfere with lanthanide chelate conjugated to the detector molecule. Lanthanide chelates of diethylenetriaminepentaacetic acid (DTPA) are extremely stable, and we used EuDTPA derivatives conjugated to antibodies as tracers in one-step immunoassays containing high concentrations of complexones or metal ions. Enhancement solutions based on different β-diketones were developed and tested for their fluorescence-enhancing capability in immunoassays with EuDTPA-labelled antibodies. Characteristics tested were fluorescence intensity, analytical sensitivity, kinetics of complex formation and signal stability. Formation of fluorescent complexes is fast (5 min) in the presented enhancement solution with EuDTPA probes withstanding strong complexones (ethylenediaminetetra acetate (EDTA) up to 100 mM) or metal ions (up to 200 μM) in the reaction mixture, the signal is intensive, stable for 4 h and the analytical sensitivity with Eu is 40 fmol/L, Tb 130 fmol/L, Sm 2.1 pmol/L and Dy 8.5 pmol/L. With the improved fluorescence enhancement technique, EDTA and citrate plasma samples as well as samples containing relatively high concentrations of metal ions can be analysed using a one-step immunoassay format also at elevated temperatures. It facilitates four-plexing, is based on one chelate structure for detector molecule labelling and is suitable for immunoassays due to the wide dynamic range and the analytical sensitivity.     

On unitary analogs of GCD reciprocal LCM matrices

A divisor d ∈ ?₊ of n ∈ ?₊ is said to be a unitary divisor of n if (d, n/d) = 1. In this article we examine the greatest common unitary divisor (GCUD) reciprocal least common unitary multiple (LCUM) matrices. At first we concentrate on the difficulty of the non-existence of the LCUM and we present three different ways to overcome this difficulty. After that we calculate the determinant of the three GCUD reciprocal LCUM matrices with respect to certain types of functions arising from the LCUM problematics. We also analyse these classes of functions, which may be referred to as unitary analogs of the class of semimultiplicative functions, and find their connections to rational arithmetical functions. Our study shows that it does make a difference how to extend the concept of LCUM.     

Solvent exchange in thermally stable resorcinarene nanotubes

The assembly of C-methyl resorcinarene into a tubular supramolecular solid-state structure, its thermal stability, and its hosting properties are reported. Careful control of the crystallisation conditions of C-methyl resorcinarene and 1,4-dimethyl-1,4-diazoniabicyclo[2.2.2]octane (1,4-dimethyl DABCO) dibromide leads to a formation of two crystallographically different, but structurally very similar, solid-state nanotube structures. These structures undergo a remarkable variety of supramolecular interactions, which lead to the formation of 0.5 nm diameter nonpolar tubes through the crystal lattice. The formation of these tubes is templated by suitably sized small alcohols, namely, n-propanol, 2-propanol, or n-butanol. The self-assembly involves close pi...pi interactions between the adjacent resorcinarenes, and C--H...pi and cation...pi interactions between the resorcinarenes and the guest 1,4-dimethyl DABCO dications. The crystals of these supramolecular tube structures are thermally very stable and the included solvent alcohol can be removed from the tubes without breaking the single-crystalline structure of the assembly. After removal of the solvent molecules the tubes can be filled with other small, less polar solvent molecules such as dichloromethane.     

Syntheses and NMR,MS and X‐ray investigations of homoadamantane‐fused pyridopyrimidinones

The reactions of ethyl 5‐oxotricyclo[4.3.1.1^3,8]undecane‐4‐carboxylate (2) with methyl‐substituted 2‐aminopyridines in polyphosphoric acid (PPA) gave two products, linearly‐condensed pyridopyrimidinones 4a‐c and 2‐pyridylcarboxamides 5a‐c , whereas the reactions with amino, hydroxy and nitro derivatives of 2‐aminopyridine furnished only linearly‐condensed pyridopyrimidinones (4g‐j). Use of a mixture of PPA and phosphorus oxychloride as solvent afforded both linearly‐ (4a‐c,e,f) and angularly‐condensed (6a–c,e,f) pyridopyrimidinones. In toluene, with p‐toluenesulfonic acid as catalyst, 2‐pyridylcarboxamides 5a‐f were obtained. In a mixture of PPA and phosphorus oxychloride at 80–120 °C, 5a‐f yielded angularly‐condensed pyridopyrimidinones 6a‐f. All the products exhibited characteristic features, as determined by NMR and electron ionization mass spectrometry and X‐ray crystallography.     

Structurally diverse second-generation [2.2]paracyclophane ketimines with planar and central chirality: syntheses, structural determination, and evaluation for asymmetric catalysis

A set of 20 novel [2.2]paracyclophane ketimines with planar and central chirality has been synthesized from enantiomerically pure and racemic 5-acyl-4-hydroxy[2.2]paracyclophane and alpha-branched chiral amines. Their X-ray structures were determined to elucidate the three-dimensional structures and the absolute configuration. The ketimines were used as catalysts in the asymmetric 1,2-addition reactions of diethylzinc with substituted benzaldehydes to furnish chiral alcohols in up to 95 % ee.