Endocyclic cleavage in glycosides with 2,3-trans cyclic protecting groups

An endocyclic pathway is proposed as a reaction mechanism for the anomerization from the β (1,2-trans) to the α (1,2-cis) configuration observed in glycosides carrying 2,3-trans cyclic protecting groups. This reaction occurs in the presence of a weak Lewis or Br?nsted acid, while endocyclic cleavage (endocleavage) in typical glycosides was observed only when mediated by protic media or strong Lewis acids. To rationalize the behavior of this class of compounds, the reaction mechanism and the promoting factors of the endocleavage are investigated using quantum-mechanical (QM) calculations and experimental studies. We examine anomerization reactions of thioglycosides carrying 2,3-trans cyclic protecting groups, employing boron trifluoride etherate (BF(3)·OEt(2)) as a Lewis acid. The estimated theoretical reactivity, based on a simple model to predict transition state (TS) energies from the strain caused by the fused rings, is very close to the TS energies calculated by the TS search along the C1-C2 bond rotation after the endo C-O bond breaking. Excellent agreement is found between the predicted TS energies and the experimental reactivity ranking. The series of calculations and experiments strongly supports the predominance of the endocyclic rather than the exocyclic mechanism. Furthermore, these investigations suggest that the inner strain is the primary factor enhancing the endocleavage reaction. The effect of the cyclic protecting group in restricting the pyranoside ring to a (4)C(1) conformation, extensively discussed in conjunction with the stereoelectronic effect theory, is shown to be a secondary factor.     

Obtaining nanocomposites of polyamide 6 and cellulose whiskers via extrusion and injection molding

Nanocomposites of polyamides with cellulose whiskers are difficult to obtain by conventional processing of extrusion and injection molding because of the low thermal stability of the cellulosic nanostructures and the relatively high processing temperature of polyamides, which is higher than the temperature of thermal degradation of cellulose whiskers. Thus, in this study cellulose whiskers were coated with polyamide 6 (PA6) in order to increase their thermal stability and prevent the formation of agglomerates. This coating on cellulose whiskers allows their application to obtain nanocomposites with polyamides, whose processing temperatures are relatively high, around 250 °C. Cellulose whiskers (CWs) were obtained from cotton fibers by acid hydrolysis. The freeze-dried CWs were coated with PA6 by dispersing them in formic acid; PA6 was solubilized in this suspension. The cellulose-coated whiskers (CCWs) were characterized by X-ray diffraction, differential scanning calorimetry (DSC), thermogravimetry (TG), scanning electron microscopy (SEM-FEG) and infrared spectroscopy. SEM-FEG and TG results showed that the PA6 coating on CWs prevented high agglomeration of dried CWs and promoted an increase in their thermal stability from 180 to 280 °C, allowing the use of CCWs to obtain nanocomposites with PA6 using conventional processing routes, such as extrusion and injection molding, at appropriate processing temperatures. In this way, 1 wt% CCWs was used to prepare nanocomposites with PA6. The PA6 + 1CW nanocomposites were compared to neat PA6 without CWs. The samples were characterized by tensile tests and DSC, and the results showed that the PA6 coating on CWs was effective in raising the thermal stability of CWs, improving the dispersion of CWs in the matrix of PA6, resulting in a 45 % increase in the elastic modulus of the nanocomposite with only 1 wt% of coated cellulose whiskers in comparison to neat PA6.     

TOF-SIMS study of cystine and cholesterol stones

Two different human stones, cystine and cholesterol from the kidney and gall bladder, were examined by time-of-flight secondary ion mass spectrometry using Ga(+) primary ions as bombarding particles. The mass spectra of kidney stone were compared with those measured for the standard compounds, cystine and cysteine. Similar spectra were obtained for the stone and cystine. The most important identification was based on the existence of the protonated molecules [M + H](+) and deprotonated molecules [M-H](-). The presence of cystine salt was also revealed in the stone through the sodiated cystine [M + Na](+) and the associated fragments, which might be due to the patient treatment history. In the gallstone, the deprotonated molecules [M-H](+) of cholesterol along with relatively intense characteristic fragments [M-OH](+) were detected.     

Multistage Yb-doped fiber amplifier generating megawatt peak-power, subnanosecond pulses

A Q-switched microchip laser generating 1064 nm wavelength, subnanosecond pulses at a 13.4 kHz repetition rate was used to seed a dual-stage amplifier featuring a 40 microm core Yb-doped photonic-crystal fiber (PCF) as the power amplifier. From this source, we obtained diffraction-limited (M2 = 1.05), approximately 450 ps pulses of energy > 0.7 mJ, peak power in excess of 1.5 MW, and an average power of approximately 9.5 W. By further amplifying the PCF output in a multimode 140 microm core Yb-doped fiber, we generated a peak power in excess of 4.5 MW, the highest obtained in a fiber source to our knowledge.     

New approach to the numerical solution of forward-backward equations

This paper is concerned with the approximate solution of functional differential equations having the form: x′(t) = αx(t) + βx(t - 1) + γx(t + 1). We search for a solution x, defined for t ∈ [−1, k], k ∈ ℕ, which takes given values on intervals [−1, 0] and (k-1, k]. We introduce and analyse some new computational methods for the solution of this problem. Numerical results are presented and compared with the results obtained by other methods.      

Convenient Michael addition/β-elimination approach to the synthesis of 4-benzyl- and 4-aryl-selenyl coumarins using diselenides as selenium sources

A concise and efficient, two-step approach toward 4-organoselenyl coumarin derivatives from the easily available 4-hydroxycoumarins, is reported. The synthesis was based on conventional tosylation followed by a tandem selena-Michael addition/β-elimination reaction of an aryl-/benzyl-selenolate anion on the corresponding 4-tosyloxycoumarins. The selenolate anions were conveniently generated in situ by exposure of the corresponding diselenides to NaBH₄. Selected compounds demonstrated to exhibit antioxidant properties in mice cortex and hippocampus.     

Thioorthoesters in the activated Pictet-Spengler cyclization. Synthesis of 1-thiosubstituted tetrahydroisoquinolines and carboncarbon bond formation via sulfonyl iminium ions generated from N,S-sulfonyl acetals

The elaboration of 1-alkylthio- and 1-arylthio-tetrahydroisoquinolines by means of the activated Pictet-Spengler reaction of N-sulfonyl-β-phenethylamines with thioorthoesters as electrophiles, and their use as sulfonyl iminium ion precursors for carboncarbon bond formation, leading to 1-substituted tetrahydroisoquinoline derivatives, is reported.     

1.1 MW peak-power, 7 W average-power, high-spectral-brightness, diffraction-limited pulses from a photonic crystal fiber amplifier

We report a large-core, Yb-doped photonic crystal fiber amplifier generating diffraction-limited (M2 = 1.04), approximately 0.45 ns, approximately 8 GHz linewidth pulses with energies of 540 microJ, peak power in excess of 1.1 MW, and average power of approximately 7.2 W at a repetition rate of 13.4 kHz. The pulse peak spectral brightness exceeds 10 kW/(sr Hz cm2) and is the highest generated by a fiber source, to our knowledge.