Star-shaped azo-based dipolar chromophores: design, synthesis, matrix compatibility, and electro-optic activity

Three new azo-benzene-based push-pull chromophores with dendritic architecture were synthesized as active materials for electro-optic applications. These chromophores were synthesized in six or seven synthetic steps with an overall yield of around 80% per step and high purity. UV-vis spectroscopy showed significant influence of the transient dipole moment on the observed r(33) values. The chromophores were stable to photochemical oxidation in ambient light and air. The electrical poling conditions were optimized for each chromophore as the T(g) of the composite material varied significantly. The highest EO coefficient achieved was 22-25 pm/V at 1550 nm wavelength. STEM analysis of the blends enabled the correlation of the activity of these large chromophores with the blend morphology. An amorphous polycarbonate host effectively disperses the chromophores in 2-20 nm aggregates in the active materials. However, macrophase separation into 200-500 nm aggregates was observed in a methacrylate host matrix.     

Syntheses of Theaspirone and Vitispirane via Palladium(II)-Catalyzed Oxaspirocyclization

Total syntheses of theaspirone (A and B) and vitispirane (A and B) are described. The key step in the syntheses is the palladium(II)-catalyzed intramolecular oxaspirocyclization of diene alcohol 4 to either vitispirane or the allylic alcohol 9. The outcome of the oxaspirocyclization is very much dependent on the solvent employed. In water-acetic acid (4:1) a 1:1 mixture of the diastereomeric alcohols 9A and 9B was exclusively formed. In water with 8 equiv of a strong non-nucleophilic acid, vitispiranes A and B (1:1) were obtained. An alternative procedure to obtain vitispirane with the use of LiCl and K(2)CO(3) is described. In the latter reaction vitispirane B is formed preferentially. This result is explained by an equilibrium between the two possible pi-allyl complexes 5A and 5B, the kinetically favored 5B being transformed into vitispirane 3B before isomerization to 5A occurs.     

One-Pot Synthesis and Applications of N-Heteroaryl Iodonium Salts

An efficient one-pot synthesis of N-heteroaryl iodonium triflates from the corresponding N-heteroaryl iodide and arene has been developed. The reaction conditions resemble our previous one-pot syntheses, with suitable modifications to allow N-heteroaryl groups. The reaction time is only 30 min, and no anion exchange is required. The obtained iodonium salts were isolated in a protonated form, these salts can either be employed directly in applications or be deprotonated prior to use. The aryl groups were chosen to induce chemoselective transfer of the heteroaryl moiety to various nucleophiles. The reactivity and chemoselectivity of these iodonium salts were demonstrated by selectively introducing a pyridyl moiety onto both oxygen and carbon nucleophiles in good yields.     

Development of a chiral non-aqueous capillary electrophoretic system using the partial filling technique with UV and mass spectrometric detection

A chiral non-aqueous CE system with UV and mass spectrometric detection has been developed. The enantioseparation was promoted by diastereomeric complex (ion-pair) formation between the amines (e.g. salbutamol, atenolol) and the chiral selector, (-)-2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid [(-)-DIKGA]. Different solvent mixtures were studied, as well as different concentrations of (-)-DIKGA and ammonium acetate in the background electrolyte. A partial filling technique was developed with a selector plug composed of (-)-DIKGA and ammonium acetate in a solvent mixture of methanol and 2-propanol. The separated enantiomers of pronethalol were detected by a Q-TOF MS system equipped with a sheath-flow electrospray ionization interface.     

Application of multivariate analysis of TOF-SIMS spectra for studying the effect of high glucose intake on aortic lipid profile

Aim

To study the effect of long-term glucose feeding on aortic lipid composition by using the time of flight-secondary ion mass spectrometry (TOF-SIMS).

Method

Rats were divided into two groups, drinking water with or without 10% glucose from birth to 6 months of age. The aortic wall was dissected out, high-pressure frozen, freeze-fractured, freeze-dried and analyzed by TOF-SIMS using a Bismuth cluster ion source. Surface spectra were taken from standardized regions of the vessel wall.

Results

Different peaks, such as cholesterol, fatty acids (FAs) and diacylglycerols (DAGs), were identified by the principal component analysis as carries of variance between two groups. These peaks were then compared by conventional t-test. Our data showed that the intensity of cholesterol, but not FAs and DAGs, was significantly decreased in the glucose-drinking rat. Moreover, the long-term glucose intake changed ratios between different FAs in the aorta.

Conclusion

The long-term glucose intake led to decreased cholesterol intensity in the aortic wall and this effect was revealed through a global analytical approach with objective selection of significant variables.     

Development of a capillary electrophoretic method for determination of plasma clearance of iohexol in dogs and cats

Renal function can be monitored by estimation of the glomerular filtration rate (GFR), for example, through measurement of the plasma clearance of a marker that is freely filtrated through the kidney without reabsorption. It has been proposed that iohexol is the most accurate marker for GFR determination in cats and dogs. However, there is a need for a validated capillary electrophoretic method that covers the concentration range for a full curve clearance estimate of iohexol. In the final method, the plasma samples were protein precipitated and the supernatant was analyzed in a background electrolyte containing borate buffer (0.06 m , pH 10.0). The method developed was proved to be linear (concentration range 18– 2900 mg/L) and had a good precision (e.g. 2.3–2.9% at 88 mg/L) and accuracy (e.g. 101–105% at 88 mg/L). Finally, the method was compared with a previously published and validated HPLC‐UV method by parallel analysis of clinical plasma samples from dogs and cats administered Omnipaque®. This comparison showed excellent agreement between the two methods and no proportional or systematic error was observed. The proposed method is simple and has a low cost per sample, which makes it applicable for routine analysis. Copyright © 2014 John Wiley & Sons, Ltd.     

Chiral separation of amines with N-benzoxycarbonylglycyl-L-proline as selector in non-aqueous capillary electrophoresis using methanol and 1,2-dichloroethane in the background electrolyte

N-Benzoxycarbonylglycyl-L-proline (L-ZGP) has been introduced as a chiral selector for enantioseparation of amines in non-aqueous capillary electrophoresis. Methanol mixed with different proportions of dichloromethane, 1,2-dichloroethane or 2-propanol containing L-ZGP and ammonium acetate was used as the background electrolyte. Enantioseparation of different types of pharmacologically active amines was performed, e.g. the local anaesthetic bupivacaine and the beta-adrenoceptor blocking agent pindolol. Addition of the solvents (dichloromethane, 1,2-dichloroethane or 2-propanol) gave an improved chiral separation partly due to a distinct decrease in the electroosmotic flow. The use of 1,2-dichloroethane in the background electrolyte gave higher precision in migration time (RSD 2.2%) compared to the systems containing dichloromethane. An enantiomeric separation of mepivacaine was performed within 72 s by use of short-end injection with an effective capillary length of 8.5 cm.     

An unsegmented extraction system for flow injection analysis

In the system described, the two phases are fed into a module containing a PTFE membrane so that no segmentation takes place, i.e., each phase is fed to only on one dise of the membrane. The groove depth on the “aqueous” side of the membrane is 0.4 mm and on the “organic” side 0.8 mm. This latter groove is filled with a porous support of polyethylene. Caffeine, sodium dodecyl sulphate and sodium dioctylsulphosuccinate samples (40—500 μl) were injected into an aqueous carrier stream which was merged and mixed with an aqueous reagent before it was fed into the module. The maximum extraction efficiency varied with the flow rate but was in the range 8–18% and was obtained by injecting sample volumes larger than 400 μl. By injecting 40 μl of sample, the efficiency dropped by a factor of 1.5–7, depending on the character of the analyte. The system is suitable for coarse liquid-liquid extraction of concentrated samples because neither segmentation nor separation of the phases is required.     

Conformational stability studies of a stapled hexa-β3-peptide library

A library of 14-helical hexa β(3)-peptides was synthesized in order to determine the influence of sequence variation as well as staple size and location on conformational stability. From this study we show that appropriately stapled hexa-β(3)-peptides can allow for a number of variations without significant perturbation of the 14-helix.