Effects of montmorillonite modification on optical properties of heterogeneous nematic liquid crystal - clay mineral nanocomposites

Investigations of montmorillonite (MMT) clay mineral modification effects on electro-optical properties of nanocomposites, based on the nematic liquid crystal 4-pentyl-4'-cyanobiphenyl (5CB) and MMT have been carried out. Only the composite with MMT modified by an organic surface-active substance, dioctadecyldimethylammonium chloride, has been shown to manifest electro-optical memory effect and contrast. A polar dopant (acetone), added to the mixture, significantly increases composite homogeneity. Results of IR spectroscopy measurements lead to the conclusion, that there is a mutual influence of components on each other in organoclay systems, which appears as an alignment of near-surface layers of both the organic and inorganic components of the composite. Due to such interactions these systems show electro-optical contrast and memory effect. A composite with organophobic Na-MMT does not show these electro-optical properties, due to the absence of component interactions, as shown by IR spectroscopic data.     

The case of RIB at intermediate energies: Isospin effects on nuclear dynamics

In the reaction dynamics of intermediate-energy radioactive beams we can probe highly asymmetric nuclear matter in compressed as well as dilute phases. In this report some predictions are presented, based on analytical results as well as on reaction simulations. We suggest a series of experiments with RIB aimed to shed light on isospin properties of nuclear interactions in the medium. Received: 1 May 2001 / Accepted: 4 December 2001     

CH Oxidation of Ingenanes Enables Potent and Selective Protein Kinase C Isoform Activation

Ingenol derivatives with varying degrees of oxidation were prepared by two‐phase terpene synthesis. This strategy has allowed access to analogues that cannot be prepared by semisynthesis from natural ingenol. Complex ingenanes resulting from divergent C? H oxidation of a common intermediate were found to interact with protein kinase C in a manner that correlates well with the oxidation state of the ingenane core. Even though previous work on ingenanes has suggested a strong correlation between potential to activate PKCδ and induction of neutrophil oxidative burst, the current study shows that the potential to activate PKCβII is of key importance while interaction with PKCδ is dispensable. Thus, key modifications of the ingenane core allowed PKC isoform selectivity wherein PKCδ‐driven activation of keratinocytes is strongly reduced or even absent while PKCβII‐driven activation of neutrophils is retained.     

Characterisation of α-chitin extracted from a lichenised fungus species Xanthoria parietina

Lichens are symbiotic associations formed mainly by ascomycete fungi and green algae or cyanobacteria. The presence of chitin in the fungal cell wall has been revealed by previous studies. Considering the presence of fungi in the lichens, this work determines the presence of chitin in a cosmopolitan lichen species Xanthoria parietina. In this study, chitin was derived from a lichen species for the first time and its physicochemical properties were determined by Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, scanning electron microscopy and elemental analysis. The dry weight chitin content of X. parietina was 4.23%, and this chitin was in the α-form. The crystalline index value of the lichen chitin was calculated as 70.1%. The chitin from X. parietina had a smooth surface.     

Cytotoxic and apoptotic activities of novel Pd(II) complexes against human leukemia cell lines in vitro

In the investigation for alternative chemotherapeutic strategies against leukemia, Pd(II) complexes were synthesized and investigated for cytotoxic and apoptotic properties on two human leukemia cell lines (HL-60 and K562). Pd(II) complexes (Pd-5a and Pd-6a) with 5a and 6a as ligands were synthesized and characterized by ¹H-NMR and F-TIR. The cytotoxicity of the compounds was quantified using MTT method. Bax, Bcl-2, and caspase 3 gene expression levels were estimated using RT-qPCR. Here we show that Pd(II) complexes have important cytotoxic activity on human leukemia cell lines. RT-qPCR indicated that Bax and caspase 3 gene expression levels were increased after 24 h treatment with Pd-5a and Pd-6a complexes in both HL-60 and K562 cells at some selected dose. Furthermore, Bcl-2 gene expression level decreased after 24 h treatment with Pd-5a and Pd-6a complexes in K562 cells at all selected dose. In HL-60 cells, only one selected Pd-5a dose (25 µM) decreased the gene expression level of Bcl-2. The results obtained in the present investigation indicate that these two newly synthesized Pd(II) complexes have apoptotic effects at appropriate doses through caspase 3 and Bax genes and might represent a novel potentially active agents for the management of human leukemia cell lines.     

Integrated quality by design (QbD) and design of experiments (DoE) approach for UFLC determination of telaprevir in rat serum

An ultrafast liquid chromatographic bioanalytical method was developed and validated for the determination of telaprevir in Wistar albino rat serum. Principles of quality by design (QbD) were implemented for enhancing the bioanalytical liquid–liquid extraction of telaprevir from rat serum. A Box–Behnken design was utilized in the studies by selecting extraction time, centrifugation speed, and vortex time as the critical method variables for evaluating their effect on the critical analytical attribute, i.e., %recovery of telaprevir. Chromatographic separation was achieved within a run time of 10?min using a C-18 column and mobile phase comprising of methanol:borate buffer of pH 9 (90:10 v/v) flowing at 1.2?mL/min. Photodiode array detection was performed at 270?nm. Results of validation studies were satisfactory. The method was linear over a concentration of 25–10,000?ng/mL. Limit of detection for the developed method was 10?ng/mL. Further, design of experiments (DoE) used for inter-day accuracy and precision study suggested superior method reliability. This integrated QbD- and DoE-based approach ensured the development of a validated and reliable analytical method for optimum bioanalysis of telaprevir in biological matrix.     

Nickel‐Catalyzed Barton Decarboxylation and Giese Reactions: A Practical Take on Classic Transforms

Two named reactions of fundamental importance and paramount utility in organic synthesis have been reinvestigated, the Barton decarboxylation and Giese radical conjugate addition. N ‐hydroxyphthalimide (NHPI) based redox‐active esters were found to be convenient starting materials for simple, thermal, Ni‐catalyzed radical formation and subsequent trapping with either a hydrogen atom source (PhSiH₃) or an electron‐deficient olefin. These reactions feature operational simplicity, inexpensive reagents, and enhanced scope as evidenced by examples in the realm of peptide chemistry.     

Unprecedented formation of benzo[d][1,2,3,6]oxatriazocine derivatives via diazo-oxygen bond formation and synthesis of enantiomerically pure 1-alkyl benzotriazole derivatives

A series of amino acid-derived enantiomerically pure substituted benzo[d][1,2,3,6]oxatriazocine derivatives and 1-alkyl substituted benzotriazoles has been prepared by the diazotization of amino acid-derived benzo-fused alicycles. The first unprecedented diazo-oxygen bond formation in acidic medium led to an entirely new kind of substituted benzo[d][1,2,3,6]oxatriazocine heterocycles.     

Synthesis of new donor-acceptor polymers containing thiadiazoloquinoxaline and pyrazinoquinoxaline moieties: low-band gap, high optical contrast, and almost black colored materials

Two low band gap conjugated polymers, poly[4,9-bis(4-hexylthien-2-yl)-6,7-di(thien-2-yl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline] (PHTTQ) and poly[5,10-bis(4-hexylthien-2-yl)-2,3,7,8-tetra(thien-2-yl)pyrazino[2,3-g]quinoxaline] (PHTPQ), consisting of alternating electron-rich 3-hexylthiophene and electron-deficient 6,7-di(thien-2-yl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline (TTQ) and 2,3,7,8-tetra(thien-2-yl)-2,3-dihydropyrazino[2,3-g]quinoxaline (TPQ) units were synthesized electrochemically. The structures of the π-conjugated monomers were tailored using thiophene as the pendant group on the acceptor units (TTQ and TPQ). The electrochemical and optical properties of the polymers were investigated by cyclic voltammetry and UV-vis-NIR spectroscopy. The absorption spectra of PHTPQ, revealing a 1.0 eV band gap, exhibited three maxima at 352 nm, 535 nm, and 750 nm. Consequently, its absorption spectra cover the region between 400 and 800 nm, which make the polymer almost black in appearance. PHTTQ shows a λ_max value of 820 nm and a band gap of 0.8 eV which is very low among other [1,2,5]thiadiazolo[3,4-g]quinoxaline-containing donor-acceptor type polymers.