(1S*,3S*,8S*,10S*)-10-Fluoro-15-oxatetracyclo[6.6.1.0(1,10).0( 3,8)]pentadeca-5,12-dien-3-ol

The title compound, C(14)H(17)FO(2), was obtained from anti-4a, 9a:8a,10a-diepoxy-1,4,4a,5,8,8a, 9,9a, 10,10a-decahydroanthracene via tandem hydrogen-fluoride-mediated epoxide ring-opening and transannular oxacyclization. With the two cyclohexene rings folded towards the oxygen bridge, the title tetracyclic fluoroalcohol molecule displays a conformation reminiscent of a pagoda. The crystal packing is effected via intermolecular O-H center dot center dot center dot O hydrogen bonds, which link the molecules into a zigzag chain along the b axis.

An Enantiospecific Approach to Irregular Ligusticum grayi Sesquiterpenes: Synthesis of cis-Preisothapsa-2,8(12)-diene

Enantiospecific syntheses of 1-epi- (or cis-)-preisothapsa-2,8(12)-diene and 1-epi- and 1,8-diepipreisothapsa-2-en-12-ols, starting from the readily available monoterpene (R)-carvone, have been accomplished.

An Enantiospecific Formal Total Synthesis of the 5-8-5 Tricyclic Diterpene ent-Fusicoauritone

An enantiospecific formal total synthesis of the 5-8-5 tricyclic diterpene fusicoauritone has been accomplished, starting from 5-isopropyl-2-methylcyclopent-1-enemethanol [available in three steps from (R)-dihydrolimonene] employing two ring-closing-metathesis reactions for the construction of the eight- and five-membered rings.

Pillar height dependent formation of unprecedented Pd-8 molecular swing and Pd-6 molecular boat via multicomponent self-assembly

Three-component self-assembly of a cis-blocked 90 degrees Pd(II) acceptor with a mixture of a tetraimidazole and a linear dipyridyl donor self-discriminated into unusual Pd-8 molecular swing (1) and Pd-6 molecular boat (2), which are characterized by single-crystal X-ray diffraction analysis; their ability to bind C-60 in solution is established by fluorescence titration.

Self-assembly of Ru-4 and Ru-8 assemblies by coordination using organometallic Ru(II)(2) precursors: Synthesis, characterization and properties

Coordination-driven self-assembly of binuclear half-sandwich p-cymene ruthenium(II) complexes [Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) or [Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)(MeOH)(2)(eta(6)-p-cymene)(2)]( O3SCF3)(2) (1b) separately with an imidazole-based tetratopic donor L in methanol affords two tetranuclear metallamacrocycles 2a and 2b, respectively. Conversely, the similar combination of L with 2,5-dihydroxy-1,4-benzoquinonato (dhbq) bridged binuclear complex [Ru-2(mu-eta(C6H2O4)-C-4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1c) in 1:2 molar ratio resulted in an octanuclear macrocyclic cage 2c. All the self-assembled macrocycles 2a-2c were isolated as their triflate salts in high yields and were characterized fully by multinuclear (H-1, C-13 and F-19) NMR, infrared (IR) and electrospray ionization mass spectrometry (ESIMS). In addition, the molecular structure of macrocycle 2a was established unequivocally by single-crystal X-ray diffraction analysis and adopts a tetranuclear rectangular geometry with the dimensions of 5.53 angstrom x 12.39 angstrom. Furthermore, the photo-and electrochemical properties of these newly synthesized assemblies have been studied by using UV-vis absorption and cyclic voltammetry analysis.

Surface electrode switching of a 16-electrode wireless EIT system using RF-based digital data transmission scheme with 8 channel encoder/decoder ICs

A Radio Frequency (RF) based digital data transmission scheme with 8 channel encoder/decoder ICs is proposed for surface electrode switching of a 16-electrode wireless Electrical Impedance Tomography (EIT) system. A RF based wireless digital data transmission module (WDDTM) is developed and the electrode switching of a EIT system is studied by analyzing the boundary data collected and the resistivity images of practical phantoms. An analog multiplexers based electrode switching module (ESM) is developed with analog multiplexers and switched with parallel digital data transmitted by a wireless transmitter/receiver (T-x/R-x) module working with radio frequency technology. Parallel digital bits are generated using NI USB 6251 card working in LabVIEW platform and sent to transmission module to transmit the digital data to the receiver end. The transmitter/receiver module developed is properly interfaced with the personal computer (PC) and practical phantoms through the ESM and USB based DAQ system respectively. It is observed that the digital bits required for multiplexer operation are sequentially generated by the digital output (D/O) ports of the DAQ card. Parallel to serial and serial to parallel conversion of digital data are suitably done by encoder and decoder ICs. Wireless digital data transmission module successfully transmitted and received the parallel data required for switching the current and voltage electrodes wirelessly. 1 mA, 50 kHz sinusoidal constant current is injected at the phantom boundary using common ground current injection protocol and the boundary potentials developed at the voltage electrodes are measured. Resistivity images of the practical phantoms are reconstructed from boundary data using EIDORS. Boundary data and the resistivity images reconstructed from the surface potentials are studied to assess the wireless digital data transmission system. Boundary data profiles of the practical phantom with different configurations show that the multiplexers are operating in the required sequence for common ground current injection protocol. The voltage peaks obtained at the proper positions in the boundary data profiles proved the sequential operation of multiplexers and successful wireless transmission of digital bits. Reconstructed images and their image parameters proved that the boundary data are successfully acquired by the DAQ system which in turn again indicates a sequential and proper operation of multiplexers as well as the successful wireless transmission of digital bits. Hence the developed RF based wireless digital data transmission module (WDDTM) is found suitable for transmitting digital bits required for electrode switching in wireless EIT data acquisition system. (C) 2011 Elsevier Ltd. All rights reserved.

NMR Analysis of Cross Strand Aromatic Interactions in an 8 Residue Hairpin and a 14 Residue Three Stranded beta-Sheet Peptide

Cross strand aromatic interactions between a facing pair of phenylalanine residues in antiparallel beta-sheet structures have been probed using two structurally defined model peptides. The octapeptide Boc-(LFVPPLFV)-P-D-P-L-OMe (peptide 1) favors the beta-hairpin conformation nucleated by the type II' beta-turn formed by the (D)Pro-(L)Pro segment, placing Phe2 and Phe7 side chains in proximity. Two centrally positioned (D)Pro-(L)Pro segments facilitate the three stranded beta-sheet formation in the 14 residue peptide Boc-LFV(D)P(L)PLFVA(D)P(L)PLFV-OMe (peptide 2) in which the Phe2/Phe7 orientations are similar to that in the octapeptide. The anticipated folded conformations of peptides 1 and 2 are established by the delineation of intramolecularly hydrogen bonded NH groups and by the observation of specific cross strand NOEs. The observation of ring current shifted aromatic protons is a diagnostic of close approach of the Phe2 and Phe7 side chains. Specific assignment of aromatic proton resonances using HSQC and HSQC-TOCSY methods allow an analysis of interproton NOEs between the spatially proximate aromatic rings. This approach facilitates specific assignments in systems containing multiple aromatic rings in spectra at natural abundance. Evidence is presented for a dynamic process which invokes a correlated conformational change about the C-alpha-C-beta(chi(1)) bond for the pair of interacting Phe residues. NMR results suggest that aromatic ring orientations observed in crystals are maintained in solution. Anomalous temperature dependence of ring current induced proton chemical shifts suggests that solvophobic effects may facilitate aromatic ring clustering in apolar solvents.

Switching of a Sixteen Electrode Array for Wireless EIT System Using a RF-Based 8-Bit Digital Data Transmission Technique

Surface electrode switching of 16-electrode wireless EIT is studied using a Radio Frequency (RF) based digital data transmission technique operating with 8 channel encoder/decoder ICs. An electrode switching module is developed the analog multiplexers and switched with 8-bit parallel digital data transferred by transmitter/receiver module developed with radio frequency technology. 8-bit parallel digital data collected from the receiver module are converted to 16-bit digital data by using binary adder circuits and then used for switching the electrodes in opposite current injection protocol. 8-bit parallel digital data are generated using NI USB 6251 DAQ card in LabVIEW software and sent to the transmission module which transmits the digital data bits to the receiver end. Receiver module supplies the parallel digital bits to the binary adder circuits and adder circuit outputs are fed to the multiplexers of the electrode switching module for surface electrode switching. 1 mA, 50 kHz sinusoidal constant current is injected at the phantom boundary using opposite current injection protocol. The boundary potentials developed at the voltage electrodes are measured and studied to assess the wireless data transmission.

Toll-Like Receptors 7, 8, and 9 Expression and Function in Primary Human Cervical Cancer Langerhans Cells Evidence of Anergy

Objective: Human papillomavirus oncoproteins E6 and E7 down modulate Toll-like receptor (TLR) 9 expression in infected keratinocytes. We explored the status of expression and function of TLR7, TLR8, and TLR9 in primary human Langerhans cells (LCs) isolated from cervical tumors. Methodology: Single-cell suspensions were made from fresh tissues of squamous cell carcinoma (International Federation of Gynecology and Obstetrics stage IB2); myeloid dendritic cells were purified using CD1c magnetic activated cell separation kits. Langerhans cells were further flow sorted into CD1a(+)CD207(+) cells. Acute monocytic leukemia cell line THP-1-derived LCs (moLCs) formed the controls. mRNA from flow-sorted LCs was reverse transcribed to cDNA and TLR7, TLR8, and TLR9 amplified. Monocyte-derived Langerhans cells and cervical tumor LCs were stimulated with TLR7, TLR8, and TLR9 ligands. Culture supernatants were assayed for interleukin (IL) 1 beta, IL-6, IL-10, IL-12p70, interferon (IFN) alpha, interferon gamma, and tumor necrosis factor (TNF) alpha by Luminex multiplex bead array. Human papillomavirus was genotyped. Results: We have for the first time demonstrated that the acute monocytic leukemia cell line THP-1 can be differentiated into LCs in vitro. Although these moLCs. expressed all the 3 TLRs, tumor LCs expressed TLR7 and TLR8, but uniformly lacked TLR9. Also, moLCs secreted IL-6, IL-1 beta, and tumor necrosis factor alpha to TLR8 ligand and interferon alpha in response to TLR9 ligand; in contrast, tumor LCs did not express any cytokine to any of the 3 TLR ligands. Human papillomavirus type 16 was one of the common human papillomavirus types in all cases. Conclusions: Cervical tumor LCs lacked TLR9 expression and were functionally anergic to all the 3: TLR7, TLR8, and TLR9 ligands, which may play a crucial role in immune tolerance. The exact location of block(s) in TLR7 and TLR8 signaling needs to be investigated, which would have important immunotherapeutic implications.

A novel DNA intercalator, 8-methoxy pyrimido4 `,5 `:4,5]thieno (2,3-b)quinoline-4(3H)-one induces apoptosis in cancer cells, inhibits the tumor progression and enhances lifespan in mice with tumor

Polycyclic aromatic molecules such as ellipticine intercalate into double-stranded DNA and interfere with physiological functions. In the present study, we evaluate the chemotherapeutic potential of MPTQ on animal models and its mode of action. In order to test the antitumor activity, monohydrochloride of MPTQ was orally administered in mice bearing tumor. Results showed a significant inhibition of tumor growth compared to that of untreated controls. More importantly, mean lifespan of tumor bearing animals treated with MPTQ was significantly higher as compared to that of untreated tumor bearing mice suggesting that the treatment affected viability of cancerous cells, but not of normal cells. Consistent with this, we find that administration of MPTQ to normal mice did not cause any major side effects as observed upon hematological and serum profiling. We also found that MPTQ induces cytotoxicity in cancer cell lines, by activating apoptosis both by intrinsic and extrinsic pathways. Thus, MPTQ could be used as a potential cancer therapeutic agent.