A New β-Ionone from Liriodendron tulipifera

Chemistry of Natural Compounds - A new β-ionone, litulipiferic acid (12), was isolated from the leaves of Liriodendron tulipifera (Magnoliaceae). The structure of the new β-ionone was...     

Direct Synthesis of Chiral 3‐Arylsuccinimides by Rhodium‐Catalyzed Enantioselective Conjugate Addition of Arylboronic Acids to Maleimides

Chiral rhodium catalysts comprising 2,5‐diaryl‐ substituted bicyclo[2.2.1]diene ligands L1 – L10 were utilized in the enantioselective 1,4‐addition reaction of arylboronic acids to N‐substituted maleimides. In the presence of 2.5 mol % of Rh^I/ L2 , enantioenriched conjugate addition adducts were isolated in 72–99 % yields with 86–98 % ee. This protocol offers a convenient method to access a variety of 3‐arylsuccinimides in a highly enantioselective manner. Maleimides with readily cleavable N‐protecting groups were tolerated enabling the synthesis of useful synthetic intermediates. Pyrrolidine 4 , a biologically active compound, and pyrrolidine 5 , an ent‐precursor to an HSD‐1 inhibitor, were synthesized to demonstrate the utility of this method.     

Stage-frit: A straightforward sub-2 μm nano-liquid chromatography column fabrication for proteomic analysis

In this work we demonstrated a facile method for the fabrication of C18 coordination polymer gel in a capillary, called stage-frit, which was efficiently applied to pack sub-2 μm C18 beads into the capillary by a high pressure bomb for the online separation of proteolytic peptides. The back pressure of the column with 10 cm × 75 μm i.d. is regularly lower than 170 bar at a flow rate of 300 nl/min, which could be operated on a common nanoLC system instead of nanoUPLC system due to the good permeability, low back pressure and high mechanical stress of the frit that will totally reduce the cost for the purchase of instrument. The stage-frit allows long-term continuous flow of the solvent and no significant beads loss or pressure instability was observed during the period. The repeatability of retention time for fifteen BSA tryptic peaks was found to be less than 1.08% (RSD) in six time nanoLC-ESI-MS/MS experiments. The average full width at half maximum (FWHM) of peptide peaks is 5.87 s. The sub-2 μm stage-frit nanoLC column showed better sensitivity than the commercial available for large scale proteomic analysis of total tissue proteins from human spleen. The number of identified peptides is approximately 0.4-fold and 0.2-fold higher than that obtained by utilizing commercial columns packed with 3 μm and 1.8 μm C18 materials, respectively. In the field of analytical chemistry, particularly the use of nanoLC systems, stage-frit nanoLC column offers a great potential for the separation of complex mixtures.     

Synthesis of five-coordinate manganese(I) carbonyl complex [(CO)<Subscript>3</Subscript>Mn (-S,-Se-C<Subscript>6</Subscript>H<Subscript>3</Subscript>-4-Me)]<Superscript>−</Superscript>: influences of non-innocent ligand to the structure,reactivity and electrochemical property

Oxidative addition of Br₂ to [Mn(CO)₅]^? leads to the formation of [(CO)₄MnBr], followed by the ligand exchange of bromide to [S,Se-C₆H₃-4-Me] ₂ ^2? to form complex (CO)₃Mn (µ-? ⁴-SC₆H₃-4-(CH₃)Se-SeC₆H₃-4-(CH₃)S)Mn(CO)₃ (1). A new five-coordinate complex [(CO)₃Mn(-S,-Se-C₆H₃-4-CH₃)]^? (2) can be synthesized through two different routes: (a) oxidative addition of diselenide [HS,Se-C₆H₃-4-Me]₂ to the [Mn(CO)₅]^? followed by deprotonation and ligand dissociation to generate complex 2; (b) reduction of diselenide bonds of complex 1 by [BH₄]^? to produce 2. Drop-wise addition of HBF₄·OEt₂ at 0 °C results in the formation of complex 1. The X-ray analysis shows that complex 2 has relative short Mn–Se and Mn–S bond distances compare to the published structures of cis-[(CO)₄Mn(EPh)₂]^? (E = S and Se; Liaw et al. in J. Chin. Chem. Soc. 43:427–431, 1996; Liaw et al. in Inorg. Chem. 35:2530, 1996). Interestingly, exposure of the coordinated unsaturated complex 2 under CO_(g) atmosphere resulted in complex cis-[(CO)₄Mn(-S,-Se-C₆H₃-4-Me)]^? (3) being formed. After purging the solution of complex 3 with N₂, it was reconverted completely back to complex 2; this observation was characterized by FTIR. The cyclic voltammetry scan of complex 2 shows a quasi-reversible redox couple with E _1/2 = ?1.94 V and I _pa/I _pc = 0.68. Ligand [HS, Se-C₆H₃-4-CH₃]₂ and complexes 1 and 2 are all characterized by IR, UV–Vis, NMR, EA and X-ray single crystal diffraction.     

Studies of Coumarin Derivatives for Constitutive Androstane Receptor (CAR) Activation

Constitutive androstane receptor (CAR) activation has found to ameliorate diabetes in animal models. However, no CAR agonists are available clinically. Therefore, a safe and effective CAR activator would be an alternative option. In this study, sixty courmarin derivatives either synthesized or purified from Artemisia capillaris were screened for CAR activation activity. Chemical modifications were on position 5,6,7,8 with mono-, di-, tri-, or tetra-substitutions. Among all the compounds subjected for in vitro CAR activation screening, 6,7-diprenoxycoumarin was the most effective and was selected for further preclinical studies. Chemical modification on the 6 position and unsaturated chains were generally beneficial. Electron-withdrawn groups as well as long unsaturated chains were hazardous to the activity. Mechanism of action studies showed that CAR activation of 6,7-diprenoxycoumarin might be through the inhibition of EGFR signaling and upregulating PP2Ac methylation. To sum up, modification mimicking natural occurring coumarins shed light on CAR studies and the established screening system provides a rapid method for the discovery and development of CAR activators. In addition, one CAR activator, scoparone, did showed anti-diabetes effect in db/db mice without elevation of insulin levels.     

Positively charged liposomes consisting of the KTTKS pentapeptide conjugated with rhodamine increase rhodamine toxicity in E. coli and zebrafish embryo

Liposomes composed of cell‐penetrating peptide derivatives increased transport across the cell membrane. Conjugating rhodamine to a cell‐penetrating peptide increased the toxicity of rhodamine in E. coli and zebrafish embryos. A similar total protein inhibition pattern with different intensities, indicating that the interaction pathways of the rho‐KTTKS‐CONH₂ monomer and liposomes were the same. It suggests that the rho‐KTTKS‐CONH₂ liposomes showed higher toxicity because better transport across the cell membrane increased the effective concentration inside cells. The staining of zebrafish embryos using rho‐KTTKS‐CONH₂ liposomes showed a longer retention time, suggesting that it can penetrate deeper tissues or organs in zebrafish.     

Thermomechanical behavior of underfill/solder mask/substrate interface under thermal cycling

With the increasing application of flip-chip technology in the microelectronics industry, the adhesion strength of interfaces in flip-chip microelectronic structures has become an important issue for manufacturing and operation. In this paper we present an experimental investigation of the adhesive strength of underfill material to solder mask coated FR-4 substrate under thermal cycling. The effects of the number of thermal cycles on interfacial strength were investigated by using the button shear test. The relationship between interfacial strength and the thickness of solder mask was also examined. Furthermore, the morphologies of fracture surfaces of the test specimens were analyzed by scanning electron microscopy. The results of this study show that the interfacial strength of the underfill/solder mask/substrate joint was significantly reduced by thermal fatigue. Finally, the degradation behavior and possible mechanisms were then determined on the basis of these observations.     

Active dielectric metasurface based on phase‐change medium

We propose all‐dielectric metasurfaces that can be actively re‐configured using the phase‐change material Ge₂Sb₂Te₅ (GST) alloy. With selectively controlled phase transitions on the composing GST elements, metasurfaces can be tailored to exhibit varied functionalities. Using phase‐change GST rod as the basic building block, we have modelled metamolecules with tunable optical response when phase change occurs on select constituent GST rods. Tunable gradient metasurfaces can be realized with variable supercell period consisting of different patterns of the GST rods in their amorphous and crystalline states. Simulation results indicate a range of functions can be delivered, including multilevel signal modulating, near‐field coupling of GST rods, and anomalous reflection angle controlling. This work opens up a new space in exploring active meta‐devices with broader applications that cannot be achieved in their passive counterparts with permanent properties once fabricated.

     

Water waves in an elastic vessel

Linear and nonlinear analyses of water waves in an elastic vessel are carried out to study the dramatic phenomena of Dragon Wash as well as related controllable experiments. It is proposed that the capillary edge waves are generated by parametric resonance, which is shown to be a possible mechanism for both rectangular an circular vessels. For circular vessel, the normal geometric resonance is also operating, thus greatly enhance the dramatic effect. The mechanism of nonlinear mode-mode interaction is proposed for the generation of axisymmetric low-frequency gravity waves by the high- frequency external excitation. A simple model system is studied numerically to demonstrate explicitly this interaction mechanism.