Total Synthesis of Bistramide A and Its 36(Z) Isomers: Differential Effect on Cell Division,Differentiation, and Apoptosis

The total synthesis of bistramide A and its 36(Z),39(S) and 36(Z),39(R) isomers shows that these compounds have different effects on cell division and apoptosis. The synthesis relies on a novel enol ether‐forming reaction for the spiroketal fragment, a kinetic oxa‐Michael cyclization reaction for the tetrahydropyran fragment, and an asymmetric crotonylation reaction for the amino acid fragment. Preliminary biological studies show a distinct pattern of influence of each of the three compounds on cell division, differentiation, and apoptosis in HL‐60 cells, thus suggesting that these effects are independent activities of the natural product.     

Cyclometalated Iridium(III)–Polyamine Complexes with Intense and Long‐Lived Multicolor Phosphorescence: Synthesis,Crystal Structure,Photophysical Behavior,Cellular Uptake,and Transfection Properties

A new class of phosphorescent cyclometalated iridium(III)–polyamine complexes [{Ir(N^C)₂}_n(bPEI)](PF₆)_n (bPEI=branched poly(ethyleneimine), average M_w=25 kDa, n=15.6–27.4; HN^C=2‐phenylpyridine Hppy ( 1 a ), 2‐((1,1′‐biphenyl)‐4‐yl)pyridine Hpppy ( 2 a ), 2‐phenylquinoline Hpq ( 3 a ), 2‐phenylbenzothiazole Hbt ( 4 a ), 2‐(1‐naphthyl)benzothiazole Hbsn ( 5 a )) and [Ir(N^C)₂(en)](PF₆) (en=ethylenediamine; HN^C=Hppy ( 1 b ), Hpppy ( 2 b ), Hpq ( 3 b ), Hbt ( 4 b ), Hbsn ( 5 b )) have been synthesized and characterized. The X‐ray crystal structure of complex 5 b was also determined. All of these complexes showed a reversible iridium(IV/III) oxidation couple at +1.01 to +1.26 V and a quasi‐reversible ligand‐based reduction couple at ?1.54 to ?2.08 V (versus SCE). Upon photoexcitation, the complexes displayed intense and long‐lived green to orange–red emission in fluid solutions at room temperature and in low‐temperature glass. Lipophilicity measurements indicated that bPEI played a dominant role in the polar nature of complexes 1 a – 5 a , thus rendering them very soluble in aqueous solutions. Inductively coupled plasma–mass spectrometry (ICP‐MS) and confocal laser scanning microscopy (CLSM) data indicated that an energy‐requiring process, such as endocytosis, was involved in the cellular uptake of all of the complexes. In addition, the cytotoxicity of the complexes toward human cervix epithelioid carcinoma (HeLa) and human embryonic kidney 293T (HEK293T) cell‐lines has been evaluated by the 3‐(4,5‐dimethyl‐2‐thiazolyl)‐2,5‐diphenyltetrazolium bromide (MTT) assay. The DNA‐binding properties of complex 5 a have been investigated by gel‐retardation assays and the polyplexes that were formed from this complex with plasmid DNA (pDNA) were studied by zeta‐potential measurements and particle‐size estimation. Furthermore, complex 5 a was grafted with poly(ethylene glycol) (PEG, average M_w=2 kDa) to different extents, thereby yielding the phosphorescent copolymers PEG_12.3‐g‐5 a , PEG_25.4‐g‐5 a , and PEG_62.1‐g‐5 a . Interestingly, these copolymers showed enhanced transfection activity, as revealed by in vitro transfection experiments with tissue‐culture‐based luciferase assays.     

A Phthalocyanine–Peptide Conjugate with High In Vitro Photodynamic Activity and Enhanced In Vivo Tumor‐Retention Property

A novel zinc(II) phthalocyanine conjugated with a short peptide with a nuclear localization sequence, Gly‐Gly‐Pro‐Lys‐Lys‐Lys‐Arg‐Lys‐Val, was synthesized by click chemistry and a standard Fmoc solid‐phase peptide synthesis protocol. The conjugate was purified by HPLC and characterized with UV/Vis and high‐resolution mass spectroscopic methods. Both this compound and its non‐peptide‐conjugated analogue are essentially non‐aggregated in N,N‐dimethylformamide and can generate singlet oxygen effectively with quantum yields (Φ_Δ) of 0.84 and 0.81, respectively, relative to unsubstituted zinc(II) phthalocyanine (Φ_Δ=0.56). Conjugation of the peptide sequence, however, can enhance the cellular uptake, efficiency in generating intracellular reactive oxygen species, and photocytotoxicity of the phthalocyanine‐based photosensitizer against HT29 human colorectal carcinoma cells. The IC₅₀ value of the conjugate is as low as 0.21 μM . In addition, the conjugate shows an enhanced tumor‐retention property in tumor‐bearing nude mice. After 72 h post‐injection, the dye concentration in the tumor was significantly higher than that in other organs. The results suggest that this phthalocyanine–peptide conjugate is a highly promising photosensitizer for photodynamic therapy.     

General Dyson–Schwinger Equations and Systems

We classify combinatorial Dyson–Schwinger equations giving a Hopf subalgebra of the Hopf algebra of Feynman graphs of the considered Quantum Field Theory. We first treat single equations with an arbitrary (eventually infinite) number of insertion operators. We distinguish two cases; in the first one, the Hopf subalgebra generated by the solution is isomorphic to the Faà di Bruno Hopf algebra or to the Hopf algebra of symmetric functions; in the second case, we obtain the dual of the enveloping algebra of a particular associative algebra (seen as a Lie algebra). We also treat systems with an arbitrary finite number of equations, with an arbitrary number of insertion operators, with at least one of degree 1 in each equation.     

Light-assisted synthesis and functionalization of silver nanoparticles with thiol derivative thioxanthones: new insights into the engineering of metal/chromophore nanoassemblies

Nanofluids are suspensions of nanometer-sized particles which significantly modify the properties of the base fluids. Nanofluids exhibit attractive properties, such as high thermal conductivity, tunable surface tension, viscosity, and rheology. Various attempts have been made to understand the mechanisms for these property modifications caused by adding nanoparticles; however, due to the lack of direct nanoscale evidence, these explanations are still controversial. This work calculated the surface tension, viscosity, and rheology of gold–water nanofluids using molecular dynamics simulations which provide a microscopic interpretation for the modified properties on the molecular level. The gold–water interaction potential parameters were changed to mimic various nanoparticle types. The results show that the nanoparticle wettability is responsible for the modified surface tension. Hydrophobic nanoparticles always tend to stay on the free surface so they behave like a surfactant to reduce the surface tension. Hydrophilic nanoparticles immersed into the bulk fluid impose strong attractive forces on the water molecules at the free surface which reduces the free surface thickness and increases the surface tension of the nanofluid. Solid-like absorbed water layers were observed around the nanoparticles which increase the equivalent nanoparticle radius and reduce the mobility of the nanoparticles within the base fluid which increases the nanofluid viscosity. The results show the water molecule solidification between two or many nanoparticles at high nanoparticle loadings, but the solidification effect is suppressed for shear rates greater than a critical shear rate; thus Newtonian nanofluids can present shear-thinning non-Newtonian behavior.     

Stability and Fourier–Mukai transforms on elliptic fibrations

We systematically develop Bridgeland's [7] and Bridgeland–Maciocia's [10] techniques for studying elliptic fibrations, and identify criteria that ensure 2-term complexes are mapped to torsion-free sheaves under a Fourier–Mukai transform. As an application, we construct an open immersion from a moduli of stable complexes to a moduli of Gieseker stable sheaves on elliptic threefolds. As another application, we give various 1–1 correspondences between fibrewise semistable torsion-free sheaves and codimension-1 sheaves on Weierstrass surfaces.     

Multitechnique characterization of lapis lazuli for provenance study

Lapis lazuli is one of the oldest precious stone, being used for glyptic as early as 7,000 years ago: jewels, amulets, seals, and inlays are examples of objects produced using this material. Only a few sources of lapis lazuli exist in the world due to the low probability of geological conditions in which it can form, so that the possibility to associate the raw material to man-made objects helps to reconstruct trade routes. Since art objects produced using lapis lazuli are valuable, only nondestructive investigations can be carried out to identify the provenance of the raw materials. Ionoluminescence (IL) is a good candidate for this task. Similar to cathodoluminescence (CL), IL consists in the collection of luminescence spectra induced by megaelectronvolt ion (usually protons) irradiation. The main advantage of IL consists in the possibility of working in air while measuring simultaneously the composition of major and trace elements by means of complementary ion beam analysis techniques like particle-induced X-ray emission (PIXE) or particle-induced gamma-ray emission (PIGE). In the present work, a systematic study of the luminescence properties of lapis lazuli under charged particle irradiation is reported. In the first phase, a multitechnique approach was adopted (CL, scanning electron microscopy with microanalysis, micro-Raman) to characterize luminescent minerals. This characterization was propaedeutic for IL/PIXE/PIGE measurements carried out on significant areas selected on the basis of results obtained previously. Criteria to identify provenance of lapis lazuli from four of the main sources (Afghanistan, Pamir Mountains in Tajikistan, Chile, and Siberia) were proposed.     

NADH oxidation on screen-printed electrode modified with a new phenothiazine diazonium salt

NADH oxidation catalysts are extremely important in the field of electrochemical biosensors and enzymatic biofuel cells. Based on the growing diazonium chemistry, we synthesized the diazonium salt of the well-known NADH mediator toluidine blue O. The electrochemical reduction of the diazonium moiety by cyclic voltammetry onto a screen-printed electrode leads to an electrocatalyst suitable for the oxidation of NADH. The amperometric response for its oxidation shows a maximal current of 1.2 μA ([NADH] = 100 μM). Based on electrochemical measurements, the surface coverage is found to be 3.78 × 10^? 11 mol cm^? 2 and the heterogeneous standard rate constant k_h is 1.21 ± 0.16 s^? 1. The sensitive layer for the oxidation of NADH is improved by electrografting the diazonium salt with a potentiostatic method. Both the surface coverage and the heterogeneous standard rate constant k_h are improved and found to be 6.08 ± 0.63 × 10^? 11 mol cm^? 2 and ~ 5.02 s^? 1, respectively. The amperometric response is also improved by an 8 fold factor, reaching 9.87 μA ([NADH] = 120 μM). These remarkably high values for screen-printed electrodes are comparable to glassy carbon electrodes making this method suitable for low-cost bioelectronical devices.     

Influence of the Electrode Material on the Electrochemical Behavior of Carbon Paste Electrodes Modified with Meldola Blue and Methylene Green Adsorbed on a Synthetic Zeolite

Carbon paste electrodes modified with a phenoxazine derivative, Meldola blue, and a phenothiazine derivative, methylene green, both strongly adsorbed on a synthetic zeolite were investigated using either glassy carbon powder (Sigradur K, SK) or single‐walled carbon nanotubes (SWCNT) as conductive electrode material. In the case of SWCNT based electrodes, the formal potential of both mediators was pH dependent, as expected for a redox process involving proton transfer. In contrast, the formal potential of both mediators of SK based modified electrodes was practically insensitive to pH. This behavior is discussed in terms of interactions existing in the heterogeneous system mediator‐zeolite‐electrode material.     

In-situ visualization of a super-accelerated synthesis of zinc oxide nanostructures through CO2 laser heating

A simple growth technique capable of growing a variety of zinc oxide (ZnO) nanostructures with record growth rates of 25 μm/s is demonstrated. Visible lengths of ZnO nanowires, nanotubes, comb-like and pencil-like nanostructures could be grown by employing a focused CO₂ laser-assisted heating of a sintered ZnO rod in ambient air, in few seconds. For the first time, the growth process of nanowires was videographed, in-situ, on an optical microscope. It showed that ZnO was evaporated and presumably decomposed into Zn and oxygen by laser heating, reforming ZnO nanostructures at places with suitable growth temperatures. Analysis on the representative nanowires shows a rectangular cross-section, with a [0 0 0 1] growth direction. With CO₂ laser heating replacing furnace heating used conventionally, and using different reactants and forming gases, this method could be easily adopted for other semiconducting inorganic nanostructures in addition to ZnO.