Investigation of the stability of polyelectrolyte multilayer coatings in open-tubular capillary electrochromatography using laser scanning confocal microscopy

A simple polyelectrolyte multilayer (PEM) coating procedure was used for the development of stable modified capillaries. PEM coatings were constructed in fused-silica capillaries using alternating rinses of cationic and anionic polyelectrolytes. The multilayer coatings investigated in this study consisted of two and twenty layer pairs, or bilayers. A bilayer is one layer of a cationic polymer and one layer of an anionic polymer. Poly(diallyldimethylammonium chloride) was used as the cationic polymer, and the polymeric surfactant poly(sodium N-undecanoyl-L-leucylvalinate) was used as the anionic polymer. Previous studies for both chiral and achiral separations have shown that PEM-coated capillaries have excellent reproducibilities, remarkable endurance, and strong stabilities against extreme pH values when used in open-tubular capillary electrochromatography (OT-CEC). In this study, the stability of the coatings was further investigated after exposure to 0.1 M and 1.0 M NaOH. Structural changes of these coatings were monitored using laser scanning confocal microscopy (LSCM) after flushing the capillaries with NaOH. This technique allowed observation of the degradation of the coatings. Observations are discussed in terms of separations using OT-CEC. Electropherograms obtained from the chiral separation of 1,1'-binaphthyl-2,2'-dihydrogenphosphate in OT-CEC showed a decrease in selectivity and an increase in electroosmotic mobility after long exposure to NaOH. The ability to recover the capillaries by exposure to NaOH was also demonstrated. Measurements of electroosmotic mobility and selectivity showed that 2-bilayer and 20-bilayer PEM coatings could be completely removed from the capillary surface after approximately 3.5 and 9.5 h, respectively, of continuous exposure to 1 M NaOH.     

Infrared focal plane array with a built-in stationary Fourier-transform spectrometer: basic concepts

A novel configuration of stationary Fourier transform infrared (FTIR) spectrometer is presented. Contrary to classic configurations, the interferometer is directly integrated in the focal plane array (FPA) during its process of fabrication. A first, to the best of our knowledge, demonstration of the spectrometric function has been achieved departing from a well-known structure of an HgCdTe photodetector. We show that the obtained FTIR-FPA can be described by intrinsic parameters such as an optical path difference and a so-called spectrometric efficiency. First experimental results are presented.     

Nonvanishing of Hecke <Emphasis Type=Italic>L</Emphasis>-functions and the Bloch–Kato conjecture

In this paper we study the central values of L-functions associated to a large class of algebraic Hecke characters of imaginary quadratic fields. When these central values are nonzero, the Bloch–Kato conjecture predicts an exact formula for the algebraic parts of the central values in terms of periods and arithmetic data, most notably the Selmer groups corresponding to the Hecke characters. We investigate the nonvanishing of these central values, and prove the p-part of the Bloch–Kato conjecture in these cases for primes p which split in K.     

Fluorinated Rings: Conformation and Application

The introduction of fluorine atoms into molecules and materials across many fields of academic and industrial research is now commonplace, owing to their unique properties. A particularly interesting feature is the impact of fluorine substitution on the relative orientation of a C−F bond when incorporated into organic molecules. In this Review, we will be discussing the conformational behavior of fluorinated aliphatic carbo- and heterocyclic systems. The conformational preference of each system is associated with various interactions introduced by fluorine substitution such as charge-dipole, dipole-dipole, and hyperconjugative interactions. The contribution of each interaction on the stabilization of the fluorinated alicyclic system, which manifests itself in low conformations, will be discussed in detail. The novelty of this feature will be demonstrated by presenting the most recent applications.     

Functionalization of the methylene groups of p-tert-butylcalix[4]arene: S-C,N-C,and C-C bond formation

Reaction of the calixarene derivative 7 with two exocyclic double bonds with carbon-, nitrogen-, oxygen-, or sulfur-containing nucleophiles afforded bis(spirodienone) derivatives substituted at two opposite methylene groups in a trans fashion. LiAlH(4) reduction of the bis(spirodienone) derivatives with two methylenes functionalized by thiomethoxy, diethyl malonate, or anilino substituents yielded trans methylene-substituted calix[4]arenes. Upon standing in solution, the calixarene derivative incorporating SMe groups on the bridges underwent trans right harpoon over left harpoon cis isomerization. An equilibration study performed on this calixarene derivative (tetrachloroethane-d(2), 430 K) indicated that the cis isomer is the form of lower free energy.     

Theoretical and experimental investigations of easy made fishnet metamaterials at microwave frequencies

In this work, we demonstrate theoretically and experimentally a left handed behaviour of a planar fishnet type metamaterial in the microwave regime. The fabrication procedure based on printed circuit board technology and mechanical micromachining technique is easy, unique and doesn’t involve optical lithography. The effective parameters have been extracted using the S parameter retrieval method and show a very good agreement between simulation and experiment. Using finite-element method based simulations and W-band (75 GHz–110 GHz) experiments. We measured a negative index of refraction of −4 at 85 GHz. The demonstrated left handed materials represent a step towards the easy fabrication of metamaterials with a negative refractive index that open a new path for the active manipulation of millimetre wavelengths.     

PARP Theranostic Auger Emitters Are Cytotoxic in BRCA Mutant Ovarian Cancer and Viable Tumors from Ovarian Cancer Patients Enable Ex-Vivo Screening of Tumor Response

Theranostics are emerging as a pillar of cancer therapy that enable the use of single molecule constructs for diagnostic and therapeutic application. As poly adenosine diphosphate (ADP)-ribose polymerase 1 (PARP-1) is overexpressed in various cancer types, and is localized to the nucleus, PARP-1 can be safely targeted with Auger emitters to induce DNA damage in tumors. Here, we investigated a radioiodinated PARP inhibitor, [¹²⁵I]KX1, and show drug target specific DNA damage and subsequent killing of BRCA1 and non-BRCA mutant ovarian cancer cells at sub-pharmacological concentrations several orders of magnitude lower than traditional PARP inhibitors. Furthermore, we demonstrated that viable tumor tissue from ovarian cancer patients can be used to screen tumor radiosensitivity ex-vivo, enabling the direct assessment of therapeutic efficacy. Finally, we showed tumors can be imaged by single-photon computed tomography (SPECT) with PARP theranostic, [¹²³I]KX1, in a human ovarian cancer xenograft mouse model. These data support the utility of PARP-1 targeted radiopharmaceutical therapy as a theranostic option for PARP-1 overexpressing ovarian cancers.     

New Synthesis of Substituted Difuryl or Dithienyl Methanes

New trisubstituted methanes derivatives are quantitatively and selectively obtained by condensation of 2-methylfuran or 2-methylthiophene with diverse aldehydes using macroporous ion-exchange resins as catalyst. Hydration rate of organic phase and sulfonic sites of catalyst determines a proper reaction progress.     

Vectorial Form of the Successive Lorentz Transformations. Application: Thomas Rotation

A complete treatment of the Thomas rotation involves algebraic manipulations of overwhelming complexity. In this paper, we show that a choice of convenient vectorial forms for the relativistic addition law of velocities and the successive Lorentz transformations allows us to obtain straightforwardly the Thomas rotation angle by three new methods: (a) direct computation as the angle between the composite vectors of the non-collinear velocities, (b) vectorial approach, and (c) matrix approach. The new expression of the Thomas rotation angle permits us to simply obtain the Thomas precession. Original diagrams are given for the first time.