The Reaction of Synechocystis Catalase–Peroxidase (KatG) with Isoniazid Investigated by Multifrequency (9–285 GHz) EPR Spectroscopy

Three distinct electron paramagnetic resonance (EPR) spectra of radical intermediates formed as reactive intermediates in the catalytic cycle of Synechocystis catalase–peroxidase were identified. Multifrequency EPR spectroscopy, combined with site-directed mutagenesis and selective deuterium labeling of Trp and Tyr residues, allowed us to unequivocally assign such intermediates to an [Fe(IV) = O Por ^·+] species, the first committed intermediate in monofunctional peroxidases and two protein-based radicals, identified as Trp106 ^· and a Tyr ^· , formed subsequently to the [Fe(IV) = O Por ^·+] species by intramolecular electron transfer. Our recent characterization of the Mycobacterium tuberculosis catalase–peroxidase showed that the Trp ^· sites differ among these enzymes, and that the [Fe(IV) = O Trp ^· ] species was the reactive intermediate with the prodrug isoniazid. Accordingly, the question to address was whether the dissimilarity in the sites for the formation of the Trp ^· intermediates and in the geometry of the distal side was reflected by differences in the peroxidase-like reaction of Synechocystis and Mycobacterium tuberculosis catalase–peroxidases with the prodrug isoniazid. Our findings show that in the Synechocystis enzyme, the isoniazid substrate can get closer to the heme distal side and can react readily with the [Fe(IV) = O Por ^·+] species, at variance to the situation in the M. tuberculosis catalase–peroxidase. These results indicate that, as in the case of monofunctional peroxidases, the difference in the sites for the formation of the Trp ^· as alternative reactive intermediates to the [Fe(IV) = O Por ^·+] species is correlated to differences in substrate binding sites.     

Bis-Benzimidazolyl Diamide Based Fluorescent Probe for Copper(II): Synthesis, Structural and Fluorescence Studies

A new fluorescent probe based on a bis-benzimidazole diamide N ²,N ^2′-bis[(1-ethyl-benzimidazol-2-yl)methyl]biphenyl-2,2′-dicarboxamide ligand L ₁ with a biphenyl spacer group and a Copper(II) trinuclear metallacycle has been synthesized and characterized by X-ray single crystallography, elemental and spectral (FT-IR, ¹H & ¹³C NMR, UV-Visible) analysis. The fluorescence spectra of L ₁ in MeOH show an emission band centered at 300 nm. This band arises due to benzimidazolyl moiety in the ligating system. The diamide L ₁ in the presence of Cu²⁺ show the simultaneous ‘quenching’ of (300 nm) and ‘enhancement’ of (375 nm) emission band. Similar fluorescence behavior was found in water–methanol mixture (9:1). The new emission band at 375 nm is attributed to intra ligand π–π* transition of the biphenyl moiety. L ₁ exhibited high selectivity and sensitivity towards Cu²⁺ in both the medium over other common metal ions like Ni²⁺, Co²⁺, Mn²⁺, Mg²⁺, Zn²⁺, Pb²⁺ and Hg²⁺. The binding constant with Cu²⁺ was calculated by the Benesi-Hildebrand equation. Selective “off-on-off” behavior of L ₁ in methanol has also been studied. The fluorescent intensity of 375 nm bands in L ₁ enhances (turns-on) upon addition of Cu²⁺ and quenches (turn-off) upon addition of Na₂-EDTA.     

New spiro[benzotetraphene-fluorene] Derivatives: Synthesis and Application in Sky-Blue Fluorescent Host Materials

Blue light-emitting spiro[benzotetraphene-fluorene] (SBTF)-based host materials, 3-(1-naphthyl)-10-naphthylspiro[benzo[ij]tetraphene-7,9′-fluorene] (1), 3-(2-naphthyl)-10-naphthylspiro[benzo[ij]tetraphene-7,9′-fluorene] (2), and 3-[2-(6-phenyl)naphthyl]-10-naphthylspiro[benzo[ij]tetraphene-7,9′-fluorene] (3) were designed and prepared via multi-step Suzuki coupling reactions. Introducing various aromatic groups into SBTF core lead to a reduction in band gap and a determination of the color purity and luminescence efficiency. Typical sky-blue fluorescent organic light emitting diodes with the configuration of ITO/N,N′-di(1-naphthyl)-N,N′-bis[(4-diphenylamino)phenyl]-biphenyl-4,4′-diamie (60 nm)/N,N,N′,N′-tetra(1-biphenyl)-biphenyl-4,4′-diamine (30 nm)/host: dopant (30 nm, 5 %)/LG201 (electron transporting layer, 20 nm)/LiF/Al were developed using SBTF derivatives as a host material and p-bis(p-N,N-diphenyl-aminostyryl)benzene (DSA-Ph) as a sky-blue dopant material. A device obtained from three materials doped with DSA-Ph showed color purity of 0.148 and 0.239, a luminance efficiency of 7.91 cd/A, and an external quantum efficiency >4.75 % at 5 V.     

Fast calculation of HELAS amplitudes using graphics processing unit (GPU)

We use the graphics processing unit (GPU) for fast calculations of helicity amplitudes of physics processes. As our first attempt, we compute $u\overline{u}\rightarrow n\gamma$ (n=2 to 8) processes in pp collisions at $\sqrt{s}=14$  TeV by transferring the MadGraph generated HELAS amplitudes (FORTRAN) into newly developed HEGET (HELAS Evaluation with GPU Enhanced Technology) codes written in CUDA, a C-platform developed by NVIDIA for general purpose computing on the GPU. Compared with the usual CPU programs, we obtain a 40–150 times better performance on the GPU.     

Influence of the degenerate d level and of the Jahn-Teller effect on the manganite electronic structure calculated in the tight-binding approximation

E(k) dispersion curves for the charge carriers in the LaMnO₃-like perovskites were calculated for the basic types of canted antiferromagnetic ordering of the Mn sublattice in the framework of the tight-binding approximation. The E(k) spectrum of the antiferromagnetic structures was calculated for the first time taking into account the degeneracy of the Mn e _g level and the Jahn-Teller distortion of the cubic perovskite structure. This calculation involved diagonalization of the 8×8 Hamiltonian matrix. Analytical expressions for the E(k) function at separate points and symmetry lines of the Brillouin zone were derived. The calculations showed that the properties of the La_1?x Ca_xMnO₃ system do not have electron-hole symmetry.     

Discovering Echinococcus granulosus thioredoxin glutathione reductase inhibitors through site-specific dynamic combinatorial chemistry

In this study, we report a strategy using dynamic combinatorial chemistry for targeting the thioredoxin (Trx)-reductase catalytic site on Trx glutathione reductase (TGR), a pyridine nucleotide thiol-disulfide oxido-reductase. We chose Echinococcus granulosus TGR since it is a bottleneck enzyme of platyhelminth parasites and a validated pharmacological target. A dynamic combinatorial library (DCL) was constructed based on thiol-disulfide reversible exchange. We demonstrate the use of 5-thio-2-nitrobenzoic acid (TNB) as a non-covalent anchor fragment in a DCL templated by E. granulosus TGR. The heterodimer of TNB and bisthiazolidine (2af) was identified, upon library analysis by HPLC (IC $_{50}$  = 24  $\upmu $ M). Furthermore, 14 analogs were synthetically prepared and evaluated against TGR. This allowed the study of a structure–activity relationship and the identification of a disulfide TNB-tricyclic bisthiazolidine (2aj) as the best enzyme inhibitor in these series, with an IC $_{50}$  = 14  $\upmu $ M. Thus, our results validate the use of DCL for targeting thiol-disulfide oxido-reductases.     

Analytic Binding Energies for Two-Baryon Bound States in 2 + 1 Strongly Coupled Lattice QCD With Two-Flavors

We consider a lattice SU(3) QCD model in 2 + 1 dimensions, with two flavors and 2 × 2 spin matrices. An imaginary time functional integral formulation with Wilson’s action is used in the strong coupling regime, i.e. small hopping parameter ${0 < \kappa \ll 1}$ , and much smaller plaquette coupling ${\beta, 0 < \beta \ll \kappa}$ . In this regime, it is known that the low-lying energy-momentum spectrum contains isolated dispersion curves identified with baryons and mesons with asymptotic masses ${m\approx-3\ln\kappa}$ and ${m_m\approx-2\ln\kappa}$ , respectively. We prove the existence of two (labelled by ±) two-baryon bound states for each of the total isospin sectors I = 0,1 and we obtain, in each case, the exact binding energies ${\epsilon_{I\,\pm} }$ (of order ${\kappa^2}$ ) which extend to jointly analytic function in ${\kappa}$ and β. We also prove that these points are the only mass spectrum up to slightly above the bound state masses. Precisely, we show, for ${\alpha_0=\frac 14, \alpha_1=\frac 1{12}, \alpha_2=\frac12, \alpha_3=\frac 34}$ and small ${\delta >0 }$ , that the bound state masses ${2m-\epsilon_{I\,\pm}}$ are the only points in the mass spectrum in ${(0,2m-\epsilon_{I\,\pm}+\delta \alpha_I\kappa^2)}$ , for I = 0,1, and in ${(0,2m-(1+\delta)\alpha_I\kappa^2)}$ , for I = 2,3. These results are exact and validate our previous results obtained in a ladder approximation. The method employs suitable two- and four-point correlations with spectral representations and a lattice Bethe-Salpeter equation. For I = 0,1, a quark, antiquark space-range one potential of order ${\kappa^2}$ is found to be the dominant contribution to the two-baryon interaction and the interaction of the individual quark isospins of one baryon with those of the other is described by permanents. A novel spectral free decomposition (but spectral representation motivated, for real κ and β) of the two-point correlation, after performing a complex extension, is a key ingredient in showing the joint analyticity of the binding energy.     

Ni(II) and Zn(II) Complexes Containing Alkynyl Functionalized Salicylaldimine Ligand and Heterocyclic Coligand: Synthesis,Characterization and Luminescence Properties

Some nickel(II) and zinc(II) complexes of the type [Ni(L)(phen/bipy)]X (1a–6a) and [Zn(L) (phen/bipy)]X (1b–6b) (where L = 2-{(E)-[(4-trimethylsilylethynylphenyl)imino]methyl}-4-(4-nitro phenylethynyl)phenol; phen = 1, 10-phenanthroline, bipy = 2, 2´-bipyridine; X = ClO₄ ^?, BF₄ ^?, PF₆ ^?) have been prepared and characterized on the basis of elemental analyses, FTIR, ¹H NMR and mass spectral studies. The molecular structure of L was determined by single crystal X-ray diffraction studies. The electrochemical behaviour of the Ni(II) complexes indicate that the phen complexes appears at more positive potential as compared to those for bipy complexes, as a consequence of its strong π-acidic character. TGA was carried out to study the thermal behavior of the complexes. Room temperature luminescence is observed for all complexes corresponds to π → π* ILCT transition. The size of the counter anion and heterocyclic coligands phen and bipy shows marked effect on emission properties of the complexes.     

Study on spin configuration in photoresponsive iron mixed-valence complexes by Mössbauer spectroscopy

We have investigated magnetic properties in a series of photoresponsive dithiooxalato (dto)-bridged iron mixed-valence complexes, (SP-R)[Fe^IIFe^III(dto)₃] (SP-R = R-substituted pyridospiropyran cation; R = Me, Et, and Pr; abbreviated as 1 ^Me, 1 ^Et, and 1 ^Pr, respectively). As for our previous reports, 1 ^Me and 1 ^Et show two-step succeeding ferromagnetic transitions at T _C?=?25 & 8 K and 22 & 5 K, respectively. However, 1 ^Et has no hysteresis in the magnetic susceptibility, while 1 ^Me undergoes the charge transfer phase transition with thermal hysteresis around 75 K. To elucidate the two-step transitions of them, we measured ⁵⁷Fe Mössbauer spectra of 1 ^Et. The spectra of Fe^II (S?=?2) and Fe^III (S?=?1/2) in the HTP were observed in the magnetically ordered state as well as the paramagnetic state, and revealed that only HTP exists in a temperature range up to 5 K. The result is consistent with that of 1 ^Pr, where one ferromagnetic phase transition occurs at T _C?=?10 K. ⁵⁷Fe Mössbauer spectroscopy is useful to clarify the origin of the succeeding magnetic transition for these systems.     

Hyperfine structure investigations of some odd levels of Co I by level crossing and optical methods

Using the level crossing technique the ratios and absolute values of the hyperfine structure (hfs) constants of the levelsz ⁴F_9/2 andz ⁴F_7/2 of the configuration 3d ⁷4s4p of Co I were measured:z ⁴ F _9/2: ¦A¦=(811±12)MHz; ¦B¦=(48±93) MHz;B/A=?0.06±0.11 A>0; B<0z ⁴ F _7/2: ¦A¦ = (659 ±11)MHz; ¦B¦=(33±84)MHz;B/A=?0.05±0.13 A>0; B<0. In addition the hfs constants of three other excited levels of Co I could be determined by optical methods:z ⁴ F _9/2:A=525±26 MHz;B=200 MHzy ⁴ F _9/2:A=300±30 MHz;B=?500 MHzy ⁴ G _11/2:A=315±20 MHz;B=400 MHz. The experimental results are compared with known experimental and also with theoretical values which where calculated using the parametric potential method.     

Nuclear magnetic resonance in noncollinear antiferromagnet Mn3Al2Ge3O12

The ⁵⁵Mn nuclear magnetic resonance spectrum of noncollinear 12-sublattice antiferromagnet Mn₃Al₂Ge₃O₁₂ has been studied in the frequency range of 200–640 MHz in the external magnetic field H ‖ [001] at T = 1.2 K. Three absorption lines have been observed in fields less than the field of the reorientation transition H _c at the polarization h ‖ H of the rf field. Two lines have been observed at H > H _c and h ⊥ H. The spectral parameters indicate that the magnetic structure of manganese garnet differs slightly from the exchange triangular 120-degree structure. The anisotropy of the spin reduction and (or) weak antiferromagnetism that are allowed by the crystal symmetry lead to the difference of ≈3% in the magnetization of sublattices in the field H < H _c. When the spin plane rotates from the orientation perpendicular to the C ₃ axis to the orientation perpendicular to the C ₄ axis, all magnetic moments of the electronic subsystem decrease by ≈2% from the average value in the zero field.     

Heat Trace and Spectral Action on the Standard Podleś Sphere

We give a new definition of dimension spectrum for non-regular spectral triples and compute the exact (i.e., not only the asymptotics) heat-trace of standard Podle? spheres \({S^2_q}\) for 0 < q < 1, study its behaviour when \({q\to 1}\) , and fully compute its exact spectral action for an explicit class of cut-off functions.     

The influence of disorder on magnetocaloric effect and the order of transition in ferromagnetic manganite (La1−x Nd x )2/3(Ca1−y Sr y )1/3MnO3

Magnetocaloric effect and order of transition in (La_1?x Nd _x )_2/3(Ca_1?y Sr _y )_1/3MnO₃, prepared by conventional solid-state reaction, have been investigated. Using Banerjee criterion, we demonstrate first-order transition for (J1) and (J2 ) as well as second-order transition for (J3 ), (J4 ), and (J5 ) samples. The ΔS _M ^max is ranging between 9.18 Jkg^?1 K^?1 and 4.87 when Nd and Sr content changes leading to relative cooling power (RCP) varying between 330 and 229.35 J/kg. Both ΔS _M ^max and the RCP are found sensitive to the disorder σ ². The universal behavior obtained from ΔS variation curves confirmed the first-order transition for (J1) and (J2 ) samples and second-order transition for (J3), (J4), and (J5 ) samples obtained by Banerjee criterion. All samples with second-order phase transition exhibit inhomogeneous character estimated from local exponent n.     

EPR,the X-ray Structure and DFT Calculations of the Nitroxide Biradical with One Acetylene Group in the Bridge

Two short nitroxide biradicals of similar composition, R6′–R6′ (B0) and R6′–(C ≡ C)–R6′ (B1), where R6′ is 1-oxyl-2,2,6,6-tetramethyl-3,4-ene-nitroxide ring, have been investigated by electron paramagnetic resonance spectroscopy and X-ray structural analysis. Quantum chemical calculations at UDFT/B3LYP/cc-pVDZ level were also performed and compared with the X-ray structural data. Zero-field splitting parameters D for B0 and B1 were found to be equal ?0.0048 and ?0.0022 cm^?1, respectively, in good agreement with quantum chemical prediction. Potential energy surface scans corresponding to pathways of the conformational rearrangements were calculated; rotation barriers for B0 and B1 were found to be 19.2 and 4.0 kJ/mol, respectively; and structural rigidity and probable differences in biradicals behavior are discussed. Calculations of spin density distribution in biradicals B0 and B1 were also carried out.     

A Real Quaternion Spherical Ensemble of Random Matrices

One can identify a tripartite classification of random matrix ensembles into geometrical universality classes corresponding to the plane, the sphere and the anti-sphere. The plane is identified with Ginibre-type (iid) matrices and the anti-sphere with truncations of unitary matrices. This paper focusses on an ensemble corresponding to the sphere: matrices of the form Y=A ^?1 B, where A and B are independent N×N matrices with iid standard Gaussian real quaternion entries. By applying techniques similar to those used for the analogous complex and real spherical ensembles, the eigenvalue joint probability density function and correlation functions are calculated. This completes the exploration of spherical matrices using the traditional Dyson indices β=1,2,4. We find that the eigenvalue density (after stereographic projection onto the sphere) has a depletion of eigenvalues along a ring corresponding to the real axis, with reflective symmetry about this ring. However, in the limit of large matrix dimension, this eigenvalue density approaches that of the corresponding complex ensemble, a density which is uniform on the sphere. This result is in keeping with the spherical law (analogous to the circular law for iid matrices), which states that for matrices having the spherical structure Y=A ^?1 B, where A and B are independent, iid matrices the (stereographically projected) eigenvalue density tends to uniformity on the sphere.     

The discovery of 3-(1-aminoethylidene)quinoline-2, 4(1H,3H)-dione derivatives as novel PSII electron transport inhibitors

Based on the structures of the 4-hydroxyphenylpyruvate dioxygenase inhibitor mesotrione and natural product fischerellin A, a series of imine derivatives of ( $E$ )-3-acyl-quinoline-2,4(1H,3H)-dione (6, 12 and 16) were designed, synthesized and systematically evaluated for their herbicidal activity. The bioassay results indicated that most of the synthesized compounds displayed good to excellent herbicidal activity, of which 6e, 6g, 6h, 6q and 6t exhibited more than 50 % inhibition against Brassica napus L., Amaranthus retroflexu or Digitaria adscendens at a dosage of $94\,\hbox {g}\,\hbox {ha}^{-1}$ or lower. The symptom of injured leaves in vivo, the high Hill reaction inhibitory activity of 6h in vitro ( $\hbox {IC}_{50}\,0.1\, \upmu \hbox {g}\,\hbox {mL}^{-1})$ and the computer-based binding model of compound 6h with D1 protein in photosystem II (PSII) reaction centre suggest this novel structure to likely be a new type of PSII electron transport inhibitor. Thus, we have found a novel type of diketone enamine structure targeted at the PSII reaction centre.     

Experimental determination of the scattering length for positron scattering from krypton

We report the first experimentally supported determination of the scattering length for positron scattering from krypton. Our result of  ?10.3 ± 1.5 a.u. compares favourably with that from a convergent close coupling calculation performed as a part of this investigation (?9.5 a.u.), and also with an earlier many body theory calculation of  ?10.1 a.u. from Gribakin and Ludlow [Phys. Rev. A 70, 032720 (2004)] and a polarized-orbital result of  ?10.4 a.u. from McEachran et al. [J. Phys. B 13, 1281 (1980)]. The present experimental scattering length supports the existence of a low-lying positron-krypton virtual state (Surko et al. [J. Phys. B 38, R57 (2005)]) at an energy ε = 0.13 eV.     

Efimov Spectrum in Bosonic Systems with Increasing Number of Particles

It is well-known that three-boson systems show the Efimov effect when the two-body scattering length a is large with respect to the range of the two-body interaction. This effect is a manifestation of a discrete scaling invariance (DSI). In this work we study DSI in the N-body system by analysing the spectrum of N identical bosons obtained with a pairwise gaussian interaction close to the unitary limit. We consider different universal ratios such as \({E_N^0/E_3^0}\) and \({E_N^1/E_N^0}\) , with \({E_N^i}\) being the energy of the ground (i = 0) and first-excited (i = 1) state of the system, for \({N \leq16}\) . We discuss the extension of the Efimov radial law, derived by Efimov for N = 3, to general N.     

A Phenylbenzothiazole Derived Fluorescent Sensor for Zn(II) Recognition in Aqueous Solution Through “Turn-On” Excited-State Intramolecular Proton Transfer Emission

A highly selective and sensitive fluorescent Zn²⁺ sensor N-(2-(benzo[d]thiazol-2-yl)phenyl)-2-((pyridin-2-ylmethyl)amino)acetamide (1) that derived from 2-(2′-aminophenyl)benzothiazole has been developed. In aqueous solution (HEPES/CH₃CN=4/6, v/v, HEPES 20 mM, pH?=?7.4), sensor 1 displays highly selective recognition to Zn²⁺ over other metal ions with a distinct longer-wavelength emission enhancement. Sensor 1 binds Zn²⁺ through its amide form with a 1:1 binding stoichiometry, which switched on the excited-state intramolecular proton transfer (ESIPT). Graphical Abstract

A simple 2-(2′-aminophenyl)benzothiazole-based fluorescent “off-on” sensor for Zn²⁺ recognition in HEPES/CH₃CN(4/6, v/v, HEPES 20 mM, pH?=?7.4) solution through switching on ESIPT has been developed.     

Fluorescence Turn on Sensor for Sulfate Ion in Aqueous Medium Using Tripodal-Cu2+ Ensemble

We report the selective recognition of sulfate anion in aqueous medium at biological pH 7.2 over the other interfering anions based on naphthoic acid bearing tripodal ligand by applying fluorescence turn off-on mechanism. The carboxylic acid groups in the ligand enhance the solubility in water and enable it to form complex with copper salt. Thus formed L-Cu²⁺ ensemble quench the fluorescence of the parent ligand and in turn recognize sulfate anion via revival of fluorescence intensity. The 1:2 stoichiometry was confirmed by ESI mass spectral data and Job’s plot. The average binding constant was found to be 6.2?×?10⁸ M^?2.