Design,synthesis, and biological evaluation of 2-benzylpyrroles and 2-benzoylpyrroles based on structures of insecticidal chlorfenapyr and natural pyrrolomycins

Based on structures of insecticidal chlorfenapyr and antibiotic natural pyrrolomycins, a series of new 2-benzylpyrroles and 2-benzoylpyrroles (with or without ethoxymethyl group on the nitrogen of pyrrole) were designed and synthesized. These compounds or their parent compounds possess weak acidity and high lipophilicity, the two characteristic properties for uncouplers of oxidative phosphorylation; therefore, they are expected to have insecticidal and acaricidal activity. The bioassay result verified that both 2-benzylpyrroles 17 and 2-benzoylpyrroles 19 had varied degrees of insecticidal activity against oriental armyworm depending on the substituents on the benzene ring, but they did not give any acaricidal activity. Conversely, most N-alkylated compounds 18 and 20 exhibited both insecticidal activity and acaricidal activity, of which compound 18i [4-bromo-2-(2,4-dichlorobenzyl)-1-(ethoxymethyl) -5-(trifluoromethyl) - 1 \(H\) -pyrrole-3-carbonitrile] has IC \(_{50}\) as low as 10–20 mg L \(^{-1}\) on both activities.     

Effect of Y3+ substitution on the structural,dielectric, and electrical properties of nanosized ZnAl 2 O 4 spinel

In the present work, we have studied the structural, dielectric, and electrical properties of a series of nanosized $\mathrm{ZnAl}_{2-2x}\mathrm{Y}_{2x}\mathrm{O}_{4}$ ( $x = 0.00$ , 0.01, 0.02, 0.03, 0.04, 0.05, 0.07, and 0.10) system prepared by chemical coprecipitation method. Powder X-ray diffraction (XRD) was carried out to study the influence of $\mathrm{Y}^{3+}$ substitution on the crystal structure of these samples. High Resolution Transmission Electron Microscopy (HRTEM) images reveal the nanocrystalline nature of the samples. The Fourier Transform Infrared (FTIR) spectra confirmed the preference of $\mathrm{Y}^{3+}$ ions at the octahedral B site. The variation of dielectric constant and loss tangent (1 kHz to 1 MHz) at room temperature for all the samples show the normal behavior of spinel compounds. AC conductivity study reveals that the conduction is due to small polaron hopping. The electrical modulus analysis shows that nanocrystalline $\mathrm{ZnAl}_{2-2x}\mathrm{Y}_{2x}\mathrm{O}_{4}$ system exhibits non-Debye-type relaxation. The DC electrical resistivity measured in the temperature range 303–373 K was found to increase with temperature and yttrium content.     

Evaluation of the thiazole Schiff bases as \upbeta -glucuronidase inhibitors and their in silico studies

Twenty eight (28) derivatives 2–29 were synthesized and four analogs were found to exhibit single-digit $\hbox {IC}_{50}$ values as $\upbeta $ -glucuronidase inhibitors. Molecular modeling indicates that three factors: substituent R, lone pair on the nitrogen of azomethine part, and the interactions made by the main skeleton of the molecule, determined the enzyme inhibitory potential of these compounds. The planar conformation of the molecules allows them to fit deep inside the pocket while blocking the entry of other physiological substrates seems to play an important role in their activity.     

Quinazoline-2,4(1H,3H)-diones inhibit the growth of multiple human tumor cell lines

Quinazoline-2,4( $1H,3H$ )-diones exhibit a wealth of biological activities including antitumor proliferation. We established an improved method for the synthesis of quinazoline-2,4( $1H,3H$ )-dione derivatives with three points of molecular diversity. Data indicate that compounds 60 (average $\text{ logGI}_{50} \!=\! -6.1$ ), 65 (average $\text{ logGI}_{50} \!=\! -6.13$ ), 69 (average $\text{ logGI}_{50} \!=\! -6.44$ ), 72 (average $\text{ logGI}_{50} \!=\! -6.39$ ), and 86 (average $\text{ logGI}_{50} = -6.45$ ) significantly inhibited the in vitro growth of 60 human tumor cell lines tested. Structure–activity relationship analyses indicate that chlorophenethylureido is the necessary substituent at the $\text{ D}_{3}$ diversity point (7-position of quinazoline-2,4( $1H,3H$ )-dione), in particular, $o$ -chlorophenethylurea (69) achieved optimal activity. $o$ - or $m$ -Chlorophenethyl substitutions (69 and 72) at the $\text{ D}_{2}$ diversity point (3-position of quinazo line-2,4( $1H,3H$ )-dione) gave the most potent compounds. Methoxyl and 4-methylpiperazin-1-yl substitution at the $\text{ D}_{1}$ diversity point (6-position of quinazoline-2,4( $1H,3H$ )-dione skeleton) may yield better activity than other groups. The quinazoline-2,4( $1H,3H$ )-dione scaffold can be effectively replaced by 2 $H$ -benzo[b][1,4]thiazin-3(4 $H$ )-one.     

Structural modification of an EGFR inhibitor that showed weak off-target activity against RET leading to the discovery of a potent RET inhibitor

Here, we describe the structural optimization of a known EGFR inhibitor (compound 1) that showed weak off-target activity against RET. Twenty-six analogs of 1 were synthesized. SAR analysis led to the discovery of several compounds that showed considerable potency against the RET-dependent thyroid cancer cell line TT. Kinase inhibitory potency was then measured for the most active compound (2u) in the cellular assay. The results showed that 2u is a potent RET inhibitor with an $\hbox {IC}_{50}$ value of 7 nM.     

Straightforward synthesis of thiazoline-incorporated chalconoids from phenacyl halides

A series of thiazoline-incorporated chalconoids, designed based on natural product scaffold, were efficiently synthesized via the reaction of 3-methyl-4-arylthiazole-2(3 $H$ )-thiones and appropriate phenacyl halides, and subsequent desulfurization. The starting 3-methyl-4- arylthiazole-2(3 $H$ )-thiones were also prepared from phenacyl halides. The structural aspects and ( $Z$ )-geometry of compounds were confirmed by IR and $^{1}$ H NMR spectral data. This chemistry provides a new library of compounds basically originated from phenacyl halides as building blocks, with potential activity for biomedical screening.     

Pyrid-2-yl and 2-CyanoPhenyl fused heterocyclic compounds as human P2X_{3} inhibitors: a combined approach based on homology modelling,docking and QSAR analysis

P2X receptors are hetero-oligomeric proteins that function as membrane ion channels and are gated by extracellular ATP. The hP2X $_{3}$ subunit is a constituent of the channels on a subset of sensory neurons involved in pain signaling, where ATP released by damaged and inflamed tissue can initiate action potentials. Hence, the inhibition of ATP-activated P2X $_{3}$ receptor is an exciting approach for the treatment of inflammatory and neuropathic pain. Recently, the crystal structures of zebrafish P2X $_{4}$ (zP2X $_{4})$ were obtained in closed, apo state (PDB ID: 3I5D) and ATP-bound, open state (PDB ID: 4DW1). These structures were used to develop a homology model of human P2X $_{3}$ (hP2X $_{3})$ in order to identify through docking studies, the binding modes of known P2X $_{3}$ inhibitors and their key active site interactions, along with a pharmacophore-based 3D-QSAR model for a series of 136 Pyrid-2-yl and 2-CyanoPhenyl fused heterocyclic compounds. These 3D-QSAR models have been developed with different combinations of training and test set divisions obtained by random separation, Jarvis–Patrick clustering, K-means clustering and sphere exclusion methods. The best predictive 3D-QSAR model resulted in training set R $^{2 }$ of 0.75, internal test set Q $^{2}$ of 0.74, Pearson-R value of 0.87 and root mean square error of 0.37. The information generated by the pharmacophore model and docking analyses using the homology model provides valuable clues to design novel potent hP2X $_{3}$ inhibitors.     

Analysis of the \frac{1} {2}^ - and \frac{3} {2}^ - heavy and doubly heavy baryon states with QCD sum rules

In this article, we study the $\frac{1} {2}^ -$ and $\frac{3} {2}^ -$ heavy and doubly heavy baryon states $\Sigma _Q \left( {\frac{1} {2}^ - } \right)$ , $\Xi '_Q \left( {\frac{1} {2}^ - } \right)$ , $\Omega _Q \left( {\frac{1} {2}^ - } \right)$ , $\Xi _{QQ} \left( {\frac{1} {2}^ - } \right)$ , $\Omega _{QQ} \left( {\frac{1} {2}^ - } \right)$ , $\Sigma _Q^* \left( {\frac{3} {2}^ - } \right)$ , $\Xi _Q^* \left( {\frac{3} {2}^ - } \right)$ , $\Omega _Q^* \left( {\frac{3} {2}^ - } \right)$ , $\Xi _{QQ}^* \left( {\frac{3} {2}^ - } \right)$ and $\Omega _{QQ}^* \left( {\frac{3} {2}^ - } \right)$ by subtracting the contributions from the corresponding $\frac{1} {2}^ +$ and $\frac{3} {2}^ +$ heavy and doubly heavy baryon states with the QCD sum rules in a systematic way, and make reasonable predictions for their masses.     

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.     

Terahertz generation by nonlinear mixing of laser and its second harmonic in a rippled density plasma

Terahertz radiation generation by second-order nonlinear mixing of laser $ (\omega_{1} ,\,\vec{k}_{1} ) $ and its frequency shifted second harmonic $ \omega_{2} = 2\omega_{1} - \omega ,\,\,\vec{k}_{2} \, $ $ (\omega \ll \omega_{1} ) $ in a plasma, in the presence of an obliquely inclined density ripple of wave number $ \vec{q} $ , are investigated. The lasers exert ponderomotive force on electrons and drive density perturbations at $ (2\omega_{1} ,\,2\vec{k}_{1} - \vec{q}) $ and $ (\omega_{1} - \omega_{2} ,\,\vec{k}_{1} - \vec{k}_{2} - \vec{q}) $ . These perturbations beat with the electron oscillatory velocities due to the lasers to produce a nonlinear current at $ \omega ,\,\vec{k} = 2\vec{k}_{1} - \vec{k}_{2} - \vec{q} $ , resonantly driving the terahertz radiation when $ \vec{q} $ satisfies the phase matching condition. The radiated THz intensity depends on the relative polarization of the lasers and scales as the square of intensity of the fundamental laser and linearly with the square root of the intensity of the second harmonic. The THz emission is maximized when the polarization of the lasers is aligned. These results are consistent with the recent experimental results.     

Long-time Asymptotic for the Derivative Nonlinear Schrödinger Equation with Step-like Initial Value

We study long-time asymptotics of the solution to the Cauchy problem for the Gerdjikov-Ivanov type derivative nonlinear Schrödinger equation i q t + q xx ? i q 2 q ? x + 1 2 | q | 4 q = 0 $$iq_{t}+q_{xx}-iq^{2}\bar{q}_{x}+\frac{1}{2}|q|^{4}{q}=0 $$ with step-like initial data q ( x , 0 ) = 0 $q(x,0)=0$ for x ≤ 0 $x \leqslant 0$ and q ( x , 0 ) = A e ? 2 iBx $q(x,0)=A\mathrm {e}^{-2iBx}$ for x > 0 $x>0$ , where A > 0 $A>0$ and B ∈ ? $B\in \mathbb R$ are constants. We show that there are three regions in the half-plane { ( x , t ) | ? ∞ < x < ∞ , t > 0 } $\{(x,t) | -\infty <x<\infty , t>0\}$ , on which the asymptotics has qualitatively different forms: a slowly decaying self-similar wave of Zakharov-Manakov type for x > ? 4 tB $x>-4tB$ , a plane wave region: x > ? 4 t B + 2 A 2 B + A 2 4 $x<-4t\left (B+\sqrt {2A^{2}\left (B+\frac {A^{2}}{4}\right )}\right )$ , an elliptic region: ? 4 t B + 2 A 2 B + A 2 4 > x > ? 4 tB $-4t\left (B+\sqrt {2A^{2}\left (B+\frac {A^{2}}{4}\right )}\right )<x<-4tB$ . Our main tools include asymptotic analysis, matrix Riemann-Hilbert problem and Deift-Zhou steepest descent method.     

Structural, morphological and optical properties of \hbox {In}_{2}\hbox {S}_{3} thin films obtained by SILAR method

$\hbox {In}_{2}\hbox {S}_{3}$ thin films have been elaborated onto glass substrate by SILAR method at room temperature using different immersion time in the solution of cation and anion and fixing the rinsing time. The film composition, morphology and structure were investigated using energy dispersive X-ray analysis (EDAX), scanning electron microscopy (SEM) and X-ray diffraction techniques. Optical properties, such transmission and band gap have been also analyzed. The effects of annealing on the morphological structure thin films are also described. The x-rays diffraction spectra indicated that the formed compounds are $\upbeta $ - $\hbox {In}_{2}\hbox {S}_{3}$ polycrystalline thin films with $\hbox {In}_{6}\hbox {S}_{7 }$ as second phase in sample S1 and sample S2 and no another phase in sample 3. SEM revealed homogeneous and relatively uniform films and EDAX shows sample 3 with S/In=1.44. For sample 1 and sample 2, we noted an increase of band gap when rinsing time increases.     

Experimental and theoretical determination of transition dipole moments of ethyl 5-(4-aminophenyl)- and 5-(4-dimethylaminophenyl)-3-amino-2,4-dicyanobenzoate

The absorption and fluorescence transition dipole moments ( $\hat M_{ge}$ and $\hat M_{eg}$ ) for ethyl 5-(4-aminophenyl)-3-amino-2, 4-dicyanobenzoate (EAADCy) and ethyl 5-(4-dimethylaminophenyl)-3-amino-2, 4-dicyanobenzoate (EDMAADCy) have been determined on the basis of the steady-state and time-resolved spectroscopic measurements and semiempirical quantum-chemical calculations. The values of the transition dipole moments of perpendicular and flattened forms of the investigated molecules were estimated as a function of the solvent polarity. Noted differences between the absorption and emission transition dipole moments (i.e., ${{\hat M_{ge} } \mathord{\left/ {\vphantom {{\hat M_{ge} } {\hat M_{eg} }}} \right. \kern-0em} {\hat M_{eg} }} \ne 1$ ) confirm that the change of the electronic and molecular structure take place in the excited state.     

Optical properties of ZnTe doped with transition metals (Ti, Cr and Mn)

The electronic and optical properties of $\text{ Zn }_{1-\mathrm{x}}\text{ M }_\mathrm{x}\text{ Te }$ with (M = Cr, Mn, Ti) have been investigated, within generalized gradient approximation (GGA) using the full potential linear augmented plane wave (FP-LAPW) method as implemented in the WIEN2K code. This work presents detailed information about optical properties like absorbance, refractive index and reflectivity. The result of this study shows that doped ZnTe material with Ti, Cr and Mn shift the absorption spectrum and reflection to the infrared spectral domain or to the ultra violet region, depending on the nature of the dopant. Dielectric functions for different compositional alloys are calculated for 16-atom cubic supercell structure. The calculated band gaps are fitted with a linear equation: ( $\upalpha \text{ h }\upnu )^{2} = \text{ A }(\text{ h }\upnu -\text{ Eg }$ ). For all types of doping the position of critical points (CP’s) $\text{ E }_{0}, \text{ E }_{1}$ and $\text{ E }_{2}$ show good agreement with the experimental data.     

On AB Bond Percolation on the Square Lattice and AB Site Percolation on Its Line Graph

We prove that AB site percolation occurs on the line graph of the square lattice when $p \in (1 - \sqrt {1 - p_c } ,\sqrt {1 - p_c } )$ , where p _c is the critical probability for site percolation in $\mathbb{Z}^2$ . Also, we prove that AB bond percolation does not occur on $\mathbb{Z}^2$ for p = $\frac{1}{2}$ .     

Delocalization and Diffusion Profile for Random Band Matrices

We consider Hermitian and symmetric random band matrices H = (h _xy ) in ${d\,\geqslant\,1}$ d ? 1 dimensions. The matrix entries h _xy , indexed by ${x,y \in (\mathbb{Z}/L\mathbb{Z})^d}$ x , y ∈ ( Z / L Z ) d , are independent, centred random variables with variances ${s_{xy} = \mathbb{E} |h_{xy}|^2}$ s x y = E | h x y | 2 . We assume that s _xy is negligible if |x ? y| exceeds the band width W. In one dimension we prove that the eigenvectors of H are delocalized if ${W\gg L^{4/5}}$ W ? L 4 / 5 . We also show that the magnitude of the matrix entries ${|{G_{xy}}|^2}$ | G x y | 2 of the resolvent ${G=G(z)=(H-z)^{-1}}$ G = G ( z ) = ( H - z ) - 1 is self-averaging and we compute ${\mathbb{E} |{G_{xy}}|^2}$ E | G x y | 2 . We show that, as ${L\to\infty}$ L → ∞ and ${W\gg L^{4/5}}$ W ? L 4 / 5 , the behaviour of ${\mathbb{E} |G_{xy}|^2}$ E | G x y | 2 is governed by a diffusion operator whose diffusion constant we compute. Similar results are obtained in higher dimensions.     

Subfactors of Index Less Than 5, Part 3: Quadruple Points

One major obstacle in extending the classification of small index subfactors beyond ${3 +\sqrt{3}}$ is the appearance of infinite families of candidate principal graphs with 4-valent vertices (in particular, the ??weeds?? ${\mathcal{Q}}$ and ${\mathcal{Q}'}$ from Part 1 (Morrison and Snyder in Commun. Math. Phys., doi:10.1007/s00220-012-1426-y, 2012). Thus instead of using triple point obstructions to eliminate candidate graphs, we need to develop new quadruple point obstructions. In this paper we prove two quadruple point obstructions. The first uses quadratic tangles techniques and eliminates the weed ${\mathcal{Q}'}$ immediately. The second uses connections, and when combined with an additional number theoretic argument it eliminates both weeds ${\mathcal{Q}}$ and ${\mathcal{Q}'}$ . Finally, we prove the uniqueness (up to taking duals) of the 3311 Goodman-de la Harpe-Jones subfactor using a combination of planar algebra techniques and connections.     

Supremum of the Airy2 Process Minus a Parabola on a Half Line

Let $\mathcal {A}_{2}(t)$ be the Airy₂ process. We show that the random variable $$\sup_{t\leq\alpha} \bigl\{\mathcal {A}_2(t)-t^2 \bigr\}+\min\{0,\alpha \}^2 $$ has the same distribution as the one-point marginal of the Airy_2→1 process at time α. These marginals form a family of distributions crossing over from the GUE Tracy-Widom distribution F _GUE(x) for the Gaussian Unitary Ensemble of random matrices, to a rescaled version of the GOE Tracy-Widom distribution F _GOE(4^1/3 x) for the Gaussian Orthogonal Ensemble. Furthermore, we show that for every α the distribution has the same right tail decay $e^{-\frac{4}{3} x^{3/2} }$ .     

Confinement, average forces, and the Ehrenfest theorem for a one-dimensional particle

The topics of confinement, average forces, and the Ehrenfest theorem are examined for a particle in one spatial dimension. Two specific cases are considered: (i) A free particle moving on the entire real line, which is then permanently confined to a line segment or ‘a box’ (this situation is achieved by taking the limit V ₀?→?∞ in a finite well potential). This case is called ‘a particle-in-an-infinite-square-well-potential’. (ii) A free particle that has always been moving inside a box (in this case, an external potential is not necessary to confine the particle, only boundary conditions). This case is called ‘a particle-in-a-box’. After developing some basic results for the problem of a particle in a finite square well potential, the limiting procedure that allows us to obtain the average force of the infinite square well potential from the finite well potential problem is re-examined in detail. A general expression is derived for the mean value of the external classical force operator for a particle-in-an-infinite-square-well-potential, $\hat{F}$ . After calculating similar general expressions for the mean value of the position ( $\hat{X}$ ) and momentum ( $\hat{P}$ ) operators, the Ehrenfest theorem for a particle-in-an-infinite-square-well-potential (i.e., $\mathrm{d}\langle\hat{X}\rangle/\mathrm{d}t=\langle\hat{P}\rangle/M$ and $\mathrm{d}\langle\hat{P}\rangle/\mathrm{d}t=\langle\hat{F}\rangle$ ) is proven. The formal time derivatives of the mean value of the position ( $\hat{x}$ ) and momentum ( $\hat{p}$ ) operators for a particle-in-a-box are re-introduced. It is verified that these derivatives present terms that are evaluated at the ends of the box. Specifically, for the wave functions satisfying the Dirichlet boundary condition, the results, $\mathrm{d}\langle\hat{x}\rangle/\mathrm{d}t=\langle\hat{p}\rangle/M$ and $\mathrm{d}\langle\hat{p}\rangle/\mathrm{d}t=\mathrm{b.t.}+\langle\hat{f}\rangle$ , are obtained where b.t. denotes a boundary term and $\hat{f}$ is the external classical force operator for the particle-in-a-box. Thus, it appears that the expected Ehrenfest theorem is not entirely verified. However, by considering a normalized complex general state that is a combination of energy eigenstates to the Hamiltonian describing a particle-in-a-box with v(x)?=?0 ( $\Rightarrow\hat{f}=0$ ), the result that the b.t. is equal to the mean value of the external classical force operator for the particle-in-an-infinite-square-well-potential is obtained, i.e., $\mathrm{d}\langle\hat{p}\rangle/\mathrm{d}t$ is equal to $\langle\hat{F}\rangle$ . Moreover, the b.t. is written as the mean value of a quantity that is called boundary quantum force, f _B. Thus, the Ehrenfest theorem for a particle-in-a-box can be completed with the formula $\mathrm{d}\langle\hat{p}\rangle/\mathrm{d}t=\langle{{f_\mathrm{B}}}\rangle$ .     

Elliptic Genera of Two-Dimensional {\mathcal{N} = 2} Gauge Theories with Rank-One Gauge Groups

We compute the elliptic genera of two-dimensional ${\mathcal{N} = (2, 2)}$ and ${\mathcal{N} = (0, 2)}$ -gauged linear sigma models via supersymmetric localization, for rank-one gauge groups. The elliptic genus is expressed as a sum over residues of a meromorphic function whose argument is the holonomy of the gauge field along both the spatial and the temporal directions of the torus. We illustrate our formulas by a few examples including the quintic Calabi–Yau, ${\mathcal{N} = (2, 2)}$ SU(2) and O(2) gauge theories coupled to N fundamental chiral multiplets, and a geometric ${\mathcal{N} = (0, 2)}$ model.