Studies on thermal,spectral, magnetic and biological properties of new Ni(II), Cu(II) and Zn(II) complexes with a bismacrocyclic ligand bearing an aromatic linker

Novel complexes of M₂LCl₄·nH₂O type (M:Ni, n = 4; M:Cu, n = 3 and M:Zn, n = 0; L: ligand resulted from 1,4-phenylenediamine, 3,6-diazaoctane-1,8-diamine and formaldehyde one-pot condensation) were synthesized and characterised by microanalytical, ESI–MS, IR, UV–Vis, ¹H NMR and EPR spectra, magnetic data at room temperature and molar conductivities as well. The electrochemical behaviour of complexes was investigated by cyclic voltammetry. Simultaneous TG/DTA measurements were performed in order to evidence the thermal behaviour of the obtained complexes. Processes such as water elimination, fragmentation and oxidative degradation of the organic ligand as well as chloride elimination occurred during thermal decomposition. The antimicrobial assays demonstrate that the compounds exhibited good antibacterial activity, especially against S. aureus and E. coli strains, the most active being the copper(II) complex, which also exhibited the most prominent anti-biofilm effect, suggesting its potential use for the development of new antimicrobial agents. The biological activity was correlated with log P _ow values. All complexes disrupt the membrane integrity of HCT 8 tumour cells.     

Thermal behaviour of some novel antimicrobials based on complexes with a Schiff base bearing 1,2,4-triazole pharmacophore

A series of complexes of type [ML(CH₃COO)(OH₂)₂] (M: Co, Ni; HL: 2-[(E)-1H-1,2,4-triazol-3-ylimino)methyl]phenol)) and [M₂L₂(CH₃COO)₂(OH₂)_n] (M: Cu, n = 2; M: Zn, n = 0) were synthesised by template condensation. The compounds were characterised with microanalytical, ESI–MS, IR, electronic, EPR spectra and magnetic data at room temperature. Based on the IR and ESI–MS spectra, a dinuclear structure with the acetate as bridge was proposed for Cu(II) and Zn(II) complexes. The dinuclear structure of Cu(II) complex is also consistent with both magnetic behaviour and EPR spectrum. The thermal analyses have evidenced processes as water elimination, acetate decomposition, as well as oxidative degradation of the Schiff base. The final decomposition product was the most stable metal oxide as indicated by powder X-ray diffraction. The cobalt and copper compounds exhibited a broad spectrum of antibacterial activity towards both planktonic and biofilm-embedded cells. The complexes exhibit a low cytotoxicity except for Cu(II) species that induces the early apoptosis for the HEp 2 cells.     

On the complexity of finding first-order critical points in constrained nonlinear optimization

The complexity of finding $\epsilon $ -approximate first-order critical points for the general smooth constrained optimization problem is shown to be no worse that $O(\epsilon ^{-2})$ in terms of function and constraints evaluations. This result is obtained by analyzing the worst-case behaviour of a first-order short-step homotopy algorithm consisting of a feasibility phase followed by an optimization phase, and requires minimal assumptions on the objective function. Since a bound of the same order is known to be valid for the unconstrained case, this leads to the conclusion that the presence of possibly nonlinear/nonconvex inequality/equality constraints is irrelevant for this bound to apply.     

Scalable subspace methods for derivative-free nonlinear least-squares optimization

Mathematical Programming - We introduce a general framework for large-scale model-based derivative-free optimization based on iterative minimization within random subspaces. We present a...     

Adaptive cubic regularisation methods for unconstrained optimization. Part I: motivation,convergence and numerical results

An Adaptive Regularisation algorithm using Cubics (ARC) is proposed for unconstrained optimization, generalizing at the same time an unpublished method due to Griewank (Technical Report NA/12, 1981, DAMTP, University of Cambridge), an algorithm by Nesterov and Polyak (Math Program 108(1):177–205, 2006) and a proposal by Weiser et al. (Optim Methods Softw 22(3):413–431, 2007). At each iteration of our approach, an approximate global minimizer of a local cubic regularisation of the objective function is determined, and this ensures a significant improvement in the objective so long as the Hessian of the objective is locally Lipschitz continuous. The new method uses an adaptive estimation of the local Lipschitz constant and approximations to the global model-minimizer which remain computationally-viable even for large-scale problems. We show that the excellent global and local convergence properties obtained by Nesterov and Polyak are retained, and sometimes extended to a wider class of problems, by our ARC approach. Preliminary numerical experiments with small-scale test problems from the CUTEr set show encouraging performance of the ARC algorithm when compared to a basic trust-region implementation.     

Second-Order Optimality and Beyond: Characterization and Evaluation Complexity in Convexly Constrained Nonlinear Optimization

High-order optimality conditions for convexly constrained nonlinear optimization problems are analysed. A corresponding (expensive) measure of criticality for arbitrary order is proposed and extended to define high-order \(\epsilon \)-approximate critical points. This new measure is then used within a conceptual trust-region algorithm to show that if derivatives of the objective function up to order \(q \ge 1\) can be evaluated and are Lipschitz continuous, then this algorithm applied to the convexly constrained problem needs at most \(O(\epsilon ^{-(q+1)})\) evaluations of f and its derivatives to compute an \(\epsilon \)-approximate qth-order critical point. This provides the first evaluation complexity result for critical points of arbitrary order in nonlinear optimization. An example is discussed, showing that the obtained evaluation complexity bounds are essentially sharp.     

Thermal,spectral and biological characterisation of copper(II) complexes with isoniazid-based hydrazones

Journal of Thermal Analysis and Calorimetry - A series of complexes [Cu(L)(CH3COO)2]·nH2O (L: isonicotinic acid 2-(2-hydroxy-8-substituted-tricyclo[7.3.1.02.7]tridec-13-ylidene)-hydrazones)...     

Spectral,thermal and biological characterization of complexes with a Schiff base bearing triazole moiety as potential antimicrobial species

Journal of Thermal Analysis and Calorimetry - A novel series of complexes ML(ClO4)·nH2O (M: Co, Ni, Cu, Zn; HL: 2-[(E)-(1H-1,2,4-triazol-3-ylimino)methyl]phenol) have been synthesized and...     

Synthesis,thermal, spectral,antimicrobial and cytotoxicity profile of the Schiff bases bearing pyrazolone moiety and their Cu(II) complexes

Journal of Thermal Analysis and Calorimetry - A series of Schiff bases resulted in the [1?+?1] condensation of 8-alkyl-2-hydroxy-tricyclo[7.3.1.02.7]-tridecan-13-one with the...