Manipulation of gold nanoparticles: influence of surface chemistry, temperature, and environment (vacuum versus ambient atmosphere)

We have manipulated raw and functionalized gold nanoparticles (with a mean diameter of 25 nm) on silicon substrates with dynamic atomic force microscopy (AFM). Under ambient conditions, the particles stick to silicon until a critical amplitude is reached by the oscillations of the probing tip. Beyond that threshold, the particles start to follow different directions, depending on their geometry and adhesion to the substrate. Higher and lower mobility were observed when the gold particles were coated with methyl- and hydroxyl-terminated thiol groups, respectively, which suggests that the adhesion of the particles to the substrate is strongly reduced by the presence of hydrophobic interfaces. Under ultrahigh vacuum conditions, where the water layer is absent, the particles did not move, even when operating the atomic force microscope in contact mode. We have also investigated the influence of the temperature (up to 150 degrees C) and of the geometrical arrangement of the particles on the manipulation process. Whereas thermal activation has an important effect in enhancing the mobility of the particles, we did not find differences when manipulating ordered versus random distributions of particles.     

A programmable microfluidic cell array for combinatorial drug screening

We describe the development of a fully automatic and programmable microfluidic cell culture array that integrates on-chip generation of drug concentrations and pair-wise combinations with parallel culture of cells for drug candidate screening applications. The device has 64 individually addressable cell culture chambers in which cells can be cultured and exposed either sequentially or simultaneously to 64 pair-wise concentration combinations of two drugs. For sequential exposure, a simple microfluidic diffusive mixer is used to generate different concentrations of drugs from two inputs. For generation of 64 pair-wise combinations from two drug inputs, a novel time dependent variable concentration scheme is used in conjunction with the simple diffusive mixer to generate the desired combinations without the need for complex multi-layer structures or continuous medium perfusion. The generation of drug combinations and exposure to specific cell culture chambers are controlled using a LabVIEW interface capable of automatically running a multi-day drug screening experiment. Our cell array does not require continuous perfusion for keeping cells exposed to concentration gradients, minimizing the amount of drug used per experiment, and cells cultured in the chamber are not exposed to significant shear stress continuously. The utility of this platform is demonstrated for inducing loss of viability of PC3 prostate cancer cells using combinations of either doxorubicin or mitoxantrone with TRAIL (TNF-alpha Related Apoptosis Inducing Ligand) either in a sequential or simultaneous format. Our results demonstrate that the device can capture the synergy between different sensitizer drugs and TRAIL and demonstrate the potential of the microfluidic cell array for screening and optimizing combinatorial drug treatments for cancer therapy.     

A microfluidic device for high throughput bacterial biofilm studies

Bacteria are almost always found in ecological niches as matrix-encased, surface-associated, multi-species communities known as biofilms. It is well established that soluble chemical signals produced by the bacteria influence the organization and structure of the biofilm; therefore, there is significant interest in understanding how different chemical signals are coordinately utilized for community development. Conventional methods for investigating biofilm formation such as macro-scale flow cells are low-throughput, require large volumes, and do not allow spatial and temporal control of biofilm community formation. Here, we describe the development of a PDMS-based two-layer microfluidic flow cell (μFC) device for investigating bacterial biofilm formation and organization in response to different concentrations of soluble signals. The μFC device contains eight separate microchambers for cultivating biofilms exposed to eight different concentrations of signals through a single diffusive mixing-based concentration gradient generator. The presence of pneumatic valves and a separate cell seeding port that is independent from gradient-mixing channels offers complete isolation of the biofilm microchamber from the gradient mixer, and also performs well under continuous, batch or semi-batch conditions. We demonstrate the utility of the μFC by studying the effect of different concentrations of indole-like biofilm signals (7-hydroxyindole and isatin), either individually or in combination, on biofilm development of pathogenic E. coli. This model can be used for developing a fundamental understanding of events leading to bacterial attachment to surfaces that are important in infections and chemicals that influence the biofilm formation or inhibition.     

Physicochemical and solvatochromic analysis of an imidazole derivative as NLO material

Bioactive imidazole derivative, 2-(2,4-difluorophenyl)-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline, has been synthesized and characterized by IR, UV-vis, NMR and elemental (CHN) analysis. The electric dipole moment (μ) and the hyperpolarizability (β) have been studied both experimentally and theoretically, which reveals that the synthesized imidazole derivative possesses non-linear optical (NLO) behavior. This chromophore possess more appropriate ratio of off-diagonal versus diagonal β tensorial component (r=β(xyy)/β(xxx)=-0.19) which reflects the in plane nonlinearity anisotropy. Since they have largest μβ(0) value, the reported imidazole can be used as potential NLO material. Within this context, reasonable conclusions concerning the steric hindrance in the chromospheres, push-pull character, hyperpolarizability of the imidazole and their application as NLO materials will be drawn. The solvent effect on the absorption and fluorescence bands was analyzed by a multi-component linear regression in which several solvent parameters were analyzed simultaneously.     

Synthesis of 2-deoxy-2-c-alkyl glycal and glycopyranosides from 2-hydroxy glycal ester

A method to convert 2-hydroxy glycal ester to the corresponding 2-deoxy-2-C-alkyl glycal in a facile manner, through key reactions including (i) C-allylation at C-1, (ii) Wittig reaction, and (iii) Cope rearrangement of a 1,5-diene derivative, is reported. The α-anomer of the 1,5-diene derivative underwent Cope rearrangement to afford 2-deoxy-2-C-glycal derivative, whereas the β-anomer was found to be unreactive. Employing this sequence, 3,4,6-tri-O-benzyl-2-O-acetyl-1,5-anhydro-d-arabino-hex-1-enitol was transformed to 3,4,6-tri-O-benzyl-2-deoxy-2-C-alkyl-1,5-anhydro-D-arabino-hex-1-enitol. 2-Deoxy-2-C-alkyl glycal derivative is a suitable glycosyl donor to prepare 2-deoxy-2-C-alkyl glycosides, mediated through haloglycosylation and a subsequent dehalogenation. A number of 2-deoxy-2-C-alkyl glycosides, with both glycosyl and nonglycosyl moieties at the reducing end, are thus prepared from the glycal.     

Stability and Scalarization of Weak Efficient, Efficient and Henig Proper Efficient Sets Using Generalized Quasiconvexities

The aim of this paper is to establish the stability of weak efficient, efficient and Henig proper efficient sets of a vector optimization problem, using quasiconvex and related functions. We establish the Kuratowski?CPainlevé set-convergence of the minimal solution sets of a family of perturbed problems to the corresponding minimal solution set of the vector problem, where the perturbations are performed on both the objective function and the feasible set. This convergence is established by using gamma convergence of the sequence of the perturbed objective functions and Kuratowski?CPainlevé set-convergence of the sequence of the perturbed feasible sets. The solution sets of the vector problem are characterized in terms of the solution sets of a scalar problem, where the scalarization function satisfies order preserving and order representing properties. This characterization is further used to establish the Kuratowski?CPainlevé set-convergence of the solution sets of a family of scalarized problems to the solution sets of the vector problem.     

Duality in ε-variational inequality problems

In this paper a general analysis of duality for an extended ε-variational inequality problem based on the notions of ε-convexity and ε-conjugacy is performed. Optimal solutions of both the primal and dual problems are also related to the saddle point of an associated Lagrangian. Gap functions for these problems are proposed. An existence theorem for the extended ε-variational inequality is also established by means of the KKM lemma.     

Levitin–Polyak well-posedness for parametric quasivariational inequality problem of the Minty type

In this paper, we introduce the notions of Levitin?CPolyak (LP) well-posedness and Levitin?CPolyak well-posedness in the generalized sense, for a parametric quasivariational inequality problem of the Minty type. Metric characterizations of LP well-posedness and generalized LP well-posedness, in terms of the approximate solution sets are presented. A parametric gap function for the quasivariational inequality problem is introduced and an equivalence relation between LP well-posedness of the parametric quasivariational inequality problem and that of the related optimization problem is obtained.     

Synthesis, Crystal Structure, Kamlet-Taft and Catalan Solvatochromic Analysis of Novel Imidazole Derivatives

Novel imidazole derivatives were synthesized and its crystal structure has been studied by single crystal XRD analysis. The photophysical properties of these imidazole derivatives were studied in several solvents, which include a wide range of apolar, polar and protic media. The observed lower fluorescence quantum yield may be due to an increase in the non-radiative deactivation rate constant. This is attributed to a loss of planarity in the excited state provided by the non co-planarity of the aryl rings attached to C(2) and N(1) atoms of the imidazole ring. Such a geometrical change in the excited state leads to an important Stokes shift, reducing the reabsorption and reemission effects in the detected emission in highly concentrated solutions. The highest fluorescence quantum yield of the imidazole derivatives are observed in polar media.     

Photosensitization of Imidazole Derivative by ZnO Nanoparticle

A sensitive imidazole based fluorescent sensor like 4, 5-diphenyl-2(E)-styryl-1H-imidazole, for ZnO has been designed and synthesized via simple steps. The absorption, fluorescence, SEM, EDX and IR studies indicate that imidazole derivative is bound on the surface of ZnO semiconductor. Based on photo-induced electron transfer (PET) mechanism, fluorescent enhancement has been explained and apparent binding constant has been calculated. Ligand adsorption on ZnO nanoparticle lowers of the HOMO and LUMO energy levels of imidazole derivative and the chemical affinity between the nitrogen atom of the imidazole and zinc ion on the surface of the nano oxide may be a reason for strong adsorption of the ligand on nanoparticle. The electron injection from photo excited imidazole derivative to the ZnO conduction band (S(*)→S(+) + e (CB) (-) ) accounts for the enhanced fluorescence.