BT-benzo-29 inhibits bacterial cell proliferation by perturbing FtsZ assembly

We have identified a potent antibacterial agent N-(4-sec-butylphenyl)-2-(thiophen-2-yl)-1H-benzod]imidazole-4-carboxa mide (BT-benzo-29) from a library of benzimidazole derivatives that stalled bacterial division by inhibiting FtsZ assembly. A short (5 min) exposure of BT-benzo-29 disassembled the cytokinetic Z-ring in Bacillus subtilis cells without affecting the cell length and nucleoids. BT-benzo-29 also perturbed the localization of early and late division proteins such as FtsA, ZapA and SepF at the mid-cell. Further, BT-benzo-29 bound to FtsZ with a dissociation constant of 24 +/- 3 m and inhibited the assembly and GTPase activity of purified FtsZ. A docking analysis suggested that BT-benzo-29 may bind to FtsZ at the C-terminal domain near the T7 loop. BT-benzo-29 displayed significantly weaker inhibitory effects on the assembly and GTPase activity of two mutants (L272A and V275A) of FtsZ supporting the prediction of the docking analysis. Further, BT-benzo-29 did not appear to inhibit DNA duplication and nucleoid segregation and it did not perturb the membrane potential of B. subtilis cells. The results suggested that BT-benzo-29 exerts its potent antibacterial activity by inhibiting FtsZ assembly. Interestingly, BT-benzo-29 did not affect the membrane integrity of mammalian red blood cells. BT-benzo-29 bound to tubulin with a much weaker affinity than FtsZ and exerted significantly weaker effects on mammalian cells than on the bacterial cells indicating that the compound may have a strong antibacterial potential.

Bimodality and re-entrant behaviour in the hierarchical self-assembly of polymeric nanoparticles

We show that a film of a suspension of polymer grafted nanoparticles on a liquid substrate can be employed to create two-dimensional nanostructures with a remarkable variation in the pattern length scales. The presented experiments also reveal the emergence of concentration-dependent bimodal patterns as well as re-entrant behaviour that involves length scales due to dewetting and compositional instabilities. The experimental observations are explained through a gradient dynamics model consisting of coupled evolution equations for the height of the suspension film and the concentration of polymer. Using a Flory-Huggins free energy functional for the polymer solution, we show in a linear stability analysis that the thin film undergoes dewetting and/or compositional instabilities depending on the concentration of the polymer in the solution. We argue that the formation via `hierarchical self-assembly' of various functional nanostructures observed in different systems can be explained as resulting from such an interplay of instabilities.

Conformation-selective coordination-driven self-assembly of a ditopic donor with Pd-II acceptors

Coordination-driven self-assembly of 3-(5-(pyridin-3-yl)-1H-1,2,4-triazol-3-yl)pyridine (L) was investigated with 90 degrees cis-blocked Pd(II) acceptors and tetratopic Pd(NO3)(2). Although the ligand is capable of binding in several different conformations (acting as a ditopic donor through the pyridyl nitrogens), the experimental results (including X-ray structures) showed that it adopts a particular conformation when it binds with 90 degrees cis-blocked Pd(II) acceptors (two available sites) to yield 2 + 2] self-assembled macrocycles. On the other hand, with Pd(NO3)(2) (where four available sites are present) a different conformer of the same donor was selectively bound to form a molecular cubic cage. The experimental findings were corroborated well with the density functional theory (B3LYP) calculations. The tetratopic Pd(NO3)(2) yielded a 6 + 12] self-assembled Pd6L12 molecular cube, which contains a potential void occupied by nitrate and perchlorate ions. Being a triazole based ligand, the free space inside the cage is enriched with several sp(2) hybridised nitrogen atoms with lone pairs of electrons to act as Lewis basic sites. Knoevenagel condensation reactions of several aromatic aldehydes with active methylene compounds were successfully performed in reasonably high yields in the presence of the cage.

Temperature dependent compressive behavior of graphene mediated three-dimensional cellular assembly

Mechanical behavior of three-dimensional cellular assembly of graphene foam (GF) presented temperature dependent characteristics evaluated at both low temperature and room temperature conditions. Cellular structure of GF comprised of polydimethyl siloxane polymer as a flexible supporting material demonstrated 94% enhancement in the storage modulus as compared to polymer foam alone. Evaluation of frequency dependence revealed an increase in both storage modulus and tan delta with the increase in frequency. Moreover, strain rate independent highly reversible behavior is measured up to several compression cycles at larger strains. It is elucidated that the interaction between graphene and polymer plays a crucial role in thermo-mechanical stability of the cellular structure. (C) 2015 Elsevier Ltd. All rights reserved.

Template-free coordination-driven self-assembly of discrete hexanuclear prismatic cages employing half-sandwich octahedral Ru-2(II) acceptors and triimidazole donors

Coordination-driven self-assembly of dinuclear half-sandwich p-cymene ruthenium(II) complexes Ru-2(mu-eta(4)-C2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) and Ru-2(mu-eta(4)-C6H2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1b) separately with imidazole-based tritopic donors (L-1-L-2) in methanol yielded a series of hexanuclear 3+2] trigonal prismatic cages (2-5), respectively L-1 = 1,3,5-tris(imidazole-1-yl) benzene; L-2 = 4,4',4 `'-tris(imidazole-1-yl) triphenylamine]. All the self-assembled cages 2-5 were characterized by various spectroscopic techniques (multinuclear NMR, Infra-red and ESI-MS) and their sizes, shapes were obtained through geometry optimization using molecular mechanics universal force field (MMUFF) computation. Despite the possibility due to the free rotation of donor sites of imidazole ligands, of two different atropoisomeric prismatic cages (C-3h or C-s) and polymeric product, the self-selection of single (C(3)h) conformational isomeric cages as the only product is a noteworthy observation. (C) 2015 Elsevier B.V. All rights reserved.

Vesicular Nanostructure Formation by Self-Assembly of Anisotropic Penta-phenol-Substituted Fullerene in Water

A study on self-assembly of anisotropically substituted penta-aryl fullerenes in water has been reported. The penta-phenol-substituted amphiphilic fullerene derivative C60Ph5(OH)(5)],exhibited self-assembled vesicular nanostructures in water under the experimental conditions. The size of the vesicles Was observed to depend upon the kinetics of self-assembly and could be varied from similar to 300 to similar to 70 nm. Our mechanistic study indicated that the self-assembly of C60Ph5(OH)(5) is driven by extensive intermolecular as well as water-mediated hydrogen :bonding along with fullerene-fullerene hydrophobic interaction in water. The cumulative effect of these interactions is responsible for the stability of vesicular structures even on the removal of solvent. The substitution of phenol with anisole resulted in different packing and interaction of the fullerene derivative, as Indicated in the molecular dynamics studies, thus resulting in different self-assembled nanostructures. The hollow vesicles were further encapsulated with a hydrophobic conjugated polymer and water-soluble dye as guest molecules. Such confinement of pi-conjugated polymers in fullerene has significance in bulk heterojunction devices for efficient exciton diffusion.

Sandwiched assembly of ZnO nanowires between graphene layers for a self-powered and fast responsive ultraviolet photodetector

A heterostructure of graphene and zinc oxide (ZnO) nanowires (NWs) is fabricated by sandwiching an array of ZnO NWs between two graphene layers for an ultraviolet (UV) photodetector. This unique structure allows NWs to be in direct contact with the graphene layers, minimizing the effect of the substrate or metal electrodes. In this device, graphene layers act as highly conducting electrodes with a high mobility of the generated charge carriers. An excellent sensitivity is demonstrated towards UV illumination, with a reversible photoresponse even for a short period of UV illumination. Response and recovery times of a few milliseconds demonstrated a much faster photoresponse than most of the conventional ZnO nanostructure-based photodetectors. It is shown that the generation of a built-in electric field between the interface of graphene and ZnO NWs effectively contributes to the separation of photogenerated electron-hole pairs for photocurrent generation without applying any external bias. Upon application of external bias voltage, the electric field further increases the drift velocity of photogenerated electrons by reducing the charge recombination rates, and results in an enhancement of the photocurrent. Therefore, the graphene-based heterostructure (G/ZnO NW/G) opens avenues to constructing a novel heterostructure with a combination of two functionally dissimilar materials.

Sandwiched assembly of ZnO nanowires between graphene layers for a self-powered and fast responsive ultraviolet photodetector

A heterostructure of graphene and zinc oxide (ZnO) nanowires (NWs) is fabricated by sandwiching an array of ZnO NWs between two graphene layers for an ultraviolet (UV) photodetector. This unique structure allows NWs to be in direct contact with the graphene layers, minimizing the effect of the substrate or metal electrodes. In this device, graphene layers act as highly conducting electrodes with a high mobility of the generated charge carriers. An excellent sensitivity is demonstrated towards UV illumination, with a reversible photoresponse even for a short period of UV illumination. Response and recovery times of a few milliseconds demonstrated a much faster photoresponse than most of the conventional ZnO nanostructure-based photodetectors. It is shown that the generation of a built-in electric field between the interface of graphene and ZnO NWs effectively contributes to the separation of photogenerated electron-hole pairs for photocurrent generation without applying any external bias. Upon application of external bias voltage, the electric field further increases the drift velocity of photogenerated electrons by reducing the charge recombination rates, and results in an enhancement of the photocurrent. Therefore, the graphene-based heterostructure (G/ZnO NW/G) opens avenues to constructing a novel heterostructure with a combination of two functionally dissimilar materials.

Structural studies on chimeric Sesbania mosaic virus coat protein: Revisiting SeMV assembly

The capsid protein (CP) of Sesbania mosaic virus (SeMV, a T=3 plant virus) consists of a disordered N-terminal R-domain and an ordered S-domain. Removal of the R-domain results in the formation of T=1 particles. In the current study, the R-domain was replaced with unrelated polypeptides of similar lengths: the B-domain of Staphylococcus aureus SpA, and SeMV encoded polypeptides P8 and P10. The chimeric proteins contained T=3 or larger virus-like particles (VLPs) and could not be crystallized. The presence of metal ions during purification resulted in a large number of heterogeneous nucleoprotein complexes. N Delta 65-B (R domain replaced with B domain) could also be purified in a dimeric form. Its crystal structure revealed T=1 particles devoid of metal ions and the B-domain was disordered. However, the B-domain was functional in N Delta 65-B VLPs, suggesting possible biotechnological applications. These studies illustrate the importance of N-terminal residues, metal ions and robustness of the assembly process. (C) 2015 Elsevier Inc. All rights reserved.

Self-assembly of a redox active water soluble Pd6L8 `molecular dice'

A water soluble `molecular dice' was synthesised via coordination driven self-assembly of a Pd(II) ion with a flexible cationic tritopic donor and was fully characterised using NMR, ESI-MS and single crystal X-ray diffraction analysis. The donor-inherited redox active nature of the `molecular dice' was studied using cyclic voltammetry.

Influence of cluster-assembly parameters on the field emission properties of nanostructured carbon films

Supersonic cluster beam deposition has been used to produce films with different nanostructures by controlling the deposition parameters such as the film thickness, substrate temperature and cluster mass distribution. The field emission properties of cluster-assembled carbon films have been characterized and correlated to the evolution of the film nanostructure. Threshold fields ranging between 4 and 10 V/mum and saturation current densities as high as 0.7 mA have been measured for samples heated during deposition. A series of voltage ramps, i.e., a conditioning process, was found to initiate more stable and reproducible emission. It was found that the presence of graphitic particles (onions, nanotube embryos) in the films substantially enhances the field emission performance. Films patterned on a micrometer scale have been conditioned spot by spot by a ball-tip anode, showing that a relatively high emission site density can be achieved from the cluster-assembled material. (C) 2002 American Institute of Physics.

Pressure Controlled Self-Assembly of High Quality Three-Dimensional Colloidal Photonic Crystals

A concise pressure controlled isothermal heating vertical deposition (PCIHVD) method is developed, which provides an optimal growing condition with better stability and reproducibility for fabricating photonic crystals (PCs) without the limitation of colloidal sphere materials and sizes. High quality PCs are fabricated with PCIHVD from polystyrene spheres with diameters ranging from 200 nm to 1 mu m. The deep photonic band gap and steep photonic band edge of the samples are most favorable for realizing ultrafast optical devices, photonic chips, and communications. This method makes a meaningful advance in the quality and diversity of PCs and greatly promotes their wide applications.