Instabilities and Waves in Thin Films of Living Fluids

We formulate the thin-film hydrodynamics of a suspension of polar self-driven particles and show that it is prone to several instabilities through the interplay of activity, polarity, and the existence of a free surface. Our approach extends, to self-propelling systems, the work of Ben Amar and Cummings [Phys. Fluids 13 1160 (2001)] on thin-film nematics. Based on our estimates the instabilities should be seen in bacterial suspensions and the lamellipodium, and are potentially relevant to the morphology of biofilms. We suggest several experimental tests of our theory.

Dynamical Transition of Water in the Grooves of DNA Duplex at Low Temperature

At low temperature (below its freezing/melting temperature), liquid water under confinement is known to exhibit anomalous dynamical features. Here we study structure and dynamics of water in the grooves of a long DNA duplex using molecular dynamics simulations with TIP5P potential at low temperature. We find signatures of a dynamical transition in both translational and orientational dynamics of water molecules in both the major and the minor grooves of a DNA duplex. The transition occurs at a slightly higher temperature (TGL ≈ 255 K) than the temperature at which the bulk water is found to undergo a dynamical transition, which for the TIP5P potential is at 247 K. Groove water, however, exhibits markedly different temperature dependence of its properties from the bulk. Entropy calculations reveal that the minor groove water is ordered even at room temperature, and the transition at T ≈ 255 K can be characterized as a strong-to-strong dynamical transition. Confinement of water in the grooves of DNA favors the formation of a low density four-coordinated state (as a consequence of enthalpy−entropy balance) that makes the liquid−liquid transition stronger. The low temperature water is characterized by pronounced tetrahedral order, as manifested in the sharp rise near 109° in the O−O−O angle distribution. We find that the Adams−Gibbs relation between configurational entropy and translational diffusion holds quite well when the two quantities are plotted together in a master plot for different region of aqueous DNA duplex (bulk, major, and minor grooves) at different temperatures. The activation energy for the transfer of water molecules between different regions of DNA is found to be weakly dependent on temperature.

Impressive Gelation in Organic Solvents by Synthetic, Low Molecular Mass, Self-Organizing Urethane Amides of L-Phenylalanine

Synthetic routes leading to 12 L-phenylalanine based mono- and bipolar derivatives (1-12) and an in-depth study of their structure-property relationship with respect to gelation have been presented. These include monopolar systems such as N-[(benzyloxy)carbonyl]-L-phenylalanine-N-alkylamides and the corresponding bipolar derivatives with flexible and rigid spacers such as with 1,12-diaminododecane and 4,4'-diaminodiphenylmethane, respectively. The two ends of the latter have been functionalized with N-[(benzyloxy)carbonyl]-L-phenylalanine units via amide connection. Another bipolar molecule was synthesized in which the middle portion of the hydrocarbon segment contained polymerizable diacetylene unit. To ascertain the role of the presence of urethane linkages in the gelator molecule protected L-phenylalanine derivatives were also synthesized in which the (benzyloxy)carbonyl group has been replaced with (tert-butyloxy)carbonyl, acetyl, and benzoyl groups, respectively. Upon completion of the synthesis and adequate characterization of the newly described molecules, we examined the aggregation and gelation properties of each of them in a number of solvents and their mixtures. Optical microscopy and electron microscopy further characterized the systems that formed gels. Few representative systems, which showed excellent gelation behavior was, further examined by FT-IR, calorimetric, and powder X-ray diffraction studies. To explain the possible reasons for gelation, the results of molecular modeling and energy-minimization studies were also included. Taken together these results demonstrate the importance of the presence of (benzyloxy)carbonyl unit, urethane and secondary amide linkages, chiral purities of the headgroup and the length of the alkyl chain of the hydrophobic segment as critical determinants toward effective gelation.

Resistance Noise in Electrically Biased Bilayer Graphene

We demonstrate that the low-frequency resistance uctuations, or noise, in bilayer graphene is strongly connected to its band structure, and displays a minimum when the gap between the conduction and valence band is zero. Using double-gated bilayer graphene devices we have tuned the zero gap and charge neutrality points independently, which oers a versatile mechanism to investigate the low-energy band structure, charge localization and screening properties of bilayer graphene.

Size-dependent elasticity of nanocrystalline titania

Synchrotron-based high-pressure x-ray diffraction measurements indicate that compressibility, a fundamental materials property, can have a size-specific minimum value. The bulk modulus of nanocrystalline titania has a maximum at particle size of 15 nm. This can be explained by dislocation behavior because very high dislocation contents can be achieved when shear stress induced within nanoparticles counters the repulsion between dislocations. As particle size decreases, compression increasingly generates dislocation networks hardened by overlap of strain fields that shield intervening regions from external pressure. However, when particles become too small to sustain high dislocation concentrations, elastic stiffening declines. The compressibility has a minimum at intermediate sizes.

Investigation of the Internal Heterostructure of Highly Luminescent Quantum Dot-Quantum Well Nanocrystals

In this paper, we report on the growth and characterization of quantum dot−quantum well nanostructures with photoluminescence (PL) that is tunable over the visible range. The material exhibits a PL efficiency as high as 60% and is prepared by reacting ZnS nanocrystals in turn with precursors for CdSe and ZnS in an attempt to form a simple “ZnS/CdSe/ZnS quantum-well structure”. Through the use of synchrotron radiation-based photoelectron spectroscopy in conjunction with detailed overall compositional analysis and correlation with the size of the final composite nanostructure, the internal structure of the composite nanocrystals is shown to consist of a graded alloy core whose composition gradually changes from ZnS at the very center to CdSe at the onset of a CdSe layer. The outer shell is ZnS with a sharp interface, probably reflecting the relative thermodynamic stabilities of the parent binary phases. These contrasting aspects of the internal structure are discussed in terms of the various reactivities and are shown to be crucial for understanding the optical properties of such complex heterostructured nanomaterials.

Copper(II) Complexes of l-Arginine as Netropsin Mimics Showing DNA Cleavage Activity in Red Light

Copper(II) complexes [Cu(L-arg)(2)](NO3)(2) (1) and [Cu(L-arg)(B)Cl]Cl (2-5), where B is a heterocyclic base, namely, 2,2'-bipyridine (bpy, 2), 1,10-phenanthroline (phen, 3), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 4), and dipyrido[3,2-a:2',3'-c)phenazine (dppz, 5), are prepared and their DNA binding and photoinduced DNA cleavage activity studied. Ternary complex 3, structurally characterized using X-ray crystallography, shows a square-pyramidal (4 + 1) coordination geometry in which the N,O-donor L-arginine and N,N-donor 1,10-phenanthroline form the basal plane with one chloride at the elongated axial site. The complex has a pendant cationic guanidinium moiety. The one-electron paramagnetic complexes display a metal-centered d-d band in the range of 590-690 nm in aqueous DMF They show quasireversible cyclic voltammetric response due to the Cu(II)/Cu(I) couple in the range of -0.1 to -0.3 V versus a saturated calomel electrode in a DMF-Tris HCl buffer (pH 7.2). The DNA binding propensity of the complexes is studied using various techniques. Copper(II) bis-arginate 1 mimics the minor groove binder netropsin by showing preferential binding to the AT-rich sequence of double-strand (ds) DNA. DNA binding study using calf thymus DNA gives an order: 5 (L-arg-dppz) >= 1 (biS-L-arg) > 4 (L-arg-dpq) > 3 (L-arg-phen) >> 2 (L-arg-bpy). Molecular docking calculations reveal that the complexes bind through extensive hydrogen bonding and electrostatic interactions with ds-DNA. The complexes cleave supercoiled pUC19 DNA in the presence of 3-mercaptopropionic acid as a reducing agent forming hydroxyl ((OH)-O-center dot) radicals. The complexes show oxidative photoinduced DNA cleavage activity in UV-A light of 365 nm and red light of 647.1 nm (Ar-Kr mixed-gas-ion laser) in a metal-assisted photoexcitation process forming singlet oxygen (O-1(2)) species in a type-II pathway. All of the complexes, barring complex 2, show efficient DNA photocleavage activity. Complexes 4 and 5 exhibit significant double-strand breaks of DNA in red light of 647.1 nm due to the presence of two photosensitizers, namely, L-arginine and dpq or dppz in the molecules.

Photoinduced DNA and Protein Cleavage Activity of Ferrocene-Appended L-Methionine Reduced Schiff Base Copper(II) Complexes of Phenanthroline Bases

Ferrocene-appended ternary copper(H) complexes of phenanthroline bases having CuN3OS coordination with an axial Cu-S bond derived from L-methionine reduced Schiff base shows red light induced oxidative DNA cleavage activity following a hydroxyl radical pathway. The dipyridophenazine complex, in addition, displays photoinduced oxidative cleavage of bovine serum albumin protein in UV-A light.

Structure and Rheology of Cationic Molecular Hydrogels of Quinuclidine Grafted Bile Salts. Influence of the Ionic Strength and Counter-Ion type

Quinuclidine grafted cationic bile salts are forming salted hydrogels. An extensive investigation of the effect of the electrolyte and counterions on the gelation has been envisaged. The special interest of the quinuclidine grafted bile salt is due to its broader experimental range of gelation to study the effect of electrolyte. Rheological features of the hydrogels are typical of enthalpic networks exhibiting a scaling law of the elastic shear modulus with the concentration (scaling exponent 2.2) modeling cellular solids in which the bending modulus is the dominant parameter. The addition of monovalent salt (NaCl) favors the formation of gels in a first range (0.00117 g cm-3 (0.02 M) < TNaCl < 0.04675 g cm-3 (0.8 M)). At larger salt concentrations, the gels become more heterogeneous with nodal zones in the micron scale. Small-angle neutron scattering experiments have been used to characterize the rigid fibers ( ≈ 68 Å) and the nodal zones. Stress sweep and creeprecovery measurements are used to relate the lack of linear viscoelastic domain to a mechanism of disentanglement of the fibers from their associations into fagots. The electrostatic interactions can be screened by addition of salt to induce a progressive evolution toward flocculation. SEM, UV absorbance, and SAXS study of the Bragg peak at large Q-values complete the investigation.

Study of Ion Transport in Lithium Perchlorate-Succinonitrile Plastic Crystalline Electrolyte via Ionic Conductivity and in Situ Cryo-Crystallography

Ion transport mechanism in lithium perchlorate (LiClO4)-succinonitrile (SN), a prototype of plastic crystalline soft matter electrolyte is discussed in the context of solvent configurational isomerism and ion solvation. Contributions of both solvent configurational isomerism and ion solvation are reflected in the activation energy for ion conduction in 0-1 M LiClO4-SN samples. Activation energy due to solvent configurational changes, that is, trans-gauche isomerism is observed to be a function of salt content and decreases in presence of salt (except at high salt concentrations, e.g. 1 M LiClO4-SN). The remnant contribution to activation energy is attributed to ion-association. The X-ray diffraction of single crystals obtained using in situ cryo-crystallography confirms directly the observations of the ionic conductivity measurements. Fourier transform infrared spectroscopy and NMR line width measurements provide additional support to our proposition of ion transport in the prototype plastic crystalline electrolyte.

Remarkable Capacity Retention of Nanostructured Manganese Oxide upon Cycling as an Electrode Material for Supercapacitor

Electrochemical capacity retention of nearly X-ray amorphous nanostructured manganese oxide (nanoMnO2) synthesized by mixing directly KMnO4 with ethylene glycol under ambient conditions for supercapacitor studies is enhanced significantly. Although X-ray diffraction (XRD) pattern of nanoMnO2 shows poor crystallinity, it is found that by Mn K-edge X-ray absorption near edge structure (XANES) measurement that the nanoMnO2 obtained is locally arranged in a δ-MnO2-type layered structure composed of edge-shared network of MnO6 octahedra. Field emission scanning electron microscopy and XANES measurements show that nanoMnO2 contains nearly spherical shaped morphology with δ-MnO2 structure, and 1D nanorods of α-MnO2 type structure (powder XRD) in the annealed (600 °C) sample. Volumetric nitrogen adsorption−desorption isotherms, inductively coupled plasma analysis, and thermal analysis are carried out to obtain physicochemical properties such as surface area (230 m2 g−1), porosity of nanoMnO2 (secondary mesopores of diameter 14.5 nm), water content, composition, etc., which lead to the promising electrochemical properties as an electrode for supercapacitor. The nanoMnO2 shows a very high stability even after 1200 cycles with capacity retention of about 250 F g−1.

Theoretical Description of Time-Resolved Photoemission Spectroscopy: Application to Pump-Probe Experiments

The theory for time-resolved, pump-probe, photoemission spectroscopy and other pump-probe experiments is developed. The formal development is completely general, incorporating all of the nonequilibrium effects of the pump pulse and the finite time width of the probe pulse, and including possibilities for taking into account band structure and matrix element effects, surface states, and the interaction of the photoexcited electrons with the system leading to corrections to the sudden approximation. We also illustrate the effects of windowing that arise from the finite width of the probe pulse in a simple model system by assuming the quasiequilibrium approximation.

Resistance Noise in Electrically Biased Bilayer Graphene

We demonstrate that the low-frequency resistance fluctuations, or noise, in bilayer graphene are strongly connected to its band structure and display a minimum when the gap between the conduction and valence band is zero. Using double-gated bilayer graphene devices we have tuned the zero gap and charge neutrality points independently, which offers a versatile mechanism to investigate the low-energy band structure, charge localization, and screening properties of bilayer graphene.

trans-Dichloro-bis-(arylazoimidazole)palladium(II): Synthesis, Structure, Photoisomerization, and DFT Calculation

Reaction between PdCl2 and 1-alkyl-2-(arylazo)imidazole (RaaiR') or 1-alkyl-2-(naphthyl-alpha/beta-azo)imidazole (alpha/beta-NaiR') under reflux in ethanol has isolated complexes of compositions Pd(RaaiR')(2)Cl-2 (5, 6) and Pd(alpha/beta-NaiR')(2)Cl-2 (7, 8). The X-ray structure determination of one of the molecules, Pd(alpha-NaiBz)(2)Cl-2 (7c), has reported a trans-PdCl2 configuration, and alpha-NaiBz acts as monodentate N(imidazole) donor ligand. The spectral (IR, UV-vis, H-1 NMR) data support the structure. UV light irradiation (light source: Perkin-Elmer LS 55 spectrofluorimeter, Xenon discharge lamp, lambda = 360-396 nm) in a MeCN solution of the complexes shows E-to-Z isomerization of the coordinated azoimidazole unit. The reverse transformation, Z-to-E, is very slow with visible light irradiation. Quantum yields (phi(E-Z)) of E-to-Z isomerization are calculated, and phi is lower than that of the free ligand but comparable with those of Cd(II) and Hg(II) complexes of the same ligand. The Z-to-E isomerization is a thermally induced process. The activation energy (E-a) of Z-to-E isomerization is calculated by controlled-temperature experimentation. cis-Pd(azoimidazole)Cl-2 complexes (azomidazole acts as N(imidazole) and N(azo) Chelating ligand) do not respond upon light irradiation, which supports the idea that the presence of noncoordinated azo-N to make free azo (-N=N-) function is important to reveal photochromic activity. DFT calculation of Pd(alpha-NaiBz)(2)Cl-2 (7c) has suggested that the HOMO of the molecule is constituted of Pd (32%) and Cl (66%), and hence photo excitation may use the energy of Pd and Cl instead of that of the photofunctional -N=N-Ar motif; thus, the rate of photoisomerization and quantum yield decrease versus the free ligand values.

Directed Synthesis of Rocksalt AuCl Crystals

We report the first-time experimental realization of rocksalt AuCl crystals. Our approach involves Au(III) complexing and reduction to Au(I) using an amine-terminated surfactant in a low dielectric permittivity solvent. The low charge screening in nonpolar solvents promotes crystallization of rocksalt AuCl, in which the bonding is predominantly ionic, in preference over tetragonal AuCl. The rocksalt AuCl crystals obtained here will facilitate studies to unveil the nexus between electronic structure and crystal structure in AuCl polymorphs, and provide insights on these relationships in other polymorphic crystal systems. Our approach provides a new means for crystallizing selective polymorphs of inorganic compounds by subtly influencing the cation electronic structure by varying the dielectric permittivity of the synthesis medium. In addition, the AuCl crystals can serve as inexpensive Au(I) precursors for forming a variety of Au nanostructures.