Optimization of a spatial light modulator driven by digital video interface graphics to generate holographic optical traps.

We propose a method to optimize spatial light modulators (SLMs) driven by digital video interface graphics in a holographic optical tweezers system. A method analogous to that used to optimize LCD televisions is used to optimize the properties of the graphics card through a diffraction-based experiment and develop a lookup table for the SLM. The optimization allows the SLM to function with its full phase modulation depth with improved diffraction efficiency. Further, we propose a simple and robust method to correct for the spatially varying phase response of the SLM to enhance its diffraction efficiency. The optimization results in an improvement of uniformity in the intensity and quality of the trap spots.

FCC-HCP coexistence in dense thermo-responsive microgel crystals.

Analogous to hard-sphere suspensions, monodisperse thermo-responsive poly (N-isopropyl acrylamide) (PNIPAM) microgel particles beyond a volume fraction (ϕ) of 0.5 freeze into face centered cubic (FCC)-hexagonal close packed (HCP) coexistence under as prepared conditions and into an FCC structure upon annealing. We report here FCC-HCP coexistence to be stable in dense PNIPAM microgel crystals (ϕ > 0.74) with particles in their deswollen state (referred to as osmotically compressed microgel crystals) and the FCC structure with particles in their swollen state by performing annealing studies with different cooling rates. The structure of PNIPAM microgel crystals is characterized using static light scattering technique and UV-Visible spectroscopy and dynamics by dynamic light scattering (DLS). DLS studies reveal that the particle motion is diffusive at short times in crystals with ϕ < 0.74 and sub-diffusive at short times in PNIPAM crystals with ϕ > 0.74. The observed sub-diffusive behavior at short times is due to the overlap (interpenetration) of the dangling polymer chains between the shells of neighbouring PNIPAM microgel particles. Overlap is found to disappear upon heating the crystals well above their melting temperature, Tm due to reduction in the particle size. Annealing studies confirm that the overlap of dangling polymer chains between the shells of neighbouring PNIPAM spheres is responsible for the stability of FCC-HCP coexistence observed in osmotically compressed PNIPAM microgel crystals. Results are discussed in the light of recent reports of stabilizing the HCP structure in hard sphere crystals by adding interacting polymer chains.

Crystalline fibrillar gel formation in aqueous surfactant-antioxidant system.

Cetyltrimethylammonium bromide (CTAB) is a well-known cationic surfactant capable to micellize into diverse morphologies in aqueous medium. We observed the formation of an opaque gel state from aqueous CTAB solution in the presence of the aromatic additive, para-coumaric acid (PCA). Optical microscopic images revealed the presence of large fibrils in the system at room temperature. Gel nature of the fibrils was confirmed by rheological measurements. Presence of interstitial water in the fibrils was recognized with Raman spectroscopy. On heating the sample above 30 (°) C, the fibrillar gel state changes to a transparent liquid state with Newtonian flow properties. Dynamic light scattering study hinted the presence of small micelles in the solution above 30 (°) C. Thus the system showed a temperature-dependent structural transition from opaque water-swollen gel to transparent micellar liquid. The formation of water-swollen fibrillar network is attributed to surfactant-additive intermolecular interactions in aqueous medium. Transition to micelle phase above 30 (°) C is related to Kraft transition which is observed at significantly lower temperature for CTAB in the absence of PCA. The structural features of PCA play a key role in promoting fibrillar network formation and elevating the Kraft transition in aqueous solution of CTAB.

pH-switchable structural evolution in aqueous surfactant-aromatic dibasic acid system.

Structural transitions triggered by pH in an aqueous micellar system comprising of a cationic surfactant (cetylpyridinium chloride) and an aromatic dibasic acid (phthalic acid) was investigated. Reversible switching between liquid-like and gel-like states was exhibited by the system on adjusting the solution pH. Self-assembled structures, responsible for the changes in flow properties were identified using rheology, light scattering techniques and cryogenic Transmission Electron Microscopy (cryo-TEM). High-viscosity, shear-thinning behavior and Maxwell-type dynamic rheology shown by the system at certain pH values suggested the growth of spheroidal/short cylindrical micelles into long and entangled structures. Light scattering profiles also supported the notion of pH-induced microstructural transitions in the solution. Cryo-TEM images confirmed the presence of spheroidal/short cylindrical micelles in the low-viscosity sample whereas very long and entangled thread-like micelles in the peak viscosity sample. pH-dependent changes in the micellar binding ability of phthalic acid is proposed as the key factor regulating the morphological transformations and related flow properties of the system.

Dynamics in thermo-responsive nanogel crystals undergoing melting.

We report here the dynamics in thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) nanogel crystals undergoing melting/freezing and verify the applicability of the dynamical criterion for melting/freezing proposed by Löwen et al. [Phys. Rev. Lett. 70, 1557 (1993)]. According to this criterion the ratio of long time diffusion coefficient (D(L)) to short time diffusion coefficients (D(S)) is ~0.1 for colloidal particles in suspension undergoing melting/freezing. Static and dynamic light scattering techniques have been employed to identify the melting/freezing transition of PNIPAM nanogel colloidal crystals of two different volume fractions φ = 0.49 and 0.79 and to measure D(L) and D(S) across the melting. In dense PNIPAM nanogel crystals undergoing melting, the ratio D(L)/D(S) is found to be less than 0.1 for the first time and this deviation is higher in the suspension with higher φ. We also show that the deviation is genuine by measuring D(L)/D(S) on shear melted charged silica colloidal liquid undergoing freezing. The mean square displacement at shorter times, close to the melting, shows subdiffusive behavior. The subdiffusive behavior, arising due to the overlap of the dangling polymer chains between shells of the neighboring particles, is argued to be the reason for the observed deviation.

Bioreduction of Cr(VI) by alkaliphilic Bacillus subtilis and interaction of the membrane groups.

Detoxification of Cr(VI) under alkaline pH requires attention due to the alkaline nature of many effluents. An alkaliphilic gram-positive Bacillus subtilis isolated from tannery effluent contaminated soil was found to grow and reduce Cr(VI) up to 100% at an alkaline pH 9. Decrease in pH to acidic range with growth of the bacterium signified the role played by metabolites (organic acids) in chromium resistance and reduction mechanism. The XPS and FT-IR spectra confirmed the reduction of Cr(VI) by bacteria into +3 oxidation state. Chromate reductase assay indicated that the reduction was mediated by constitutive membrane bound enzymes. The kinetics of Cr(VI) reduction activity derived using the monod equation proved (K s = 0.00032) high affinity of the organism to the metal. This study thus helped to localize the reduction activity at subcellular level in a chromium resistant alkaliphilic Bacillus sp.

Phase behavior of poly(N-isopropylacrylamide) nanogel dispersions: temperature dependent particle size and interactions.

The phase behavior of poly(N-isopropylacrylamide) nanoparticles dispersed in aqueous medium is investigated as a function of temperature using static and dynamic light scattering techniques. The diameter, d of the particles, as determined by dynamic light scattering measurements on dilute dispersion showed a decrease in size from 273 nm at 25 degrees C to 114 nm at 40 degrees C as function of temperature with a sudden collapse of particle volume (volume phase transition) at 32.4 degrees C. Further this nanoparticle dispersion is found to turn turbid beyond volume phase transition. Static light scattering measurements on samples with intermediate concentration and high concentration showed liquid-like order and crystalline order respectively. The intensity of the Bragg peak of the crystallized sample when monitored as a function of temperature showed crystal to liquid transition at 26.2 degrees C and a fluid to fluid transition at 31 degrees C. The occurrence of melting at a volume fraction of 0.85 and the absence of change in number density across the fluid-to-fluid transition suggest that interparticle interaction is repulsive soft-sphere below the volume phase transition. The reported results on the phase behavior of poly(N-isopropylacrylamide) nanogel suspensions are discussed in the light of the present results.

Random hcp and fcc structures in thermoresponsive microgel crystals.

Monodisperse thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) microgel particles having a diameter of 520 nm were synthesized by free-radical precipitation polymerization and centrifuged to obtain a concentrated suspension. The centrifuged mother suspension was made to self-order into a crystalline state by repeated annealing beyond the volume phase transition (VPT) of the particles. We report here the three-dimensional (3D) real space structure, determined using a confocal laser scanning microscope, of PNIPAM microgel crystal samples prepared by two different recrystallized routes: (1) solidifying a shear melted colloidal liquid (referred as as-prepared sample) and (2) slow cooling of a colloidal liquid (referred as recrystallized sample). We have recorded images of several regions of the crystal with each region containing 15 horizontal crystal planes for determining the in-plane [two-dimensional (2D)] and 3D pair-correlation functions. The 2D pair-correlation function g(r) revealed hexagonal long-range order of particles in the layers with a lattice constant of 620 nm. The analysis of stacking sequence of layers recorded on as-prepared sample has revealed the existence of stacking disorder with an average stacking probability alpha approximately 0.42. This value of alpha together with the analysis of 3D pair-correlation function determined from particle positions revealed the structure of microgel crystals in the as-prepared sample to be random hexagonal close packing. We report the first observation of a split second peak in the 3D g(r) of the microgel crystals obtained from a shear melted liquid. Upon melting the sample above VPT and recrystallizing it the split second peak disappeared and the crystals are found to have a face centered cubic (fcc) structure with alpha approximately 0.95. From simulations, the split second peak is shown to arise from the displacement of some of the B-planes from the ideal hcp positions. The present results are discussed in light of those reported for charged and hard sphere colloidal crystals and plausible reasons for observing two different structures are also explained.

Biomineralisation of manganese on titanium surfaces exposed to seawater.

A 2-year long study was carried out to isolate and characterise various bacterial species present in the biofilm formed on titanium surfaces exposed to seawater and to assess the manganese oxidizing potential of the marine isolates. The amount of manganese present in the biofilm was also measured using atomic absorption spectrometry (AAS). The results showed that titanium was susceptible to biofouling. More than 50% of the culturable marine bacterial isolates were capable of bringing about oxidation of Mn(II). All these manganese oxidizing bacteria were heterotrophic. Autotrophic manganese oxidizing bacteria such as Leptothrix was not isolated in the present study. The AAS results confirmed that the manganese content in the biofilms increased with increasing exposure time. Hence, the study indicates that the titanium surfaces when exposed to seawater were colonised by a large number of heterotrophic bacteria, which have the ability of bringing about biomineralisation of manganese.

Dynamics of Deinococcus radiodurans under controlled growth conditions.

Deinococcus radiodurans is a potent radiation resistant bacterium with immense potential in nuclear waste treatment. In this investigation, the translational and rotational dynamics of dilute suspensions of D. radiodurans cultured under controlled growth conditions was studied by the polarized and depolarized dynamic light-scattering (DLS) techniques. Additionally, confocal laser scanning microscopy was used for characterizing the cultured samples and also for identification of D. radiodurans dimer, tetramer, and multimer morphologies. The data obtained showed translational diffusion coefficients (DT) of 1.2 x 10(-9), 1.97 x 10(-9), and 2.12 x 10(-9) cm2 /s, corresponding to an average size of 3.61, 2.22, and 2.06 microm, respectively, for live multimer, tetramer, and dimer forms of D. radiodurans. Depolarized DLS experiments showed very slow rotational diffusion coefficients (DR) of 0.182/s for dimer and 0.098/s for tetramer morphologies. No measurable rotational diffusion was observed for multimer form. Polarized DLS measurements on live D. radiodurans confirmed that the bacterium is nonmotile in nature. The dynamics of the dead dimer and tetramer D. radiodurans were also studied using polarized and depolarized DLS experiments and compared with the dynamics of live species. The dead cells were slightly smaller in size when compared to the live cells. However, no additional information could be obtained for dead cells from the polarized and depolarized dynamic light-scattering studies.

Gas-solid coexistence in highly charged colloidal suspensions.

Aqueous suspensions of highly charged polystyrene particles with different volume fractions have been investigated for structural ordering and phase behavior using static light scattering (SLS) and confocal laser scanning microscope (CLSM). Under deionized conditions, suspensions of high-charge-density colloidal particles remained disordered whereas suspensions of relatively low charge density showed crystallization by exhibiting iridescence for the visible light. Though for the unaided eye crystallized suspensions appeared homogeneous, SLS measurements and CLSM observations have revealed their inhomogeneous nature in the form of the coexistence of voids with dense ordered regions. CLSM investigations on disordered suspensions showed their inhomogeneous nature in the form coexistence of voids with dense disordered (amorphous) regions. Our studies on highly charged colloids confirm the occurrence of gas-solid transition and are in accordance with predictions of Monte Carlo simulations using a pair-potential having a long-range attractive term [Mohanty, P. S.; Tata, B. V. R. J. Colloid Interface Sci. 2003, 264, 101]. On the basis of our experimental and simulation results, we argue that the reported reentrant disordered state [Yamanaka et al. Phys. Rev. Lett. 1998, 80, 5806 and Toyotama et al. Langmuir 2003, 19, 3236] in charged colloids observed at high charge densities is a gas-solid coexistence state.

Long-wavelength transverse modes in charged colloidal crystals.

The dynamics of closely index matched colloidal crystals of charged silica spheres dispersed in deionized ethylene glycol-water mixture is investigated using dynamic light scattering. At variance with the reports of phonon dispersion measurements on thin colloidal crystals, our observations on millimeter-sized crystals show unambiguous evidence for overdamped transverse modes turning propagative in the range of small wave numbers in agreement with the theory of hydrodynamic interactions in charged colloidal crystals.

Charge and salt-driven reentrant order-disorder and gas-solid transitions in charged colloids.

Monte Carlo simulations have been performed for aqueous charged colloidal suspensions as a function of effective charge density (sigma) on the particles and salt concentration C(s). We vary the effective charge density in our simulations over a range where a reentrant solid-liquid transition in suspensions of silica and polymer latex particles has been reported by Yamanaka et al. (Phys. Rev. Lett. 80 (1998) 5806). We show that at low ionic strengths a homogeneous liquid-like ordered suspension undergoes crystallization upon increasing sigma. Further increase in sigma resulted once again in a disordered state, which is in agreement with experimental observations. In addition to this reentrant order-disorder transition, we observe an inhomogeneous-to-homogeneous transition in our simulations when salt is added to the disordered inhomogeneous state. This inhomogeneous-to-homogeneous disordered transition is analogous to the solid-gas transition of atomic systems and has not yet been observed in charged colloids. The reported experimental observations on charged colloidal suspensions are discussed in the light of present simulation results.

Glass transition and dynamical heterogeneities in charged colloidal suspensions under pressure.

Constant-pressure Monte Carlo simulations have been performed to study the static and dynamical properties of a liquidlike ordered suspension of like-charged colloidal particles subjected to a sudden compression. We report for the first time a liquidlike ordered monodisperse suspension undergoing a glass transition at a very low volume fraction ( straight phi = 0.003) and existence of dynamical heterogeneities near the glass transition. Mobile particles have been identified using the non-Gaussian parameter for the self-part of the Van Hove correlation function, and they are found to form clusters. The pressure dependence of mean cluster size and the cluster-size distribution of the mobile particles are discussed.