Anopore Membranes Research Articles

Anopore confinement in the cyanobiphenyl-based liquid crystal dimer CB7CB. A dielectric study

ABSTRACT We report an experimental work on the liquid crystal dimer 1’’,7’-bis(4-cyanobiphenyl-4’-yl) heptane (CB7CB) confined to Anopore membranes. We have studied the behaviour of the dielectric relaxation modes in the isotropic (I), nematic (N) and twist-bend nematic (NTB) phases by broadband dielectric spectroscopy and compared to the results of the bulk sample. We have found that the strength of the components of the static dielectric permittivity for bulk and confined samples diminishes when cooling but, once in the NTB phase, those of the confined CB7CB tend to decrease in a slower rate compared to the ones of bulk CB7CB. This work is meant to play a humble tribute to the first report on a cyanobiphenyl-based LC in its 50th anniversary.

The molecular dynamics of nematic liquid crystal confined in porous membranes treated by different surfactants

The molecular dynamics of the well-known nematic liquid crystal 4-n-pentyl-4′-cyanobiphenyl geometrically restricted in Anopore and Synpor porous membranes with various pore structure and treated by different surfactants (namely decanoic acid and lecithin) is compared. In the Anopore membrane the chosen surfactants induce the homeotropic orientation of the molecules on the walls of the cylindrical pores and observed corresponding relaxation processes (librational modes) are practically the same. The dielectric measurements of lecithin treated Synpor membranes reveals the reorientation of the molecules from planar to homeotropic on the complex multilayer structure present in their volume. The dielectric strengths of the observed two molecular processes (δ-process and librational mode) are inversed in the ratio compared to the untreated membranes. The observed differences in molecular dynamics results from the orientation of the liquid crystal molecules in untreated and treated membranes and the structure of the membranes themselves.

Behavior of oil droplets at the membrane surface during crossflow microfiltration of oil–water emulsions

A fundamental study of microfiltration membrane fouling by emulsified oil was conducted using a combination of real-time visualization, force balance on a droplet, and permeate flux analysis. The model 0.1% v/v hexadecane-in-water emulsions contained sodium dodecyl sulfate (0.1mM, 0.4mM, or 0.8mM) to regulate interfacial tension. Direct Observation Through the Membrane tests with Anopore (dpore=0.2µm) and track-etch (dpore=5µm) membranes revealed three characteristic stages of membrane fouling: (1) droplet attachment and clustering, (2) droplet deformation, and (3) droplet coalescence. In qualitative agreement with visualization results, the force balance predicted that droplets ≲36–40µm would remain pinned at dpore=5µm pores while larger droplets would be swept off the surface by the crossflow drag. In a separate set of constant pressure crossflow filtration tests with track-etch membranes, the average oil rejection was ≥98% while the permeate flux decreased to a pseudo-steady-state ~10% of the initial value. The results indicate that membrane fouling by emulsified oil is controlled by droplet coalescence and crossflow shear: the transport of oil to the membrane surface by the permeate flow is balanced by the shear-induced removal of the droplets that coalesce to exceed a critical size.

Proteome analysis identifies the Dpr protein of Streptococcus mutans as an important factor in the presence of early streptococcal colonizers of tooth surfaces.

Oral streptococci are primary colonizers of tooth surfaces and Streptococcus mutans is the principal causative agent of dental caries in humans. A number of proteins are involved in the formation of monospecies biofilms by S. mutans. This study analyzed the protein expression profiles of S. mutans biofilms formed in the presence or absence of S. gordonii, a pioneer colonizer of the tooth surface, by two-dimensional gel electrophoresis (2-DE). After identifying S. mutans proteins by Mass spectrometric analysis, their expression in the presence of S. gordonii was analyzed. S. mutans was inoculated with or without S. gordonii DL1. The two species were compartmentalized using 0.2-μl Anopore membranes. The biofilms on polystyrene plates were harvested, and the solubilized proteins were separated by 2-DE. When S. mutans biofilms were formed in the presence of S. gordonii, the peroxide resistance protein Dpr of the former showed 4.3-fold increased expression compared to biofilms that developed in the absence of the pioneer colonizer. In addition, we performed a competition assay using S. mutans antioxidant protein mutants together with S. gordonii and other initial colonizers. Growth of the dpr-knockout S. mutans mutant was significantly inhibited by S. gordonii, as well as by S. sanguinis. Furthermore, a cell viability assay revealed that the viability of the dpr-defective mutant was significantly attenuated compared to the wild-type strain when co-cultured with S. gordonii. Therefore, these results suggest that Dpr might be one of the essential proteins for S. mutans survival on teeth in the presence of early colonizing oral streptococci.

Photoisomerization-Controlled Phase Segregation in a Submicron Confined Azonematic Liquid Crystal

Deuteron nuclear magnetic resonance is used to study the phase segregation behavior of photoisomerizable liquid crystal diheptylazobenzene (7AB) confined into cylindrical pores of Anopore membranes. It is demonstrated that the concentration of both components in a binary trans-7AB and cis-7AB mixture can be controlled dynamically using UV-illumination stimulated trans-to-cis photoisomerization and thermally induced cis-to-trans backisomerization. The so far elusive temperature-concentration phase diagram of such system is determined by comparative analysis of the behavior in bulk, thin-planar, and Anopore-confining geometry.

Transmission of and fouling by long chain molecules during crossflow microfiltration of algal suspensions: influence of shear

Fouling is the main obstacle in membrane filtration, especially in the water industries. Membrane fouling by algae and its secreted extracellular polysaccharide is still an ongoing problem. Flux stepping microfiltration experiments of Chlorella Sorokiniana were carried out using Direct Observation Through Membrane (DOTM) equipment. The trend of extracellular polysaccharide (EPS) transmission during micro-filtration of Chlorella Sorokiniana was found to be dependent on flux as well as crossflow velocity (CFV). Increases in flux during flux stepping experiments generally resulted in an initial increase in transmission of EPS through the membrane. Further increases in flux, however led to unexpected results. At low crossflow velocity, EPS transmission did not vary significantly with flux. At higher crossflow velocity, EPS transmission initially increased as flux increased however the transmission then reduced as flux was increased to higher values. Interestingly, EPS concentration in the permeate was much higher than that of the feed supernatant at higher crossflow velocities. This implies that Cp >Cb , or negative retention, therefore the effect of concentration polarisation alone of solutes in the supernatant cannot be used to explain this phenomena. Furthermore EPS transmission through Anopore membranes was unexpectedly higher for the 0.1 μm membrane than for the 0.2 μm membrane. PVDF, with its broader pore size distribution and interconnected pores, resulted in greater amounts of EPS transmission than Anopore membranes of the same 0.2 μm pore size. These phenomena could result from the changes in the structure and composition of the concentration polarization layer especially near the pore entrances and from shear within the system which may act to remove some of the gelatinous sheath around the cells. The effects due to shear within the system are highlighted here. In order to relate the effect of shear and basic polymeric transport to EPS transmission through membrane pores, a brief review of transport of a polymer through a pore is presented. From this a rationalisation of observations on the deposition and removal mechanisms of algal cells (a physical model of interaction of algae and EPS with the membrane) as seen using DOTM is proposed.

Critical behaviour in liquid-crystalline phase transitions: a comparative study of 9OCB in bulk and Anopore membranes

As a humble contribution to this special commemorative issue to Professor Alfred Saupe, we present an experimental study on the critical behaviour of the nematic-to-isotropic (N–I) and smectic A-to-nematic (SmA–N) phase transitions of the liquid crystal 4-nonyloxy-4′-cyanobiphenyl (9OCB). Measurements of the specific heat and the dielectric permittivity were performed for bulk 9OCB as well as for 9OCB confined to Anopore membranes, and the influence of the slight-restrictive confinement was analysed. The possibility of driving the weakly first-order SmA–N phase transition to second-order in nature by means of the confinement was confirmed.

Cylindrical Sub-micrometer Confinement Results for the Odd-Symmetric Dimer α,ω-Bis[(4-cyanobiphenyl)-4′-yloxy]undecane (BCB.O11)

Broadband dielectric spectroscopy (10(2) Hz to 1.9 x 10(9) Hz) and specific heat measurements have been performed on the odd-symmetric dimer alpha,omega-bis[(4-cyanobiphenyl)-4'-yloxy]undecane (BCB.O11) in the isotropic (I) and nematic (N) phases confined to 200 nm diameter parallel cylindrical pores of Anopore membranes. Unlike previous studies on liquid crystal monomers, untreated and hexadecyltrimethylammonium bromide-treated membranes give rise to radial and axial confinements, respectively. An attempt is made to explain these unexpected results by means of a qualitative model for the dimer arrangement on alumina substrates. The model suggests that the population of conformers, which follow the bulk-like dynamics, is modified by confinement. Such a fact seems to be consistent with other distinctive features attributed to confinement, as for example, the increasing of the entropy change at the N-to-I phase transition for both axial and radial confinements. Specific-heat measurements have shown how confinement affects the N-to-I phase transition by a downward shift in transition temperature as well as by broadened and rounded specific-heat peaks. However, these modifications are revealed to be substantially different from what has been found previously in similar studies on liquid crystal monomers. Dynamic dielectric measurements have probed the different molecular motions in both confinements and how these motions are developed in a way similar to the bulk-dimer. Dielectric results have also proved that the surface-pinned molecular layer (where molecular motions are very restricted) adjacent to the pore-wall is temperature-dependent as already found previously for liquid crystal monomers.

Diminution of the Ordering in Plastic and Liquid Crystalline Phases by Confinement

In a compound exhibiting plastic (crystal B) and liquid crystalline (smectic A) phases, we report calorimetric and X-ray features that are drastically affected by confinement and orientation in Anopore membranes. Data on the untreated membranes in which the molecules aligned parallel to the pore axes, show a significant diminution in the correlation length corresponding to the positional order of the plastic phase suggesting that finite size effects can perhaps transform the plastic phase to a hexatic one. In the orthogonal case, having the molecules in the plane of the membrane, a new phase is induced, whose structural possibilities are discussed. Calorimetric measurements corroborate these results and also bring out the different thermal behaviors, not only between the bulk and the confined cases, but also between the situations wherein the orientations of the molecules are different. These findings are expected to open up a new path to understand the melting phenomenon, especially that which occurs in lower dimensions.

Confinement and Surface Effects on the Molecular Dynamics of a Nematic Mixture Investigated by Dielectric Relaxation Spectroscopy

Broadband dielectric spectroscopy (10(-2)-10(9) Hz) was employed to investigate the molecular dynamics of the liquid crystalline mixture E7 confined in both untreated and lecithin-treated 20 nm Anopore membranes. Because E7 does not crystallize, it was possible to cover a temperature range of more than 200 K, providing an exhaustive dielectric characterization of a liquid crystal confined to Anopore membranes for the first time. In the nematic state, the tumbling (alpha-) and the delta-relaxation are observed, also under confinement conditions. The analysis of their relative intensities give that the orientation of the E7 molecules is preferentially axial in untreated but opposite radial in lecithin-treated pores. The radial alignment of the liquid crystals in the modified membrane is understood as a tail-to-tail conformation of E7 molecules imposed by the adsorbed lecithin molecules. The relaxation rate of the alpha-process is enhanced for E7 confined in native Anopore compared with the bulk and E7 in treated pores. This is interpreted as resulting from a less dense molecular packing of E7 in the middle of the pore compared to the bulk. In both untreated and treated membranes, the relaxation rate of the delta-process is higher than in the bulk, and the values of the respective Vogel-Fulcher-Tammann temperatures depend on the actual surface treatment. Additionally, a surface process, due to molecular fluctuations of molecules within an adsorbed layer at the pore wall, was detected.

Rich polymorphism of a rod-like liquid crystal (8CB) confined in two types of unidirectional nanopores

We present a neutron and X-rays scattering study of the phase transitions of 4-n-octyl-4' -cyanobiphenyl (8CB) confined in unidirectional nanopores of porous alumina and porous silicon (PSi) membranes with an average diameter of 30 nm. Spatial confinement reveals a rich polymorphism, with at least four different low temperature phases in addition to the smectic A phase. The structural study as a function of thermal treatments and conditions of spatial confinement allows us to get insights into the formation of these phases and their relative stability. It gives the first description of the complete phase behavior of 8CB confined in PSi and provides a direct comparison with results obtained in bulk conditions and in similar geometric conditions of confinement but with reduced quenched disorder effects using alumina anopore membranes.

Influence of Cylindrical Submicrometer Confinement on the Static and Dynamic Properties in Nonyloxycyanobiphenyl (9OCB)

Broadband dielectric spectroscopy (10(2)-1.9 x 10(9) Hz) and specific heat measurements have been performed on nonyloxycyanobiphenyl (9OCB) in the isotropic (I), nematic (N), and smectic A (SmA) phases confined to 200 nm diameter parallel cylindrical pores of Anopore membranes. Untreated and HTBA-treated membranes have been found to obtain axial and radial confinements, respectively. However, structural or configurational transitions in untreated membranes have been reported to exist in the SmA-mesophase of 9OCB. Both confinements clearly affect the N-I and SmA-N phase transitions. In the axial confinement, the analysis of the specific heat and static dielectric permittivity data leads to a second order SmA-N phase transition, which is known to be weakly first order for bulk 9OCB. Dynamic dielectric measurements have accounted for the different molecular motions in both confinements. On both mesophases, either N or SmA, the relaxation processes in axial configuration are faster than in the bulk. However, in radial confinement, they are either equal or slower than in the bulk. Additionally, there are no differences in the energy barrier hindering the molecular motions between the axial and radial confinements and even in relation to bulk. Likewise, dielectric results suggest that the extension inside the pores of the surface pinned molecular layer (proved to be temperature-dependent) persists at high enough temperature as a residual-thin layer adjacent to the pore wall.

Segmental Dynamics of Poly(methyl acrylate)-d3 Adsorbed on Anopore: A Deuterium NMR Study

The segmental dynamics of poly(methyl acrylate-d3) (PMA-d3) adsorbed in the pores of anopore membranes has been investigated using deuterium NMR over the temperature range 25-80 degrees C. The onset of the NMR glass-transition temperature (Tg) for the adsorbed samples was approximately 15 degrees C higher than that for the bulk sample. The adsorbed polymer contained segments with restricted mobility (glassy), even at the highest temperatures studied, at which the bulk polymer showed only mobile segments. The spectra from samples with different adsorbed amounts of PMA-d3, between 1.1 and 4.2 mg/m2, were similar in their temperature-dependent mobilities. Neither was there much difference in the spectra of PMA-d3 on anopore samples with pore sizes of 0.2 and 0.02 microm. However, for a solvent-washed sample with an adsorbed amount of 0.7 mg/m2, additional restriction in PMA-d3 mobility was observed.

The dielectric relaxation processes in an antiferroelectric liquid crystal under cylindrical confinement

In the cylindrical pore geometry of inorganic Anopore membranes the collective relaxation processes observed in a bulk antiferroelectric liquid crystal change considerably under confinement. The frequency degeneration of the soft and Goldstone modes present at the smectic A* (SmA*)–chiral smectic C (SmC*) phase transition in the bulk phase is removed under geometrical restrictions. The relaxation rate of the soft mode is strongly modified due to the deformation of the smectic layers in the curved geometry of the pores and is superimposed by the molecular relaxation process in the SmA* and SmC* phases. The soft mode in confinement splits into two relaxation processes, which are present through all other mesophases (SmC* and SmCa*). One of them is nearly temperature independent and slightly decreases in frequency in the SmCa* phase. This Goldstone‐like process can be assigned to the highly deformed helical structure fluctuations. The second one exhibits the characteristic features for the molecular and soft mode relaxation processes depending on the temperature range. The biquadratic and the piezoelectric coupling between the tilt angle and spontaneous polarization are revealed in their temperature dependence. †Permanent address: Higher Vocational State School in Piła, ul. Podchorążych 10, 64‐920 Piła, Poland.

Electrically Switchable Liquid Crystal Polymer Rod Actuators

AbstractStimulus responsive liquid crystal nanorods, 60 μm in length and 200 nm in diameter, were fabricated by a template synthesis technique. The liquid crystal, RM 257, is a reactive monomer which polymerizes with the application of UV light. After polymerization the liquid crystal's orientational order is permanently “frozen”. Therefore, the subsequent structures are temperature independent after curing. In this study the liquid crystal was confined in the pores of Anopore membranes before curing, which results in rod structures after photo-polymerization. After fabrication, the rods were observed under the application of both AC and DC electric fields. DC fields were noted by either up and down or translational movement of the rods. Application of AC fields resulted in random movement of the rods.

Evidence for a tilted smectic phase in Anopore membranes by dielectric spectroscopy

Collective relaxation processes are completely undetectable in a ferroelectric liquid crystal confined in porous Anopore membranes, as a result of perfect orientation of the smectic layers perpendicular both to the long axis of the pores and the direction of the measuring electric field. In the ferroelectric liquid crystal – Anopore composite only one relaxation process, assigned to rotation of the molecule around the molecular short axis, appears throughout all smectic phases. The temperature dependence of the relaxation frequency and of the dielectric strength of this process also shows no irregularity at the point of polarization sign reversal. The temperature dependence of the relaxation frequency follows the Arrhenius law with an activation energy slightly higher in the ferroelectric SmC* phase. Analysis of the non‐linear changes of temperature dependence of the dielectric strength at the SmA–SmC* phase transition enables one to obtain the temperature dependence of the tilt angle of the molecules in the SmC* phase in the Anopore membrane. Dielectric measurements confirm the existence of the tilted smectic phase in Anopore cylindrical channels with no tilt anomaly at the point of polarization sign reversal.

Dielectric spectroscopy of aerosil-dispersed liquid crystal embedded in Anopore membranes

The complex dielectric permittivity epsilon* values are presented for aerosil-dispersed 4-pentyl-4-cyanobiphenyl (5CB) confined in Anopore membranes. The dielectric permittivities are measured in the frequency range from 10(-2) Hz to 1 GHz at temperatures ranging from 50 degrees C down to -20 degrees C. In bulk 5CB, which has only a nematic phase, there exist two main relaxation processes: one due to the rotation of molecules around their short axes for parallel orientation of the director to the probing field and another fast relaxation process due to the librational motion of molecules for perpendicular orientation. Inside Anopore membranes both these main relaxation processes can be observed, but with subtle differences. The relaxation process due to the rotation of molecules around the short axis is faster in Anopores at all temperatures in comparison with the bulk process. Hydrophilic aerosil particles, when dispersed in the liquid-crystal (LC) phase, attach to each other via hydrogen bonds and form a three-dimensional interconnecting aerosil network, thus dividing the LC phase into small domains. Dispersing 5CB with different concentrations of hydrophilic aerosils leads to a decrease in relaxation time with aerosil concentration. In these dispersed systems a slow additional relaxation process emerges. This slow process becomes stronger with higher concentrations of aerosil. From our experiments we conclude that this process is the relaxation of 5CB molecules homeotropically aligned to the surface of the aerosil particles. In the case of 5CB-aerosil dispersions enclosed in Anopore membranes this slow process still exists and increases also with aerosil concentration. The relaxation time of the rotation of the 5CB molecules around their short axis systematically increases in these 5CB-aerosil samples in Anopore membranes with aerosil concentration from the 5CB-Anopore behavior towards the behavior observed for 5CB-aerosil dispersions. We explain the evolution as resulting from opposing tendencies from size effects (in the Anopore membranes) and disorder effects (in the aerosil dispersions).

Thermodynamic and Dielectric Studies Concerning the Influence of Cylindrical Submicrometer Confinement on Heptyloxycyanobiphenyl

Measurements of the specific heat and the static dielectric permittivity of heptyloxycyanobiphenyl (7OCB) confined to the 0.2 microm diameter parallel cylindrical pores of Anopore membranes in the isotropic phase and nematic mesophase, are presented. A comparison between the bulk and the confined 7OCB in treated and untreated pore wall surfaces using a chemical surfactant (HTBA) is performed. Both the treated and untreated membrane confinements seem to affect the nematic-to-isotropic phase transition by a downshift in transition temperature and some rounding at the specific-heat maximum, in a way similar to that which was earlier published for other liquid crystals confined in the same geometry. The static dielectric measurements clearly point out that untreated membrane confinement is axial, with the nematic director aligned parallel to the pore axis being homeotropic bulklike, i.e., with the nematic director aligned perpendicular to the electrode cell surfaces. After chemical surfactant treatment, the nematic director is constrained in a radial alignment being perpendicular to the pore walls. The dielectric measurements are revealed to be specially sensible to analyze the surface-induced nematic order due to the pore wall. The tricritical nature of the nematic-to-isotropic phase transition in bulk 7OCB as well as in treated and untreated Anopore confined geometries is discussed through both the specific heat and the static dielectric data.

Influence of nanosized confinements on 4-n-decyl-4′-cyanobiphenyl (10CB): A broadband dielectric study

Real (epsilon') and imaginary (epsilon") parts of the complex dielectric permittivity (epsilon*) of the liquid crystal (LC) 4-n-decyl-4'-cyanobiphenyl (10CB) embedded in Anopore membranes and Vycor porous glass, as well as dispersed with hydrophilic aerosils, have been studied by means of broadband dielectric spectroscopy in the frequency range from 10(-2) Hz to 1 GHz . In bulk 10CB, which has a direct transition from an isotropic to a smectic- A phase, there exists one main relaxation process for the parallel orientation of the director with respect to the probing field and a faster one for the perpendicular orientation. All molecular relaxation processes in 10CB are of Debye type and have Arrhenius like temperature dependence. For 10CB embedded in untreated and surface treated cylindrical pores of Anopore membranes the dielectric spectra are similar to the bulk with the exception that both the rotation around the short axis and the libration motion are faster in the pores. In the case of 10CB dispersed with two different concentrations of hydrophilic aerosils an emergence of a slow relaxation process, which is stronger for the higher concentration, is additionally observed along with the bulklike processes. The slow process in the LC-hydrophilic aerosil system is attributed to the relaxation of the molecules that are homeotropically aligned close to the surfaces of the aerosil particles. This process also has an Arrhenius type of temperature dependence. For 10CB embedded in narrow channels of Vycor porous glass three relaxation processes are observed. Two of these processes are bulklike and are due to the librational motion of molecules and the rotation of molecules around their short axes. The slowest process seems to be a surface process, similar in origin to that observed for 10CB dispersed with hydrophilic aerosils, and is prominent amongst all. The material in the Vycor porous glass could be supercooled by at least 185 degrees below bulk crystallization temperature. The slow process has a Vogel-Fulcher-Tamman (VFT) type of temperature dependence typical for glass formers in this wide temperature range. In addition, the bulklike processes are found to be strongly modified and also have a VFT like temperature dependence from measurements done in a wide temperature range. This behavior is in contrast to other reports of glassy behavior in confined LC, where the glassy behavior as concluded from a slow relaxation process observed in a narrow temperature range.

INFLUENCE OF CONFINING GEOMETRY ON THE DIELECTRIC BEHAVIOR OF A FLC SAMPLE HAVING TGBA PHASE

We report on the dielectric permittivities in 1 kHz to 4 MHz frequency region of the ferroelectric liquid crystal (FLC) material CB500 having a TGBA phase. Molecular and collective relaxation processes have been studied in bulk and in confined environment. In the bulk sample, a Goldstone mode (GM) and a molecular mode were observed in the SmC* phase and the softmode (SM) was observed in the TGBA phase. The Goldstone mode was also present in the FLC sample confined in 0.2 μm Anopore membranes. The relaxation frequency of this mode was shifted to the higher-frequency region in comparison to that observed in the bulk sample. In the Anopore confined FLC sample, another relaxation process (AP) was observed, which possibly arises due to some collective movement of the molecules attached to the cavity walls. The relaxation frequency of this process is almost independent of temperature and this process is only observed in the SmC* phase.