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1.  The genetic basis of female multiple mating in a polyandrous livebearing fish 
Ecology and Evolution  2013;3(1):61-66.
The widespread occurrence of female multiple mating (FMM) demands evolutionary explanation, particularly in the light of the costs of mating. One explanation encapsulated by “good sperm” and “sexy-sperm” (GS-SS) theoretical models is that FMM facilitates sperm competition, thus ensuring paternity by males that pass on genes for elevated sperm competitiveness to their male offspring. While support for this component of GS-SS theory is accumulating, a second but poorly tested assumption of these models is that there should be corresponding heritable genetic variation in FMM – the proposed mechanism of postcopulatory preferences underlying GS-SS models. Here, we conduct quantitative genetic analyses on paternal half-siblings to test this component of GS-SS theory in the guppy (Poecilia reticulata), a freshwater fish with some of the highest known rates of FMM in vertebrates. As with most previous quantitative genetic analyses of FMM in other species, our results reveal high levels of phenotypic variation in this trait and a correspondingly low narrow-sense heritability (h2 = 0.11). Furthermore, although our analysis of additive genetic variance in FMM was not statistically significant (probably owing to limited statistical power), the ensuing estimate of mean-standardized additive genetic variance (IA = 0.7) was nevertheless relatively low compared with estimates published for life-history traits across a broad range of taxa. Our results therefore add to a growing body of evidence that FMM is characterized by relatively low additive genetic variation, thus apparently contradicting GS-SS theory. However, we qualify this conclusion by drawing attention to potential deficiencies in most designs (including ours) that have tested for genetic variation in FMM, particularly those that fail to account for intersexual interactions that underlie FMM in many systems.
PMCID: PMC3568843  PMID: 23403856
Cryptic female choice; genetic correlation; polyandry; promiscuity
2.  Langmuir Films of Flexible Polymers Transferred to Aqueous/Liquid Crystal Interfaces Induce Uniform Azimuthal Alignment of the Liquid Crystal 
We reported recently that amphiphilic polymers can be assembled at interfaces created between aqueous phases and thermotropic liquid crystals (LCs) in ways that (i) couple the organization of the polymer to the order of the LC and (ii) respond to changes in the properties of aqueous phases that can be characterized as changes in the optical appearance of the LC. This investigation sought to characterize the behavior of aqueous-LC interfaces decorated with uniaxially compressed thin films of polymers transferred by Langmuir-Schaefer (LS) transfer. Here, we report physicochemical characterization of interfaces created between aqueous phases and the thermotropic LC 4-cyano-4’-pentylbiphenyl (5CB) decorated with Langmuir films of a novel amphiphilic polymer (polymer 1), synthesized by the addition of hydrophobic and hydrophilic side chains to poly(2-vinyl-4,4’-dimethylazlactone). Initial characterization of this system resulted in the unexpected observation of uniform azimuthal alignment of 5CB after LS transfer of the polymer films to aqueous-5CB interfaces. This paper describes characterization of Langmuir films of polymer 1 hosted at aqueous-5CB interfaces as well as the results of our investigations into the origins of the uniform ordering of the LC observed upon LS transfer. Our results, when combined, support the conclusion that uniform azimuthal alignment of 5CB is the result of long-range ordering of polymer chains in the Langmuir films (in a preferred direction orthogonal to the direction of compression) that is generated during uniaxial compression of the films prior to LS transfer. Although past studies of Langmuir films of polymers at aqueous-air interfaces have demonstrated that in-plane alignment of polymer backbones can be induced by uniaxial compression, these past reports have generally made use of polymers with rigid backbones. One important outcome of this current study is thus the observation of anisotropy and long-range order in Langmuir films of a novel flexible polymer. A second important outcome is the observation that the existence, extent, and dynamics of this order can be identified and characterized optically by transfer of the Langmuir film to a thin film of LC. Additional characterization of Langmuir films of two other flexible polymers [poly(methyl methacrylate) and poly(vinyl stearate)] using this method also resulted in uniform azimuthal alignment of 5CB, suggesting that the generation of long-range order in uniaxially compressed Langmuir films of polymers may also occur more generally over a broader range of polymers with flexible backbones.
PMCID: PMC2785073  PMID: 19836025
Langmuir-Schaefer; Polymer; Liquid Crystals; Interfaces; Uniform Alignment
3.  Scanning electrochemical microscopy studies of micropatterned copper sulfide (CuxS) thin films fabricated by a wet chemistry method 
Electrochimica Acta  2011;56(14-7):5016-5021.
► Copper sulfide (CuxS) microstructures on Si wafer has been prepared using a wet chemistry method. ► To obtain high quality CuxS films, preparative conditions were optimized. Scanning electrochemical microscopy (SECM) was employed to examine the properties of the CuxS films. ► The apparent electron-transfer rate constant (k) of CuxS surface was estimated as 0.04 cm/s. ► The SECM current map showed high edge acuity of the micro-patterned CuxS.
Patterned copper sulfide (CuxS) microstructures on Si (1 1 1) wafers were successfully fabricated by a relatively simple solution growth method using copper sulfate, ethylenediaminetetraacetate and sodium thiosulfate aqueous solutions as precursors. The CuxS particles were selectively deposited on a patterned self-assembled monolayer of 3-aminopropyltriethoxysilane regions created by photolithography. To obtain high quality CuxS films, preparative conditions such as concentration, proportion, pH and temperature of the precursor solutions were optimized. Various techniques such as optical microscopy, atomic force microscopy (AFM), X-ray diffraction, optical absorption and scanning electrochemical microscopy (SECM) were employed to examine the topography and properties of the micro-patterned CuxS films. Optical microscopy and AFM results indicated that the CuxS micro-pattern possessed high selectivity and clear edge resolution. From combined X-ray diffraction analysis and optical band gap calculations we conclude that Cu9S5 (digenite) was the main phase within the resultant CuxS film. Both SECM image and cyclic voltammograms confirmed that the CuxS film had good electrical conductivity. Moreover, from SECM approach curve analysis, the apparent electron-transfer rate constant (k) in the micro-pattern of CuxS dominated surface was estimated as 0.04 cm/s. The SECM current map showed high edge acuity of the micro-patterned CuxS.
PMCID: PMC3112495  PMID: 21785491
Copper sulfide (CuxS); Micro-pattern; Self-assembled monolayer (SAM); Scanning electrochemical microscopy (SECM)
4.  Functionality and Antioxidant Properties of Tilapia (Oreochromis niloticus) as Influenced by the Degree of Hydrolysis 
Freeze dried protein powders (Fresh minced meat, FMM and Hot water dip, HWD) from tilapia (Oreochromis niloticus) were hydrolyzed by Alcalase 2.4 L (Alc), Flavourzyme (Flav) and Neutrase (Neut), and investigated for antioxidant activity and their functional properties. FMM and HWD hydrolysed by Alc, exhibiting superior antioxidant activity, had estimated degrees of hydrolysis (DH) of 23.40% and 25.43%, respectively. The maximum values of the 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), 3-(2-pyridyl) 5,6-bis(4-phenyl-sulphonic acid)-1,2,4-triazine (ferrozine), radical scavenging activities and metal chelating properties were 86.67%, 91.27% and 82.57%, and 84.67%, 92.60% and 78.00% for FMM and HWD, respectively, with a significant difference (P < 0.05) between the samples. Essential amino acids were above the amounts recommended by the Food and Agricultural Organization/World Health Organization (FAO/WHO/UNU) for humans. Lower molecular weight sizes <3,000 Da were more predominant in FMM and HWD hydrolysed by Alc, while in hydrolysed by Flav and Neut they were >8,000 Da. At pH 2, FMM and HWD hydrolysates have varying solubilities above 85% (Alc FMM; 91.33%, Flav FMM; 79.5%, Neut FMM; 83.8% and Alc HWD; 90.45%, Flav HWD; 83.5%, and Neut HWD; 85.8%). They have ‘U’ shaped solubility curves, water holding capacity was in the range of 2.77 and 1.77 mL/g, while oil holding capacity ranged between 3.13 and 2.23 mL/g. FMM and HWD have the highest bulk density of 0.53 and 0.53 for Neutrase and Alcalase 2.4 L, respectively. Foam capacity and stability ranged from 125.5 to 61.4, 138.5 to 45.2, 130.0 to 62.5, and 124.5 to 55.0, 137.5 to 53.3, 129.6 to 62.7 for FMM and HWD hydrolyzed with Alcalase 2.4 L, Flavourzyme and Neutrase, respectively. Tilapia fish protein hydrolysates are thus potential functional food ingredients.
PMCID: PMC2871142  PMID: 20480046
tilapia; fresh minced meat; hot water dip; hydrolysis; antioxidant activity; functional foods
5.  Extension of adaptive tree code and fast multipole methods to high angular momentum particle charge densities 
Journal of computational chemistry  2008;29(12):1895-1904.
The development and implementation of a tree code (TC) and fast multipole method (FMM) for the efficient, linear-scaling calculation of long-range electrostatic interactions of particle distributions with variable shape and multipole character are described. The target application of these methods are stochastic boundary molecular simulations with polarizable force fields and/or combined quantum mechanical/molecular mechanical potentials. Linear-scaling is accomplished through the adaptive decomposition of the system into a hierarchy of interacting particle sets. Two methods for effecting this decomposition are evaluated: fluc-splitting and box-splitting, for which the latter is demonstrated to be generally more accurate. In addition, a generalized termination criterion is developed that delivers optimal performance at fixed error tolerance that, in the case of quadrupole-represented Drude water, effects a speed-up by a factor of 2–3 relative to a multipole-independent termination criteria. The FMM is shown to be approximately 2–3 times faster than the TC, independent of the system size and multipole order of the particles. The TC and FMM are tested for a variety of static and polarizable water systems, and for the the 70S ribosome functional complex containing an assembly of transfer and messenger RNAs.
PMCID: PMC2716046  PMID: 18432622
6.  Surface Chemical and Mechanical Properties of Plasma Polymerized N-isopropylacrylamide 
Surface immobilized poly(N-isopropyl acrylamide) (pNIPAM) is currently used for a wide variety of biosensor and biomaterial applications. A thorough characterization of the surface properties of pNIPAM thin films will benefit those applications. In this work, we present analysis of a plasma polymerized NIPAM (ppNIPAM) coating by multiple surface analytical techniques, including time-of-flight secondary ion mass spectrometry (ToF-SIMS), contact angle measurement, atomic force microscopy (AFM) and sum frequency generation (SFG) vibrational spectroscopy. ToF-SIMS data show that the plasma-deposited NIPAM polymer on the substrate is crosslinked with a good retention of the monomer integrity. Contact angle results confirm the thermoresponse of the film as observed by a change of surface wettability as a function of temperature. Topographic and force distance curve measurements by AFM further demonstrate that the grafted film shrinks or swells depending on the temperature of the aqueous environment. A clear transition of the elastic modulus is observed at 31-32°C. The change of the surface wettability and mechanical properties vs. temperature are attributed to different conformations taken by the polymer, which is reflected on the outmost surface as distinct side chain groups orienting outwards at different temperatures as measured by SFG. The results suggest that a ppNIPAM thin film on a substrate experiences similar mechanical and chemical changes to pNIPAM bulk polymers in solution. The SFG result provides evidence supporting the current theory of the lower critical solution temperature (LCST) behavior of pNIPAM.
PMCID: PMC2527476  PMID: 16089389
N-isopropylacrylamide; plasma polymerized NIPAM (ppNIPAM); thermoresponsive polymer; surface analysis; elastic modulus; ToF-SIMS; AFM; SFG
7.  Characterization of Nanoscale Transformations in Polyelectrolyte Multilayers Fabricated from Plasmid DNA Using Laser Scanning Confocal Microscopy in Combination with Atomic Force Microscopy 
Microscopy research and technique  2010;73(9):834-844.
Laser scanning confocal microscopy (LSCM) and atomic force microscopy (AFM) were used to characterize changes in nanoscale structure that occur when ultrathin polyelectrolyte multilayers (PEMs) are incubated in aqueous media. The PEMs investigated here were fabricated by the deposition of alternating layers of plasmid DNA and a hydrolytically degradable polyamine onto a precursor film composed of alternating layers of linear poly(ethylene imine) (LPEI) and sodium poly(styrene sulfonate) (SPS). Past studies of these materials in the context of gene delivery revealed transformations from a morphology that is smooth and uniform to one characterized by the formation of nanometer-scale particulate structures. We demonstrate that in-plane registration of LSCM and AFM images acquired from the same locations of films fabricated using fluorescently labeled polyelectrolytes allows the spatial distribution of individual polyelectrolyte species to be determined relative to the locations of topographic features that form during this transformation. Our results suggest that this physical transformation leads to a morphology consisting of a relatively less disturbed portion of film composed of polyamine and DNA juxtaposed over an array of particulate structures composed predominantly of LPEI and SPS. Characterization by scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) microanalysis provides additional support for this interpretation. The combination of these different microscopy techniques provides insight into the structures and dynamics of these multicomponent thin films that cannot be achieved using any one method alone, and that could prove useful for the further development of these assemblies as platforms for the surface-mediated delivery of DNA.
PMCID: PMC2889202  PMID: 20155860
Thin Films; Nanostructure; Polymers; Layer-by-Layer; DNA Delivery
8.  Stability and Morphology of Gold Nanoisland Arrays Generated from Layer-by-Layer Assembled Nanoparticle Multilayer Films: Effects of Heating Temperature and Particle Size 
This article reports the effects of heating temperature and composition of nanoparticle multilayer films on the morphology, stability, and optical property of gold nanoisland films prepared by nanoparticle self-assembly/heating method. First, nanoparticle-polymer multilayer films are prepared by the layer-by-layer assembly. Nanoparticle multilayer films are then heated at temperature ranging from 500 °C to 625 °C in air to induce an evaporation of organic matters from the films. During the heating process, the nanoparticles on the solid surface undergo coalescence, resulting in the formation of nanostructured gold island arrays. Characterization of nanoisland films using atomic force microscopy and UV-vis spectroscopy suggests that the morphology and stability of gold island films change when different heating temperatures are applied. Stable gold nanoisland thin film arrays can only be obtained after heat treatments at or above 575 °C. In addition, the results show that the use of nanoparticles with different sizes produces nanoisland films with different morphologies. Multilayer films containing smaller gold nanoparticles tend to produce more monodisperse and smaller island nanostructures. Other variables such as capping ligands around nanoparticles and molecular weight of polymer linkers are found to have only minimal effects on the structure of island films. The adsorption of streptavidin on the biotin-functionalized nanoisland films is studied for examining the biosensing capability of nanoisland arrays.
PMCID: PMC3102539  PMID: 21625329
Nanoislands; Nanoparticles; Self-Assembly; Plasmonics; Au
9.  Tuning the mechanical properties of bioreducible multilayer films for improved cell adhesion and transfection activity 
Biomaterials  2010;31(27):7167-7174.
A simple approach to the mechanical modulation of layer-by-layer (LbL) films is through manipulation of the film assembly. Here, we report results based on altering the salt concentration during film assembly and its effect on film rigidity. Based on changes in film rigidity, cell adhesion characteristics and transfection activity were investigated in vitro. LbL films consisting of reducible hyperbranched poly(amide amine) (RHB) have been implemented along with DNA for investigating fibroblast adhesion on [RHB/DNA]n/2 films with varying rigidities. The rigidity was varied by changing the ionic concentration of the deposition solution between 0.01 M NaCl and 1.0 M NaCl. Molecular force probe (MFP) measurements were performed to measure the apparent Young’s modulus, EAPP, of the films in situ. Cell adhesion and stress-fiber characteristics were investigated using total internal reflectance microscopy (TIRF-M). The average cell peripheral area, fiber density and average fiber length during 5 days of cell growth on films with either low (below 2.0 MPa) or high (above 2.0 MPa) film elastic modulus were investigated. Transfection studies were performed using gfpDNA and SEAP-DNA to investigate if changes in cell adhesion affect transfection activity. Furthermore, cell proliferation and cytotoxicity studies were used to investigate cellular viability over a week. The results have shown that surface modification of bioreducible LbL films of controlled thickness and roughness promotes cellular adhesion, stress-fiber growth and increased transfection activity without the need for an additional adhesive protein pre-coating of the surface or chemical cross-linking of the film.
PMCID: PMC2904610  PMID: 20580430
molecular force probe; MFP; cell adhesion; transfection; TIRF-M; stress fiber orientation; layer-by-layer; LbL; mechanical properties; thin films; elastic modulus; film rigidity
10.  High-speed focal modulation microscopy using acousto-optical modulators 
Biomedical Optics Express  2010;1(3):1026-1037.
Focal Modulation Microscopy (FMM) is a single-photon excitation fluorescence microscopy technique which effectively rejects the out-of-focus fluorescence background that arises when imaging deep inside biological tissues. Here, we report on the implementation of FMM in which laser intensity modulation at the focal plane is achieved using acousto-optic modulators (AOM). The modulation speed is greatly enhanced to the MHz range and thus enables real-time image acquisition. The capability of FMM is demonstrated by imaging fluorescence labeled vasculatures in mouse brain as well as self-made tissue phantom.
PMCID: PMC3018057  PMID: 21258527
(180.2520) Fluorescence microscopy; (110.0113) Imaging through turbid media; (170.0170) Medical optics and biotechnology; (120.4570) Optical design of instruments
11.  Comparison of physicomechanical properties of films prepared from organic solutions and aqueous dispersion of Eudragit RL 
Background and the purpose of the study
Mechanical properties of films prepared from aqueous dispersion and organic solutions of Eudragit RL were assessed and the effects of plasticizer type, concentration and curing were examined.
Films were prepared from aqueous dispersion and solutions of Eudragit RL (isopropy alcohol-water 9:1) containing 0, 10 or 20% (based on polymer weight) of PEG 400 or Triethyl Citrate (TEC) as plasticizer using casting method. Samples of films were stored in oven at 60°C for 24 hrs (Cured). The stress-strain curve was obtained for each film using material testing machine and tensile strength, elastic modulus, %elongation and work of failure were calculated.
Results and major conclusion
The films with no plasticizer showed different mechanical properties depending on the vehicle used. Addition of 10% or 20% of plasticizer decreased the tensile strength and elastic modulus and increased %elongation and work of failure for all films. The effect of PEG 400 on mechanical properties of Eudragit RL films was more pronounced. The differences in mechanical properties of the films due to vehicle decreased with addition of plasticizer and increase in its concentration. Curing process weakened the mechanical properties of the films with no plasticizer and for films with 10% plasticizer no considerable difference in mechanical properties was observed before and after curing. For those with 20% plasticizer only films prepared from aqueous dispersion showed remarkable difference in mechanical properties before and after curing. Results of this study suggest that the mechanical properties of the Eudragit RL films were affected by the vehicle, type of plasticizer and its concentration in the coating liquid.
PMCID: PMC3232102  PMID: 22615646
Eudragit RL; Aqueous polymeric dispersion; Plasticizer; Polymeric film
12.  In vivo skin fluorescence imaging in young Caucasian adults with early malignant melanomas 
Human cutaneous malignant melanoma (CMM) is an aggressive cancer showing a dramatic worldwide increase in incidence over the past few decades. The most prominent relative epidemiological increase has been disclosed in young women. The aim of the study was to assess the effects of chronic sun exposures in order to rate the extend of melanocytic stimulations in the vicinity of CMM.
The study was designed to evaluate the melanin distribution and density using ultraviolet light illumination. The present study was performed on surgical excision specimens of thin CMM lesion removed from the upper limbs of 55 Caucasian adults (37 women and 18 men). Two control groups comprised 23 men and 21 women of similar ages who had medium-size congenital melanocytic nevi, also present on the upper limbs. The peritumoral skin was scrutinized using a Visioscan® VC98 device, revealing the faint mosaic melanoderma (FMM) pattern that grossly indicates early signs of chronic photodamage in epidermal melanin units.
The median extent of relative FMM was significantly higher in the CMM male group. By contrast, the CMM female group showed a reverse bimodal distribution in FMM size. Only 12/37 (32.5%) of the CMM female group had an increased FMM size, whereas 25/37 (67.5%) of females with CMM had a global FMM extent in the normal range, relative to the controls.
Thin CMM supervening in young women appear unrelated to repeat photoexposure. Other mechanisms are possibly involved.
PMCID: PMC4149332  PMID: 25187731
gender; HOX gene; ULEV method; genotoxicity; faint mosaic melanoderma
13.  Direct monitoring of opto-mechanical switching of self-assembled monolayer films containing the azobenzene group 
The potential for manipulation and control inherent in molecule-based motors holds great scientific and technological promise. Molecules containing the azobenzene group have been heavily studied in this context. While the effects of the cis–trans isomerization of the azo group in such molecules have been examined macroscopically by a number of techniques, modulations of the elastic modulus upon isomerization in self-assembled films were not yet measured directly. Here, we examine the mechanical response upon optical switching of bis[(1,1'-biphenyl)-4-yl]diazene organized in a self-assembled film on Au islands, using atomic force microscopy. Analysis of higher harmonics by means of a torsional harmonic cantilever allowed real-time extraction of mechanical data. Quantitative analysis of elastic modulus maps obtained simultaneously with topographic images show that the modulus of the cis-form is approximately twice that of the trans-isomer. Quantum mechanical and molecular dynamics studies show good agreement with this experimental result, and indicate that the stiffer response in the cis-form comprises contributions both from the individual molecular bonds and from intermolecular interactions in the film. These results demonstrate the power and insights gained from cutting-edge AFM technologies, and advanced computational methods.
PMCID: PMC3257510  PMID: 22259768
AFM; azobenzene; elastic modulus; molecular dynamics; nanomechanics; photoswitch; quantum mechanics computation; self-assembled monolayer
14.  Automatic Mapping Extraction from Multiecho T2-Star Weighted Magnetic Resonance Images for Improving Morphological Evaluations in Human Brain 
Mapping extraction is useful in medical image analysis. Similarity coefficient mapping (SCM) replaced signal response to time course in tissue similarity mapping with signal response to TE changes in multiecho T2-star weighted magnetic resonance imaging without contrast agent. Since different tissues are with different sensitivities to reference signals, a new algorithm is proposed by adding a sensitivity index to SCM. It generates two mappings. One measures relative signal strength (SSM) and the other depicts fluctuation magnitude (FMM). Meanwhile, the new method is adaptive to generate a proper reference signal by maximizing the sum of contrast index (CI) from SSM and FMM without manual delineation. Based on four groups of images from multiecho T2-star weighted magnetic resonance imaging, the capacity of SSM and FMM in enhancing image contrast and morphological evaluation is validated. Average contrast improvement index (CII) of SSM is 1.57, 1.38, 1.34, and 1.41. Average CII of FMM is 2.42, 2.30, 2.24, and 2.35. Visual analysis of regions of interest demonstrates that SSM and FMM show better morphological structures than original images, T2-star mapping and SCM. These extracted mappings can be further applied in information fusion, signal investigation, and tissue segmentation.
PMCID: PMC3863404  PMID: 24379892
15.  Characterization of 10,12-pentacosadiynoic acid Langmuir–Blodgett monolayers and their use in metal–insulator–metal tunnel devices 
The characterization of Langmuir–Blodgett thin films of 10,12-pentacosadiynoic acid (PDA) and their use in metal–insulator–metal (MIM) devices were studied. The Langmuir monolayer behavior of the PDA film was studied at the air/water interface using surface tension–area isotherms of polymeric and monomeric PDA. Langmuir–Blodgett (LB, vertical deposition) and Langmuir–Schaefer (LS, horizontal deposition) techniques were used to deposit the PDA film on various substrates (glass, quartz, silicon, and nickel-coated film on glass). The electrochemical, electrical and optical properties of the LB and LS PDA films were studied using cyclic voltammetry, current–voltage characteristics (I–V), and UV–vis and FTIR spectroscopies. Atomic force microscopy measurements were performed in order to analyze the surface morphology and roughness of the films. A MIM tunnel diode was fabricated using a PDA monolayer assembly as the insulating barrier, which was sandwiched between two nickel layers. The precise control of the thickness of the insulating monolayers proved critical for electron tunneling to take place in the MIM structure. The current–voltage characteristics of the MIM diode revealed tunneling behavior in the fabricated Ni–PDA LB film–Ni structures.
PMCID: PMC4273284  PMID: 25551052
Langmuir–Blodgett monolayer; tunnel devices; ultrathin insulator
16.  Quantitative Methods Based on Twisted Nematic Liquid Crystals for Mapping Surfaces Patterned with Bio/Chemical Functionality Relevant to Bioanalytical Assays 
Analytical chemistry  2008;80(8):2637-2645.
We report methods for the acquisition and analysis of optical images formed by thin films of twisted nematic liquid crystals (LCs) placed into contact with surfaces patterned with bio/chemical functionality relevant to surface-based assays. The methods are simple to implement and are shown to provide easily interpreted maps of chemical transformations on surfaces that are widely exploited in the preparation of analytic devices. The methods involve acquisition of multiple images of the LC as a function of the orientation of a polarizer; data analysis condenses the information present in the stack of images into a spatial map of the twist angle of the LC on the analytic surface. The potential utility of the methods is illustrated by mapping (i) the displacement of a monolayer formed from one alkanethiol on a gold film by a second thiol in solution, (ii) coadsorption of mixtures of amine-terminated and ethyleneglycol-terminated alkanethiols on gold films, which leads to a type of mixed monolayer that is widely exploited for immobilization of proteins on analytic surfaces, and (iii) patterns of antibodies printed onto surfaces. These results show that maps of the twist angle of the LC constructed from families of optical images can be used to reveal surface features that are not apparent in a single image of the LC film. Furthermore, the twist angles of the LC can be used to quantify the energy of interaction of the LC with the surface with a spatial resolution of <10 µm. When combined, the results described in this paper suggest non-destructive methods to monitor and validate chemical transformations on surfaces of the type that are routinely employed in the preparation of surface-based analytic technologies.
PMCID: PMC2712289  PMID: 18355089
liquid crystals; patterned chemistry; bioanalytics; chemically functionalized surfaces; imaging; printed antibodies
17.  Reactive Polymer Multilayers Fabricated by Covalent Layer-by-Layer Assembly: 1,4-Conjugate Addition-Based Approaches to the Design of Functional Biointerfaces 
Biomacromolecules  2012;13(5):1523-1532.
We report on conjugate addition-based approaches to the covalent layer-by-layer assembly of thin films and the post-fabrication functionalization of biointerfaces. Our approach is based on a recently reported approach to the ‘reactive’ assembly of covalently-crosslinked polymer multilayers driven by the 1,4-conjugate addition of amine functionality in poly(ethyleneimine) (PEI) to the acrylate groups in a small-molecule pentacrylate species (5-Ac). This process results in films containing degradable β-amino ester crosslinks and residual acrylate and amine functionality that can be used as reactive handles for the subsequent immobilization of new functionality. Layer-by-layer growth of films fabricated on silicon substrates occurred in a supra-linear manner to yield films ~750 nm thick after the deposition of 80 PEI/5-Ac layers. Characterization by AFM suggested a mechanism of growth that involves the reactive deposition of nanometer-scale aggregates of PEI and 5-Ac during assembly. IR spectroscopy studies revealed covalent assembly to occur by 1,4-conjugate addition without formation of amide functionality. Additional experiments demonstrated that acrylate-containing films could be post-functionalized via conjugate addition reactions with small-molecule amines that influence important bio-interfacial properties, including water contact angles and the ability of film-coated surfaces to prevent or promote the attachment of cells in vitro. For example, whereas conjugation of the hydrophobic molecule decylamine resulted in films that supported cell adhesion and growth, films treated with the carbohydrate-based motif D-glucamine resisted cell attachment and growth almost completely for up to 7 days in serum-containing media. We demonstrate that this conjugate addition-based approach also provides a means of immobilizing functionality through labile ester linkages that can be used to promote the long-term, surface-mediated release of conjugated species and promote gradual changes in interfacial properties upon incubation in physiological media (e.g., over a period of at least one month). These covalently-crosslinked films are relatively stable in biological media for prolonged periods, but they begin to physically disintegrate after ~30 days, suggesting opportunities to use this covalent layer-by-layer approach to design functional biointerfaces that ultimately erode or degrade to facilitate elimination.
PMCID: PMC3351563  PMID: 22468967
18.  Optical properties and electrical transport of thin films of terbium(III) bis(phthalocyanine) on cobalt 
The optical and electrical properties of terbium(III) bis(phthalocyanine) (TbPc2) films on cobalt substrates were studied using variable angle spectroscopic ellipsometry (VASE) and current sensing atomic force microscopy (cs-AFM). Thin films of TbPc2 with a thickness between 18 nm and 87 nm were prepared by organic molecular beam deposition onto a cobalt layer grown by electron beam evaporation. The molecular orientation of the molecules on the metallic film was estimated from the analysis of the spectroscopic ellipsometry data. A detailed analysis of the AFM topography shows that the TbPc2 films consist of islands which increase in size with the thickness of the organic film. Furthermore, the cs-AFM technique allows local variations of the organic film topography to be correlated with electrical transport properties. Local current mapping as well as local I–V spectroscopy shows that despite the granular structure of the films, the electrical transport is uniform through the organic films on the microscale. The AFM-based electrical measurements allow the local charge carrier mobility of the TbPc2 thin films to be quantified with nanoscale resolution.
PMCID: PMC4273272  PMID: 25551034
current sensing AFM; ellipsometry; spintronics; TbPc2; transport properties
19.  Influence of water content in mixed solvent on surface morphology, wettability, and photoconductivity of ZnO thin films 
Nanoscale Research Letters  2014;9(1):485.
ZnO thin films have been synthesized by means of a simple hydrothermal method with different solvents. The effect of deionized water content in the mixed solvents on the surface morphology, crystal structure, and optical property has been investigated by scanning electron microscopy, X-ray diffraction, and UV-Vis spectrophotometer. A large number of compact and well-aligned hexagonal ZnO nanorods and the maximal texture coefficient have been observed in the thin film, which is grown in the mixed solvent with x = 40%. A lot of sparse, diagonal, and pointed nanorods can be seen in the ZnO thin film, which is grown in the 40-mL DI water solution. The optical band gap decreases firstly and then increases with the increase of x. Reversible wettability of ZnO thin films were studied by home-made water contact angle apparatus. Reversible transition between hydrophobicity and hydrophilicity may be attributed to the change of surface chemical composition, surface roughness and the proportion of nonpolar planes on the surface of ZnO thin films. Photocurrent response of ZnO thin films grown at different solvents were measured in air. The response duration of the thin film, which is grown in the solvent with x = 40%, exhibits a fast growth in the beginning but cannot approach the saturate current value within 100 s. The theoretical mechanism for the slower growth or decay duration of the photocurrent has been discussed in detail.
PMCID: PMC4171712  PMID: 25249823
Thin films; Chemical synthesis; Electron microscopy; Electrical conductivity
20.  Preparation and Characterization of Covalently Binding of Rat Anti-human IgG Monolayer on Thiol-Modified Gold Surface 
Nanoscale Research Letters  2009;4(12):1403-1408.
The 16-mercaptohexadecanoic acid (MHA) film and rat anti-human IgG protein monolayer were fabricated on gold substrates using self-assembled monolayer (SAM) method. The surface properties of the bare gold substrate, the MHA film and the protein monolayer were characterized by contact angle measurements, atomic force microscopy (AFM), grazing incidence X-ray diffraction (GIXRD) method and X-ray photoelectron spectroscopy, respectively. The contact angles of the MHA film and the protein monolayer were 18° and 12°, respectively, all being hydrophilic. AFM images show dissimilar topographic nanostructures between different surfaces, and the thickness of the MHA film and the protein monolayer was estimated to be 1.51 and 5.53 nm, respectively. The GIXRD 2θ degrees of the MHA film and the protein monolayer ranged from 0° to 15°, significantly smaller than that of the bare gold surface, but the MHA film and the protein monolayer displayed very different profiles and distributions of their diffraction peaks. Moreover, the spectra of binding energy measured from these different surfaces could be well fitted with either Au4f, S2p or N1s, respectively. Taken together, these results indicate that MHA film and protein monolayer were successfully formed with homogeneous surfaces, and thus demonstrate that the SAM method is a reliable technique for fabricating protein monolayer.
PMCID: PMC2893859  PMID: 20652126
Rat anti-human IgG; Self-assembled monolayer; Covalent binding; Contact angle; Atomic force microscopy; Grazing incidence X-ray diffraction; X-ray photoelectron spectroscopy
21.  Preparation and Characterization of Covalently Binding of Rat Anti-human IgG Monolayer on Thiol-Modified Gold Surface 
Nanoscale Research Letters  2009;4(12):1403-1408.
The 16-mercaptohexadecanoic acid (MHA) film and rat anti-human IgG protein monolayer were fabricated on gold substrates using self-assembled monolayer (SAM) method. The surface properties of the bare gold substrate, the MHA film and the protein monolayer were characterized by contact angle measurements, atomic force microscopy (AFM), grazing incidence X-ray diffraction (GIXRD) method and X-ray photoelectron spectroscopy, respectively. The contact angles of the MHA film and the protein monolayer were 18° and 12°, respectively, all being hydrophilic. AFM images show dissimilar topographic nanostructures between different surfaces, and the thickness of the MHA film and the protein monolayer was estimated to be 1.51 and 5.53 nm, respectively. The GIXRD 2θ degrees of the MHA film and the protein monolayer ranged from 0° to 15°, significantly smaller than that of the bare gold surface, but the MHA film and the protein monolayer displayed very different profiles and distributions of their diffraction peaks. Moreover, the spectra of binding energy measured from these different surfaces could be well fitted with either Au4f, S2p or N1s, respectively. Taken together, these results indicate that MHA film and protein monolayer were successfully formed with homogeneous surfaces, and thus demonstrate that the SAM method is a reliable technique for fabricating protein monolayer.
PMCID: PMC2893859  PMID: 20652126
Rat anti-human IgG; Self-assembled monolayer; Covalent binding; Contact angle; Atomic force microscopy; Grazing incidence X-ray diffraction; X-ray photoelectron spectroscopy
22.  The interfacial structure and Young's modulus of peptide films having switchable mechanical properties 
We report the structure and Young's modulus of switchable films formed by peptide self-assembly at the air–water interface. Peptide surfactant AM1 forms an interfacial film that can be switched, reversibly, from a high- to low-elasticity state, with rapid loss of emulsion and foam stability. Using neutron reflectometry, we find that the AM1 film comprises a thin (approx. 15 Å) layer of ordered peptide in both states, confirming that it is possible to drastically alter the mechanical properties of an interfacial ensemble without significantly altering its concentration or macromolecular organization. We also report the first experimentally determined Young's modulus of a peptide film self-assembled at the air–water interface (E=80 MPa for AM1, switching to E<20 MPa). These findings suggest a fundamental link between E and the macroscopic stability of peptide-containing foam. Finally, we report studies of a designed peptide surfactant, Lac21E, which we find forms a stronger switchable film than AM1 (E=335 MPa switching to E<4 MPa). In contrast to AM1, Lac21E switching is caused by peptide dissociation from the interface (i.e. by self-disassembly). This research confirms that small changes in molecular design can lead to similar macroscopic behaviour via surprisingly different mechanisms.
PMCID: PMC2605502  PMID: 17550885
peptide; Young's modulus; interface; film; neutron reflectometry
23.  Uniform Thin Films of CdSe and CdSe(ZnS) Core(shell) Quantum Dots by Sol-Gel Assembly: Enabling Photoelectrochemical Characterization and Electronic Applications 
ACS nano  2013;7(2):1215-1223.
Optoelectronic properties of quantum dot (QD) films are limited by (1) poor interfacial chemistry and (2) non-radiative recombination due to surface traps. To address these performance issues, sol-gel methods are applied to fabricate thin films of CdSe and core(shell) CdSe(ZnS) QDs. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging with chemical analysis confirms that the surface of the QDs in the sol-gel thin films are chalcogen-rich, consistent with an oxidative-induced gelation mechanism in which connectivity is achieved by formation of dichalcogenide covalent linkages between particles. The ligand removal and assembly process is probed by thermogravimetric, spectroscopic and microscopic studies. Further enhancement of inter-particle coupling via mild thermal annealing, which removes residual ligands and reinforces QD connectivity, results in QD sol-gel thin films with superior charge transport properties, as shown by a dramatic enhancement of electrochemical photocurrent under white light illumination relative to thin films composed of ligand-capped QDs. A more than 2-fold enhancement in photocurrent, and a further increase in photovoltage can be achieved by passivation of surface defects via overcoating with a thin ZnS shell. The ability to tune interfacial and surface characteristics for the optimization of photophysical properties suggests that the sol-gel approach may enable formation of QD thin films suitable for a range of optoelectronic applications.
PMCID: PMC3590068  PMID: 23350924
Quantum dots; Sol-gel methods; Photocurrent; surface passivation; ligand exchange
24.  AFM study of morphology and mechanical properties of a chimeric spider silk and bone sialoprotein protein for bone regeneration 
Biomacromolecules  2011;12(5):1675-1685.
Atomic force microscopy (AFM) was used to assess a new chimeric protein consisting of a fusion protein of the consensus repeat for Nephila clavipes spider dragline protein and bone sialoprotein (6mer+BSP). The elastic modulus of this protein in film form was assessed through force curves, and film surface roughness was also determined. The results showed a significant difference between the elastic modulus of the chimeric silk protein, 6mer+BSP, and control films consisting of only the silk component (6mer). The behaviour of the 6mer+BSP and 6mer proteins in aqueous solution in the presence of calcium (Ca) ions was also assessed to determine interactions between the inorganic and organic components related to bone interactions, anchoring and biomaterial network formation. The results demonstrated the formation of protein networks in the presence of Ca2+ ions, characteristics that may be important in the context of controlling materials assembly and properties related to bone-formation with this new chimeric silk-BSP protein.
PMCID: PMC3090475  PMID: 21370930
Atomic force microscope; chimeric proteins; silk; mechanical properties; calcium mediated networks; bone regeneration
25.  Solid-State Densification of Spun-Cast Self-Assembled Monolayers for Use in Ultra-Thin Hybrid Dielectrics 
Applied surface science  2012;261:10.1016/j.apsusc.2012.09.013.
Ultra-thin self-assembled monolayer (SAM)-oxide hybrid dielectrics have gained significant interest for their application in low-voltage organic thin film transistors (OTFTs). A [8-(11-phenoxy-undecyloxy)-octyl]phosphonic acid (PhO-19-PA) SAM on ultrathin AlOx (2.5 nm) has been developed to significantly enhance the dielectric performance of inorganic oxides through reduction of leakage current while maintaining similar capacitance to the underlying oxide structure. Rapid processing of this SAM in ambient conditions is achieved by spin coating, however, as-cast monolayer density is not sufficient for dielectric applications. Thermal annealing of a bulk spun-cast PhO-19-PA molecular film is explored as a mechanism for SAM densification. SAM density, or surface coverage, and order are examined as a function of annealing temperature. These SAM characteristics are probed through atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure spectroscopy (NEXAFS). It is found that at temperatures sufficient to melt the as-cast bulk molecular film, SAM densification is achieved; leading to a rapid processing technique for high performance SAM-oxide hybrid dielectric systems utilizing a single wet processing step. To demonstrate low-voltage devices based on this hybrid dielectric (with leakage current density of 7.7×10−8 A cm−2 and capacitance density of 0.62 µF cm−2 at 3 V), pentacene thin-film transistors (OTFTs) are fabricated and yield sub 2 V operation and charge carrier mobilites of up to 1.1 cm2 V−1 s−1.
PMCID: PMC3840438  PMID: 24288423
Self Assembled Monolayer (SAM); SAM Dielectric; Hybrid Dielectric; SAM Processing; Organic Field Effect Transistor (OFET); Organic Thin Film Transistor (OTFT)

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