Monolithic 3D printing of embeddable and highly stretchable strain sensors using conductive ionogels.

Medical training simulations that utilize 3D-printed, patient-specific tissue models improve practitioner and patient understanding of individualized procedures and capacitate pre-operative, patient-specific rehearsals. The impact of these novel constructs in medical training and pre-procedure rehearsals has been limited, however, by the lack of effectively embedded sensors that detect the location, direction, and amplitude of strains applied by the practitioner on the simulated structures. The monolithic fabrication of strain sensors embedded into lifelike tissue models with customizable orientation and placement could address this limitation. The demonstration of 3D printing of an ionogel as a stretchable, piezoresistive strain sensor embedded in an elastomer is presented as a proof-of-concept of this integrated fabrication for the first time. The significant hysteresis and drift inherent to solid-phase piezoresistive composites and the dimensional instability of low-hysteresis piezoresistive liquids inspired the adoption of a 3D-printable piezoresistive ionogel composed of reduced graphene oxide and an ionic liquid. The shear-thinning rheology of the ionogel obviates the need to fabricate additional structures that define or contain the geometry of the sensing channel. Sensors are printed on and subsequently encapsulated in polydimethylsiloxane (PDMS), a thermoset elastomer commonly used for analog tissue models, to demonstrate seamless fabrication. Strain sensors demonstrate geometry- and strain-dependent gauge factors of 0.54-2.41, a high dynamic strain range of 350% that surpasses the failure strain of most dermal and viscus tissue, low hysteresis (<3.5% degree of hysteresis up to 300% strain) and baseline drift, a single-value response, and excellent fatigue stability (5000 stretching cycles). In addition, we fabricate sensors with stencil-printed silver/PDMS electrodes in place of wires to highlight the potential of seamless integration with printed electrodes. The compositional tunability of ionic liquid/graphene-based composites and the shear-thinning rheology of this class of conductive gels endows an expansive combination of customized sensor geometry and performance that can be tailored to patient-specific, high-fidelity, monolithically fabricated tissue models.

Impact of sphingomyelin acyl chain (16:0 vs 24:1) on the interfacial properties of Langmuir monolayers: A PM-IRRAS study.

Membrane structure is a key factor for the cell`s physiology, pathology, and therapy. Evaluating the importance of lipid species such as N-nervonoyl sphingomyelin (24:1-SM) -able to prevent phase separation- to membrane structuring remains a formidable challenge. This is the first report in which polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) is applied to investigate the lipid-lipid interactions in 16:0 vs 24:1-SM monolayers and their mixtures with 1,2-Dioleoyl-sn-glycero-3-phosphocholine (DOPC) and cholesterol (Chol) (DOPC/SM/Chol 2:1:1). From the results we inferred that the cis double bond (Δ15) in 24:1-SM molecule diminishes intermolecular H-bonding and chain packing density compared to that of 16:0-SM. In ternary mixtures containing 16:0-SM, the relative intensity of the two components of the Amide I band reflected changes in the H-bonding network due to SM-Chol interactions. In contrast, the contribution of the main components of the Amide I band in DOPC/24:1-SM/Chol remained as in 24:1-SM monolayers, with a larger contribution of the non-H-bonded component. The most interesting feature in these ternary films is that the CO stretching mode of DOPC appeared with an intensity similar to that of SM Amide I band in DOPC/16:0-SM/Chol monolayers (a two-phase [Lo/Le] system), whereas an extremely low intensity of the CO band was detected in DOPC/24:1-SM/Chol monolayers (single Le phase). This is evidence that the unsaturation in 24:1-SM affected not only the conformational properties of acyl chains but also the orientation of the chemical groups at the air/water interface. The physical properties and overall H-bonding ability conferred by 24:1-SM may have implications in cell signaling and binding of biomolecules.

Interaction of acylated and unacylated forms of E. coli alpha-hemolysin with lipid monolayers: a PM-IRRAS study.

Uropathogenic strains of Escherichia coli produce virulence factors, such as the protein toxin alpha-hemolysin (HlyA), that enable the bacteria to colonize the host and establish an infection. HlyA is synthetized as a protoxin (ProHlyA) that is transformed into the active form in the bacterial cytosol by the covalent linkage of two fatty-acyl moieties to the polypeptide chain before the secretion of HlyA into the extracellular medium. The aim of this work was to investigate the effect of the fatty acylation of HlyA on protein conformation and protein-membrane interactions. Polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) experiments were performed at the air-water interface, and lipid monolayers mimicking the outer leaflet of red-blood-cell membranes were used as model systems for the study of protein-membrane interaction. According to surface-pressure measurements, incorporation of the acylated protein into the lipid films was faster than that of the nonacylated form. PM-IRRAS measurements revealed that the adsorption of the proteins to the lipid monolayers induced disorder in the lipid acyl chains and also changed the elastic properties of the films independently of protein acylation. No significant difference was observed between HlyA and ProHlyA in the interaction with the model lipid monolayers; but when these proteins became adsorbed on a bare air-water interface, they adopted different secondary structures. The assumption of the correct protein conformation at a hydrophobic-hydrophilic interface could constitute a critical condition for biologic activity.

Experimental evidence for the mode of action based on electrostatic and hydrophobic forces to explain interaction between chitosans and phospholipid Langmuir monolayers.

The interaction between chitosans and Langmuir monolayers mimicking cell membranes has been explained with an empirical scheme based on electrostatic and hydrophobic forces, but so far this has been tested only for dimyristoyl phosphatidic acid (DMPA). In this paper, we show that the mode of action in such a scheme is also valid for dipalmitoyl phosphatidyl choline (DPPC) and dipalmitoyl phosphatidyl glycerol (DPPG), whose monolayers were expanded and their compressibility modulus decreased by interacting with chitosans. In general, the effects were stronger for the negatively charged DPPG in comparison to DPPC, and for the low molecular weight chitosan (LMWChi) which was better able to penetrate into the hydrophobic chains than the high molecular weight chitosan (Chi). Penetration into the hydrophobic chains was confirmed with polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS) and sum frequency generation (SFG) spectroscopy. A slight reduction in conformational order of the lipid chains induced by the chitosans was quantitatively estimated by measuring the ratio between the intensities of the methyl (r(+)) and methylene (d(+)) peaks in the SFG spectra for DPPG. The ratio decreased from 35.6 for the closely packed DPPG monolayer to 7.0 and 6.6 for monolayers containing Chi and LMWChi, respectively. Since in both cases there was a significant phospholipid monolayer expansion, the incorporation of chitosans led to chitosan-rich and lipid-rich condensed domains, which mantained conformational order for their hydrophobic tails. The stronger effects from LMWChi are ascribed to an easier access to the hydrophobic tails, as corroborated by measuring aggregation in solution with dynamic light scattering, where the hydrodynamic radius for LMWChi was close to half of that for Chi. Taken together, the results presented here confirm that the same mode of action applies to different phospholipids that are important constituents of mammalian (DPPC) and bacterial (DPPG) cell membranes.

Molecular-Level Modifications Induced by Photo-Oxidation of Lipid Monolayers Interacting with Erythrosin.

Incorporation into cell membranes is key for the action of photosensitizers in photomedicine treatments, with hydroperoxidation as the prominent pathway of lipid oxidation. In this paper, we use Langmuir monolayers of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) as cell membrane models to investigate adsorption of the photosensitizer erythrosin and its effect on photoinduced lipid oxidation. From surface pressure isotherms and polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) data, erythrosin was found to adsorb mainly via electrostatic interaction with the choline in the head groups of both DOPC and DPPC. It caused larger monolayer expansion in DOPC, with possible penetration into the hydrophobic unsaturated chains, while penetration into the DPPC saturated chains was insignificant. Easier penetration is due to the less packed DOPC monolayer, in comparison to the more compact DPPC according to the monolayer compressibility data. Most importantly, light irradiation at 530 nm made the erythrosin-containing DOPC monolayer become less unstable, with a relative surface area increase of ca. 19%, in agreement with previous findings for bioadhesive giant vesicles. The relative area increase is consistent with hydroperoxidation, supporting the erythrosin penetration into the lipid chains, which favors singlet oxygen generation close to double bonds, an important requirement for photodynamic efficiency.

Impedance sensing device enables early detection of pressure ulcers in vivo.

When pressure is applied to a localized area of the body for an extended time, the resulting loss of blood flow and subsequent reperfusion to the tissue causes cell death and a pressure ulcer develops. Preventing pressure ulcers is challenging because the combination of pressure and time that results in tissue damage varies widely between patients, and the underlying damage is often severe by the time a surface wound becomes visible. Currently, no method exists to detect early tissue damage and enable intervention. Here we demonstrate a flexible, electronic device that non-invasively maps pressure-induced tissue damage, even when such damage cannot be visually observed. Using impedance spectroscopy across flexible electrode arrays in vivo on a rat model, we find that impedance is robustly correlated with tissue health across multiple animals and wound types. Our results demonstrate the feasibility of an automated, non-invasive 'smart bandage' for early detection of pressure ulcers.

N-terminal microdomain peptide from human dihydroorotate dehydrogenase: structure and model membrane interactions.

The N-terminus of the human dihydroorotate dehydrogenase (HsDHODH) has been described as important for the enzyme attachment in the inner mitochondrial membrane and possibly to regulate enzymatic activity. In this study, we synthesized the peptide acetyl-GDERFYAEHLMPTLQGLLDPESAHRL AVRFTSLGamide, comprising the residues 33-66 of HsDHODH N-terminal conserved microdomain. Langmuir monolayers and circular dichroism (CD) were employed to investigate the interactions between the peptide and membrane model, as micelles and monolayers of the lipids phosphatidylcholine (PC), 3-phosphatidylethanolamine (PE) and cardiolipin (CL). These lipids represent the major constituents of inner mitochondrial membranes. According to CD data, the peptide adopted a random structure in water, whereas it acquired α-helical structures in the presence of micelles. The π-A isotherms and polarization- modulated infrared reflection-absorption spectroscopy on monolayers showed that the peptide interacted with all lipids, but in different ways. In DPPC monolayers, the peptide penetrated into the hydrophobic region. The strongest initial interaction occurred with DPPE, but the peptide was expelled from this monolayer at high surface pressures. In CL, the peptide could induce a partial dissolution of the monolayer, leading to shorter areas at the monolayer collapse. These results corroborate the literature, where the HsDHODH microdomain is anchored into the inner mitochondrial membrane. Moreover, the existence of distinct conformations and interactions with the different membrane lipids indicates that the access to the enzyme active site may be controlled not only by conformational changes occurring at the microdomain of the protein, but also by some lipid-protein synergetic mechanism, where the HsDHODH peptide would be able to recognize lipid domains in the membrane.

Printed and flexible biosensor for antioxidants using interdigitated ink-jetted electrodes and gravure-deposited active layer.

Printing techniques have been extensively used in the fabrication of organic electronic devices, such as light-emitting diodes and display backplanes. These techniques, in particular inkjet printing, are being employed for the localized dispensing of solutions containing biological molecules and cells, leading to the fabrication of bio-functional microarrays and biosensors. Here, we report the fabrication of an all-printed and flexible biosensor for antioxidants. Gold (Au) interdigitated electrodes (IDEs) with sub-100 µm features were directly inkjet-printed on plastic substrates using a nanoparticle-based ink. Conductivities as high as 5×10(6) S/m (12% of bulk Au) were attained after sintering was conducted at plastic-compatible 200 °C for 6 h. The enzyme Tyrosinase (Tyr) was used in the active layer of the biosensors, being innovatively deposited by large-area rotogravure printing. A tailor-made ink was studied, and the residual activity of the enzyme was 85% after additives incorporation, and 15.5% after gravure printing. Au IDEs were coated with gravure films of the Tyr-containing ink, and the biosensor was encapsulated with a cellulose acetate dip-coating film to avoid dissolution. The biosensor impedance magnitude increases linearly with the concentration of a model antioxidant, allowing for the construction of a calibration curve. Control experiments demonstrated the molecular recognition characteristic inferred by the enzyme. We found that the biosensor sensitivity and the limit of detection were, respectively, 5.68 Ω/µm and 200 µM. In conclusion, a disposable, light-weight, all-printed and flexible biosensor for antioxidants was successfully fabricated using fast and large-area printing techniques. This opens the door for the fabrication of technological products using roll-to-roll processes.

Chitosan does not inhibit enzymatic action of human pancreatic lipase in Langmuir monolayers of 1,2-didecanoyl-glycerol (DDG).

In this study, we tested the hypothesis according to which chitosan reduces lipid digestion by blocking the access of lipases to ingested fat. Because lipase action takes place mostly at interfaces, we produced Langmuir films of 1,2-didecanoyl-glycerol (DDG), which is the substrate for human pancreatic lipase (HPL). The experimental assays were carried out in acidic medium, at pH 3.0, to ensure that chitosan is completely soluble. Chitosan was found to affect strongly the surface activity of HPL that forms a Gibbs monolayer at the air/water interface, but did not inhibit the enzymatic action of HPL toward the DDG monolayer. The latter was observed using two surface-specific spectroscopic techniques, namely polarization-modulated infrared reflection-absorption and sum-frequency generation (SFG). The extension of DDG hydrolysis calculated using SFG spectroscopy was 33% in the absence of chitosan, and ranged from 29 to 50% in the presence of chitosan at concentrations of 0.20 g L(-1) and 0.30 g L(-1), respectively. Therefore, fat "protection" by chitosan is unlikely to be an important factor in fat reduction.

The negligible effects of the antifungal natamycin on cholesterol-dipalmitoyl phosphatidylcholine monolayers may explain its low oral and topical toxicity for mammals.

Natamycin is an effective, broad spectrum antifungal with no reported resistance, in contrast to most antimicrobials. It also exhibits reduced (oral and topical) toxicity to humans, which is probably associated with the lack of effects on mammalian cell membranes. In this paper we employ Langmuir monolayers to mimic a cell membrane, whose properties are interrogated with various techniques. We found that natamycin has negligible effects on Langmuir monolayers of dipalmitoyl phosphatidylcholine (DPPC), but it strongly affects cholesterol monolayers. Natamycin causes the surface pressure isotherm of a cholesterol monolayer to expand even at high surface pressures since it penetrates into the hydrophobic chains. It also reduces the compressibility modulus, probably because natamycin disturbs the organization of the cholesterol molecules, as inferred with polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS). In mixed cholesterol/DPPC monolayers, strong effects from natamycin were only observed when the cholesterol concentration was 50mol% or higher, well above its concentration in a mammalian cell membrane. For a sterol concentration that mimics a real cell membrane in mammals, i.e. with 25mol% of cholesterol, the effects were negligible, which may explain why natamycin has low toxicity when ingested and/or employed to treat superficial fungal infections.

Vibrational spectroscopy for probing molecular-level interactions in organic films mimicking biointerfaces.

Investigation into nanostructured organic films has served many purposes, including the design of functionalized surfaces that may be applied in biomedical devices and tissue engineering and for studying physiological processes depending on the interaction with cell membranes. Of particular relevance are Langmuir monolayers, Langmuir-Blodgett (LB) and layer-by-layer (LbL) films used to simulate biological interfaces. In this review, we shall focus on the use of vibrational spectroscopy methods to probe molecular-level interactions at biomimetic interfaces, with special emphasis on three surface-specific techniques, namely sum frequency generation (SFG), polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS) and surface-enhanced Raman scattering (SERS). The two types of systems selected for exemplifying the potential of the methods are the cell membrane models and the functionalized surfaces with biomolecules. Examples will be given on how SFG and PM-IRRAS can be combined to determine the effects from biomolecules on cell membrane models, which include determination of the orientation and preservation of secondary structure. Crucial information for the action of biomolecules on model membranes has also been obtained with PM-IRRAS, as is the case of chitosan removing proteins from the membrane. SERS will be shown as promising for enabling detection limits down to the single-molecule level. The strengths and limitations of these methods will also be discussed, in addition to the prospects for the near future.

Interaction of O-acylated chitosans with biomembrane models: probing the effects from hydrophobic interactions and hydrogen bonding.

One of the major challenges in establishing the mechanisms responsible for the chitosan action in biomedical applications lies in the determination of the molecular-level interactions with the cell membrane. In this study, we probed hydrophobic interactions and H-bonding in experiments with O,O'-diacetylchitosan (DACT) and O,O'-dipropionylchitosan (DPPCT) incorporated into monolayers of distinct phospholipids, the zwitterionic dipalmitoyl phosphatidyl choline (DPPC), and the negatively charged dipalmitoyl phosphatidyl glycerol (DPPG) and dimyristoyl phosphatidic acid (DMPA). The importance of hydrophobic interactions was confirmed with the larger effects observed for DACT and DPPCT than for parent chitosan (Chi), particularly for the more hydrophobic DPPCT. Such larger effects were noted in surface pressure isotherms and elasticity of the monolayers. Since H-bonding is hampered for the chitosan derivatives, which have part of their hydroxyl groups shielded by O-acylation, these effects indicate that H-bonding does not play an important role in the chitosan-membrane interactions. Using polarization-modulated infrared reflection absorption (PM-IRRAS) spectroscopy, we found that the chitosan derivatives were incorporated into the hydrophobic chain of the phospholipids, even at high surface pressures comparable to those in a real cell membrane. Taken together, these results indicate that the chitosan derivatives containing hydrophobic moieties would probably be more efficient than parent chitosan as antimicrobial agents, where interaction with the cell membrane is crucial.

Optical storage in azobenzene-containing epoxy polymers processed as Langmuir Blodgett films.

In this study, azocopolymers containing different main-chain segments have been synthesized with diglycidyl ether of bisphenol A (DGEBA, DER 332, n=0.03) and the azochromophore Disperse Orange 3 (DO3) cured with two monoamines, viz. benzylamine (BA) and m-toluidine (MT). The photoinduced birefringence was investigated in films produced with these azopolymers using the spin coating (SC) and Langmuir Blodgett (LB) techniques. In the LB films, birefringence increased with the content of azochromophore and the film thickness, as expected. The nanostructured nature of the LB films led to an enhanced birefringence and faster dynamics in the writing process, compared to the SC films. In summary, the combination of azocopolymers and the LB method may allow materials with tuned properties for various optical applications, including in biological systems were photoisomerization may be used to trigger actions such as drug delivery.

Low molecular-weight chitosans are stronger biomembrane model perturbants.

The influence from the chitosan molecular weight on its interaction with cell membrane models has been studied. A low molecular weight chitosan (LMWChi) adsorbed from the subphase expanded the surface pressure-area and surface potential-area isotherms of dimyristoyl phosphatidic acid (DMPA) monolayers and decreased the compressional modulus. The expansion in the monolayers and the decrease in the compressional modulus were larger for LMWChi than for a high molecular weight chitosan (Chi). The polymeric nature is still essential for the interaction though, which was demonstrated by measuring negligible changes in the mechanical properties of the DMPA monolayer when the subphase contained glucosamine and acetyl-glucosamine. The results were rationalized in a model through which chitosan interacted with the membrane via electrostatic and hydrophobic interactions, with the smaller chains of LMWChi having less steric hindrance to be accommodated in the membrane. In summary, the activity based on membrane interactions depends on the distribution of molar mass, with lower molecular weight chitosan more likely to have stronger effects.

Information visualization to enhance sensitivity and selectivity in biosensing.

An overview is provided of the various methods for analyzing biosensing data, with emphasis on information visualization approaches such as multidimensional projection techniques. Emphasis is placed on the importance of data analysis methods, with a description of traditional techniques, including the advantages and limitations of linear and non-linear methods to generate layouts that emphasize similarity/dissimilarity relationships among data instances. Particularly important are recent methods that allow processing high-dimensional data, thus taking full advantage of the capabilities of modern equipment. In this area, now referred to as e-science, the choice of appropriate data analysis methods is crucial to enhance the sensitivity and selectivity of sensors and biosensors. Two types of systems deserving attention in this context are electronic noses and electronic tongues, which are made of sensor arrays whose electrical or electrochemical responses are combined to provide "finger print" information for aromas and tastes. Examples will also be given of unprecedented detection of tropical diseases, made possible with the use of multidimensional projection techniques. Furthermore, ways of using these techniques along with other information visualization methods to optimize biosensors will be discussed.

Interaction of chitosan and mucin in a biomembrane model environment.

Chitosans have been widely exploited in biological applications, including drug delivery and tissue engineering, especially owing to their mucoadhesive properties, but the molecular-level mechanisms for the chitosan action are not known in detail. It is believed that chitosan could affect the mucus by interacting with the proteins mucins, in a process mediated by the cell membrane. In this study we used Langmuir monolayers of dimyristoylphosphatidic acid (DMPA) as simplified membrane models to investigate the interplay between the activity of mucins and chitosan. Surface pressure and surface potential measurements were performed with DMPA monolayers onto which chitosan and/or mucin was adsorbed. We found that the expanding effect from mucin was considerably reduced when chitosan was injected after mucin had been adsorbed on the DMPA monolayer. The results were consistent with the formation of complexes between mucin and chitosan, thus highlighting the importance of electrostatic interactions. Furthermore, chitosan could remove mucin that was co-deposited along with DMPA in Langmuir-Blodgett (LB) films, which could be ascribed to molecular-level interactions between chitosan and mucin inferred from the FTIR spectra of the LB films. In conclusion, the results with Langmuir and LB films suggest that electrostatic interactions are crucial for the mucoadhesive mechanism, which is affected by the complexation between chitosan and mucin.

The role of the C-terminal region of pulchellin A-chain in the interaction with membrane model systems.

Pulchellin is a Ribosome Inactivating Protein containing an A-chain (PAC), whose toxic activity requires crossing the endoplasmic reticulum (ER) membrane. In this paper, we investigate the interaction between recombinant PAC (rPAC) and Langmuir monolayers of dipalmitoyl phosphatidyl glycerol (DPPG), which served as membrane model. Three catalytically active, truncated PACs with increasing deletion of the C-terminal region, possessing 244, 239 and 236 residues (rPAC(244), rPAC(239) and rPAC(236)), were studied. rPAC had the strongest interaction with the DPPG monolayer, inducing a large expansion in its surface pressure-area isotherm. The affinity to DPPG decreased with increased deletion of the C-terminal region. When the C-terminal region was deleted completely (rPAC(236)), the interaction was recovered, probably because other hydrophobic regions were exposed to the membrane. Using Polarization Modulated-Infrared Reflection Absorption Spectroscopy (PM-IRRAS) we observed that at a bare air/water interface rPAC comprised mainly α-helix structures, the C-terminal region had unordered structures when interacting with DPPG. For rPAC(236) the α-helices were preserved even in the presence of DPPG. These results confirm the importance of the C-terminal region for PAC-ER membrane interaction. The partial unfolding only with preserved C-terminal appears a key step for the protein to reach the cytosol and develop its toxic activity.

The lipid composition of a cell membrane modulates the interaction of an antiparasitic peptide at the air-water interface.

The antiparasitic property of peptides is believed to be associated with their interactions with the protozoan membrane, which calls for research on the identification of membrane sites capable of peptide binding. In this study we investigated the interaction of a lipophilic glutathioine peptide known to be effective against the African Sleeping Sickness (ASS - African Trypanosomiasis) and cell membrane models represented by Langmuir monolayers. It is shown that even small amounts of the peptide affect the monolayers of some phospholipids and other lipids, which points to a significant interaction. The latter did not depend on the electrical charge of the monolayer-forming molecules but the peptide action was particularly distinctive for cholesterol + sphingomyelin monolayers that roughly resemble rafts on a cell membrane. Using in situ polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS), we found that the orientation of the peptide is affected by the phospholipids and dioctadecyldimethylammonium bromide (DODAB), but not in monolayers comprising cholesterol + sphingomyelin. In this mixed monolayer resembling rafts, the peptide still interacts and has some induced order, probably because the peptide molecules are fitted together into a compact monolayer. Therefore, the lipid composition of the monolayer modulates the interaction with the lipophilic glutathioine peptide, and this may have important implications in understanding how the peptide acts on specific sites of the protozoan membrane.

Detection of catechol using mixed Langmuir-Blodgett films of a phospholipid and phthalocyanines as voltammetric sensors.

The combination of metallic phthalocyanines (MPcs) and biomolecules has been explored in the literature either as mimetic systems to investigate molecular interactions or as supporting layers to immobilize biomolecules. Here, Langmuir-Blodgett (LB) films containing the phospholipid dimyristoyl phosphatidic acid (DMPA) mixed either with iron phthalocyanine (FePc) or with lutetium bisphthalocyanine (LuPc(2)) were applied as ITO modified-electrodes in the detection of catechol using cyclic voltammetry. The mixed Langmuir films of FePc + DMPA and LuPc(2) + DMPA displayed surface-pressure isotherms with no evidence of molecular-level interactions. The Fourier Transform Infrared (FTIR) spectra of the multilayer LB films confirmed the lack of interaction between the components. The DMPA and the FePc molecules were found to be oriented perpendicularly to the substrate, while LuPc(2) molecules were randomly organized. The phospholipid matrix induced a remarkable electrocatalytic effect on the phthalocyanines; as a result the mixed LB films deposited on ITO could be used to detect catechol with detection limits of 4.30 × 10(-7) and 3.34 × 10(-7) M for FePc + DMPA and LuPc(2) + DMPA, respectively. Results from kinetics experiments revealed that ion diffusion dominated the response of the modified electrodes. The sensitivity was comparable to that of other non-enzymatic sensors, which is sufficient to detect catechol in the food industry. The higher stability of the electrochemical response of the LB films and the ability to control the molecular architecture are promising for further studies with incorporation of biomolecules.

Chitosan in nanostructured thin films.

This review paper brings an overview of the use of chitosans in nanostructured films produced with the Langmuir-Blodgett (LB) or the electrostatic layer-by-layer (LbL) techniques, with emphasis on their possible applications. From a survey in the literature one may identify three main types of study with chitosan in nanostructured films. First, the interaction between chitosans and phospholipid Langmuir monolayers has been investigated for probing the mechanisms of chitosan action in their biological applications, with the monolayers serving as cell membrane models. In the second type, chitosan serves as a matrix for immobilization of biomolecules in LB as well as in LbL films, for which chitosan is suitable to help preserve the bioactivity of such biomolecules for long periods of time even in dry, solid films. An important application of these chitosan-containing films is in sensing and biosensing. The third type of study involves exploiting the mechanical and biocompatibility properties of chitosan in producing films with enhanced properties, for example, for tissue engineering. It is emphasized that chitosans have been proven excellent building blocks to produce films with controlled molecular architecture, allowing for synergy between distinct materials. We also discuss the prospects of the field, following a critical review of the latest developments in nanostructured chitosan films.