LB technique

Mono- and multilayers may be fonned by the LB technique from polymers bearing both hydrophilic and hydrophobic side groups that are already spread as a polymer at the water-air interface. 

Experiments witli chemically grafted SAMs displayed much larger wear resistance tlian films produced by tire LB technique [188]. Also it was found tliat wear properties of SAMs can be furtlier improved by chemically grafting CgQ molecules onto SAM surfaces [189]. 

LB Films of Long-Chain Fatty Acids. LB films of saturated long-chain fatty acids have been studied since the inception of the LB technique. The most stable films of long-chain fatty acids are formed by cadmium arachidate deposited from a buffered CdCl2 subphase. These films, considered to be standards, have been widely used as spacer layers (23) and for examining new analytical techniques. Whereas the chains are tilted - 25° from the surface normal in the arachidic acid, CH2(CH2) gCOOH, films (24), it is nearly perpendicular to the surface in the cadmium arachidate films (25). 

The advantage of the LB technique is that it allows systematic studies of 2-D organization, both before and after transfer from the air—water interface onto a soHd substrate. However, the coupling of 3-D self-organization of macromolecules in solution with organization at a soHd surface may best be achieved using the self-assembly technique. 

One of the new trends in chemical analysis appeared in the last decade is that the miniaturization. It becomes apparent in the miniaturization of analytical devices, separation procedures, measuring tools, analyzing samples and as a consequent the term micro have appeared. Further development of this trend have led to transfer from the term micro to nano one (nanoparticles, nanofluides, nanoprobes, nanoelectrodes, nanotubes, nanoscale, nanobarcode, nanoelectrospray, nanoreactors, etc). Thereupon a nanoscale films produced by Langmuir-Blodgett (LB) technique are proposed for modifying of chemical sensors. 

Salts of fatty acids are classic objects of LB technique. Being placed at the air/water interface, these molecules arrange themselves in such a way that its hydrophilic part (COOH) penetrates water due to its electrostatic interactions with water molecnles, which can be considered electric dipoles. The hydrophobic part (aliphatic chain) orients itself to air, because it cannot penetrate water for entropy reasons. Therefore, if a few molecnles of snch type were placed at the water surface, they would form a two-dimensional system at the air/water interface. A compression isotherm of the stearic acid monolayer is presented in Figure 1. This curve shows the dependence of surface pressure upon area per molecnle, obtained at constant temperature. Usually, this dependence is called a rr-A isotherm. 

A large number of potential applications for organized protein monolayers have recently motivated considerable research activity in this field (Boussaad et al. 1998, Kiselyova et al. 1999). Construction of specific interaction-directed, self-assembled protein films has been performed at the air-water interface. The Langmuir-Blodgett (LB) technique has been extensively used to order and immobilize natural proteins on solid surfaces (Tronin et... 

Described differences in the initial protein solution conditions, of course, differentiates the processes of film formation, both in the case of the LB technique and in the case of self-assembling. 

The Langmuir-Blodgett (LB) technique was successfully applied for the deposition of thin protein layers (Langmuir and Schaefer 1938, Tiede 1985, Lvov et al. 1991). LB organization of protein molecules in film not only preserved the structure and functionality of the molecules, but also resulted in the appearance of new, useful properties, such as enhanced thermal stability (Nicolini et al. 1993 Erokhin et al. 1995). 

Enhanced thermal stability enlarges the areas of application of protein films. In particular it might be possible to improve the yield of reactors in biotechnological processes based on enzymatic catalysis, by increasing the temperature of the reaction and using enzymes deposited by the LB technique. Nevertheless, a major technical difficulty is that enzyme films must be deposited on suitable supports, such as small spheres, in order to increase the number of enzyme molecules involved in the process, thus providing a better performance of the reactor. An increased surface-to-volume ratio in the case of spheres will increase the number of enzyme molecules in a fixed reactor volume. Moreover, since the major part of known enzymatic reactions is carried out in liquid phase, protein molecules must be attached chemically to the sphere surface in order to prevent their detachment during operation. 

The LB technique was chosen for covering the spheres because it was shown to provide enhanced thermal stability of many types of proteins in deposited layers (Nicolini et al. 1993, Erokhin et al. 1995, Antolini et al. 1995), which no other technique is able to achieve. Since only the upper protein layer is involved in the catalytic activity, no special attention was paid to check whether the deposited layer is a monolayer or multilayer. However, the samples were thoroughly washed to remove protein molecnles not bound covalently to the sphere surface, since during the functional test these molecules could contribute to the measured apparent catalytic activity. 

The Langmuir-Blodged (LB) technique allows one to form a monolayer at the water surface and to transfer it to the surface of supports. Formation of the BR monolayer at the air/water interface, however, is not a trivial task, for it exists in the form of membrane fragments. These fragments are rather hydrophilic and can easily penetrate the subphase volume. In order to decrease the solubility, the subphase usually contains a concentrated salt solution. The efficiency of the film deposition by this approach (Sukhorukov et al. 1992) was already shown. Nevertheless, it does not allow one to orient the membrane fragments. Because the hydrophilic properties of the membrane sides are practically the same, fragments are randomly oriented in opposite ways at the air/water interface. Such a film cannot be useful for this work, because the proton pumping in the transferred film will be automatically compensated i.e., the net proton flux from one side of the film to the other side is balanced by a statistically equal flux in the opposite direction. 

X-ray measurements of the deposited multilayers revealed practically the same structure in films prepared with the usual LB technique and electric field-assisted monolayer... 

TABLE 3 Photocurent Observed in a System Using Porous Membranes Covered with BR Film Deposited by the Usual LB Technique and Electric Field-Assisted Technique... 

It was indeed shown recently that it is possible to deposit DNA-aliphatic amine complexes onto solid substrate via the Langmuir-Blodgett (LB) technique (Erokhin et al. 

Transfer of Langmuir fdms of particles from the air-water interface onto solid supports, e.g., by the Langmuir-Blodgett (LB) technique [71-83]... 

In 1997, a Chinese research group [78] used the colloidal solution of 70-nm-sized carboxylated latex particles as a subphase and spread mixtures of cationic and other surfactants at the air-solution interface. If the pH was sufficiently low (1.5-3.0), the electrostatic interaction between the polar headgroups of the monolayer and the surface groups of the latex particles was strong enough to attract the latex to the surface. A fairly densely packed array of particles could be obtained if a 2 1 mixture of octadecylamine and stearic acid was spread at the interface. The particle films could be transferred onto solid substrates using the LB technique. The structure was studied using transmission electron microscopy. 

In order to study the structure of Langmuir films of polymers spheres, most researchers deposited the films on solid substrates using the LB technique [158-162] and analyzed the structure using a microscope. A modified version of the LB method allowing the transfer of particle monolayers is outlined in Figure 8a. 

Fabrication of Porous Thin Film using the Langmuir-Blogdett (LB) Technique... 

Figure 10. Fabrication of porous Pt nanoparticle membranes by the LB technique. (Reprinted with permission from Ref. [31], 2005, Wiley-VCH.)...

Porous Membranes of Nanoparticies from Templating Against AAO Membranes Using LB Technique. AAO-porous substrate has broad applications in making metal and semiconductor nanowires, aligned mesostructured nanorods, inorganic nanotubes. 

The LB technique is amenable to the fabrication of ECDs as demonstrated by the report of a thin-film display based on bis(phthalocyaninato)praseodymium(III).75 The electrochromic electrode in the display was fabricated by deposition of multilayers (10-20 layers, r+00-200 A) of the complex onto ITO-coated glass (7 x4cm2) slides. The display exhibited blue-green-yellow-red polyelectrochromicity over a potential range of —2 to +2V. After 105 cycles no significant... 

Figure 11.5. Langmuir-Blodgett (LB) technique-assisted NW assembly (a) Schematic of LB-guided assembly. NWs are floated on a water surface and compressed through computer guided pressure, (b) SEM image of silver NWs deposited on Si wafer. Reprinted with permission from Ref. 54. Copyright 2003 American Chemical Society.

In the LB technique, the fluid to be simulated consists of a large set of fictitious particles. Essentially, the LB technique boils down to tracking a collection of these fictitious particles residing on a regular lattice. A typical lattice that is commonly used for the effective simulation of the NS equations (Somers, 1993) is a 3-D projection of a 4-D face-centred hypercube. This projected lattice has 18 velocity directions. Every time step, the particles move synchronously along these directions to neighboring lattice sites where they collide. The collisions at the lattice sites have to conserve mass and momentum and obey the so-called collision operator comprising a set of collision rules. The characteristic features of the LB technique are the distribution of particle densities over the various directions, the lattice velocities, and the collision rules. 

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