Nanotechnology in Solving Problems of Chemical Processing by Self-Assembly INTRODUCTION The many impressive laboratory demonstrations of controllable self-assembly methods generate considerable hope and interest in self-assembly as a manufacturing method for nanostructured products, Thepractcal realisation of his hope will require several achievements in chemical engineering, including the recision manufacturing of precursors, expansion of our ideas of molecular chemistry to super: noleclarchemistry from a bonding, kinetics and mechanistic point of view and a focus on self-assembly processes that can be scaled up to interesting levels. This leads toa rich array of research and process development issues for chemical engineers Chemical engineers are playing very significant roles in developinga new science base in phenomena, snafus and potential applications where understanding at nanometre length scales is crucial, Synthesis and demonstration of new catalysts, new multi-component polymers and new biomaterials are al fine trample of areas to which chemical engineers are making major contributions to nanoscale science, in pariularbutnot exclusively, via the self-assembly route that isthe subject of this chapter, Whether this tew science base leads to important technological developments depends even more on chemical Segineers, Tis chapter highlights the opportunities for chemical engineers to advance nanotechnology enand an emphasis on developing suitably effective processing technologies, Treating self-assembly %Sa serious chemical process is rich with chemical engineering opportunities. StlF-assembly is a spontaneous process, guided by information content intrinsic to the assembling ee Toultplelevels of structural organisation are built into a product. Owing to the complexity bea a pane and the nominal ease of spontaneous organisation, Seikascembly is inereasingly Rey Sra ae cena processng met, is akin etalon sep Hae Sige latiog cae et emenIS involved is greater in self-assembly and length-seales beyon icing «2M eMeTBE in the product. In some eases, selPassembly can result in iit, Dita eee athitectures of mater. The resultant structures are being atively explored as new » Surface treatments, catalysts, membranes, photonic materials and electronic devices, to name afew — = —————— fs Tuy pose SuTEHT engineering exploration. Self-assembly is one ofthe key mechanisms By which cas from biological molecules such as proteins to larger structures such as cells and built Matrices, the spatial arrangement of atoms is determined, in large part, by information sembly i “ssembling units. Complexity, in the sense of development of emergent properties of an at cannot readily be envisioned from the constituents, can arise spontaneously during 227 =.> Number of building blocks along the chain Fig. 24.1. Schematic diagram showing how complexity of self-assembly may increase as the number of building blocks in a copolymer increases Indeed, other routes to self-organisation, including those far from equilibrium, may also be of interest for nanotechnology. The ability to form structures spontaneously from the bottom up, using principles akin to’ biological assembly, has inspired considerable research among chemists, physicists and chemical engineer f0 develop useful products. The high level of scientific activity in this field creates several kinds of major ‘opportunities for chemical engineering research. The overall opportunity might be characterised a8 @ shift from product to processing research in self-assembly As self-assembly attempis to evolve from laboratory techniques and provocative demonstrations of structure, to practical, larger-scale, processing methods, a broad spectrum of important engineering research problems is being & at) ‘s es for new chemical engineering research in self-assembly are the focus of this ‘requires, among other matters, is taking self-assembly seriously as @ processing What are the barriers to its development and widespread implementation in the co ew takes a processing perspective, appropriate to motivate this under g research. A recent review, from a surface science perspective, 4colloidal crys ‘ ples multimolecular objects. The rules of chemical bonding kinetics for reactions among objects such as these to form stable, us explored to form a good basis for process development, BRIEF SUMMARY AND CRITIQUE OF THE STATE-OF-THE-ART OF SELF PROCESSING ia Numerous processes for producing chemical products, surface layers or new materials by have been developed. Table 24.1 gives a substantial but not exhaustive list, A short discussi is included, and what is omitted, and why, is warranted. Adsorption of pot ist ai ft honepolme (not on the list), is a ides ant Tere ae a m materials surfaces. However, it is a random process without any particular guidance to the asse coming from the molecular structure, and therefore it lacks an important ingredient (a trajectory ty information content of the assemblers) in the definition of self-assembly. On the other hand, in the adsorption of multi-component polymers, such as block copolymers or hydrophobically modified polymers, some pieces of the molecule are driven by their chemical nature to stick to interfaces, anol. The resulting molecular rrangeneal B aetet ey oo (internal structure) in the adsorbing molecules. Amphiphilic molecules “know” which end is up when placed in a surface or interfacial region, Table 24.1. Processes incorporating self-assembly. Adsorption of multicomponent polymers Cooperative supramolecular self-assembly of surfactant organic mesostructures Grafting of polymers on interfaces Langmuir-Blodgett deposition ed a ‘ayer-by-layer deposition or sequential adsorption is Micellar control of reactions Microcontact printing Organising colloids into arrays and erystals Self-assembly of monolayers Spin and dip coating of supramolecular solutions and dispersions Surface directed ordering of molecules at interfaces (liquid erystals) Surface modification by monolayer or multilayer deposition Templating Vesicle fusionsling objects plays a major role. ; singe (LB) deposition as a processing meth w examples of self-assembly processing. , bly method that seems to lend itself to scale-up and to continuous proo S great versatility in the range of components that can be used in the process, j th (LbL), pioneered by Decher and co-workers, and now being much more broadly explored, successive dipping cycles of subsjrates into solutions of molecules with some interactive arity (usually of opposite ce) | and co-workers have generalised this method to LbL on particle surfaces developing the ‘destruction of the templating particle (usually by dissolution), to make self-assembled vith controlled structure, contents and wall properties (mechanical and transport). Destruction ganic template to leave a self-assembled inorganic Eee has proven a very effective route to ‘Materials for catalysts, sorbents and membranes, a ‘Printing (MCP) is another burgeoning laboratory-scale method incorporating self the basic application ofthis methodology, a stamp is ‘inked? with a self assembled layer h then used in MCP processing to transfer the self-assembled material to another surface. fe ties for making MCP an efficient, versatile, even continuous, process seem very achievable, e ‘on classical printing technology. Clearly, many of the processes in Table 24.1, MCP Purely self-as oreven directed assembly processes but involve the interventionprocessing and certain combustion/aerosol processes ontrolled nanostructured products. i ‘there are serious competitors to self-assembly processing. Engine ion Synthesis of Precursors ‘to form a desired state of organisation spontaneously depends on the inter tis then clear that information must be built into the assembling obj synthesised with p isolated as pure compounds. The abi ity to make micellar and b is a direct‘of nucleic acids are also increasingly recog, mation is built into polysaccharides by control of archit ~ gevelopment of self-assembly processes will place a premium on n utes 0 PUrE, precise macromolecular synthesis and production or will be fruitful to understand, in much more detail than we currently sic self-assembly processes to the lack of precision in tf 'A second lesson that may be extracted arising from consideration of standing of how nature achieves precision synthesis, Biological systems do: rather, considerable effort is expended in detecting and correcting errors en route fo 1g analogues of this are online measurement, control and post- ssary control over molecular architecture, it will be: both chemical and biological synthesis routes with a realistic eye toward process ¢ Expanding the Idea of the Molecule Since self-assembly often, even usually, involves the spontaneous organisation of object larger than molecules, it is useful to begin to think about larger assembling objects in s edo about molecules in chemical reactions. The atomic and molecular: .ct but pragmatic counterparts when applied to interactions: macromolecules, nanotubes, particles and other important self-assembly constituents. that composite or structured, collodial nanoparticles can be formed by the controlled e primary particles. The symmetry of these structured particles endows them with the p directional bonding, the molecular analogue of the symmetry of electronic wavelHydrophilic active site ———> | Nt Polymerised ~@ Covalently linked hydrophiie cores, @™ hydrophobic SQ Fee wer = of peptide amphiphiles bear many similarities to protein macromolecules ophilic bioactive exteriors, globular shapes, and sizes in the tens if. duced via polymerisable lipid tals. ‘context of Langmuir-Blodgett: deposition, scale-up of self-assem nt scales has not been pursued to an appreciable degree. That is pert nt of the field. Nevertheless, lack of ways to scale-up can be tt ‘in a technological arena, Some of the most innovative d ite have been achieved by chemists, where advances in assem he ability to assemble macroscopic, three dimension Some tools of process systems research le engineering in general, Success in enlargi | Or repetitive processing would b .ci aa trajectories and rates of assembly. san example of work in this direction, we offer our r eqs ths pysico-emica) reaction are depicted in Fig. 24.6(a). Vesicle fusion, fel ingly useful laboratory method to coat surfaces with monolay Janological applications, particularly selective o es been interested in its tect For this we felt we needed kinetic data and a mechanistic inter ricofabricted devices. ituations such as deposition on textured surfaces, in comers, et wre could extrapolate to neW si sry has proven to bea useful tool in kinetic studies, Figure 24.6() shows modulated elipsomet ayers (we have proven that the plateau deposi ‘accumulation of monol ‘model where we have ‘considered both the diffusive rate of supply to the: tsimporant potentially rate-controling steps. Our unambiguous conclusion is that surface re dominates in this case. These kinds of studies are very important to the advancement of this: ‘Amphiphile ‘Small hydrophilic hhead-group Hydration and ‘extrusion Large hydrophilic. tails \Vesicle solution on surface Planar lipid bilayer ehh oor ahuch chatty th a