The widespread use of controlled molecular-level motion in key natural processes suggests that great rewards could come from bridging the gap between the present generation of synthetic molecular systems, which by and large rely upon electronic and chemical effects to carry out their functions, and the machines of the macroscopic world, which utilize the synchronized movements of smaller parts to perform specific tasks. This is a scientific area of great contemporary interest and extraordinary recent growth, yet the notion of molecular-level machines dates back to a time when the ideas surrounding the statistical nature of matter and the laws of thermodynamics were first being formulated. Here we outline the exciting successes in taming molecular-level movement thus far, the underlying principles that all experimental designs must follow, and the early progress made towards utilizing synthetic molecular structures to perform tasks using mechanical motion. We also highlight some of the issues and challenges that still need to be overcome.

Synthetic molecular motors and mechanical machines.

Functional π-Gelators and Their Applications

The widespread use of molecular machines in biology has long suggested that great rewards could come from bridging the gap between synthetic molecular systems and the machines of the macroscopic world. In the last two decades, it has proved possible to design synthetic molecular systems with architectures where triggered large amplitude positional changes of submolecular components occur. Perhaps the best way to appreciate the technological potential of controlled molecular-level motion is to recognize that nanomotors and molecular-level machines lie at the heart of every significant biological process. Over billions of years of evolution, nature has not repeatedly chosen this solution for performing complex tasks without good reason. When mankind learns how to build artificial structures that can control and exploit molecular level motion and interface their effects directly with other molecular-level substructures and the outside world, it will potentially impact on every aspect of functional molecule and materials design. An improved understanding of physics and biology will surely follow.

The first steps on the long path to the invention of artificial molecular machines were arguably taken in 1827 when the Scottish botanist Robert Brown observed the haphazard motion of tiny particles under his microscope.1,2 The explanation for Brownian motion, that it is caused by bombardment of the particles by molecules as a consequence of the kinetic theory of matter, was later provided by Einstein, followed by experimental verification by Perrin.3,4 The random thermal motion of molecules and its implications for the laws of thermodynamics in turn inspired Gedankenexperiments (“thought experiments”) that explored the interplay (and apparent paradoxes) of Brownian motion and the Second Law of Thermodynamics. Richard Feynman’s famous 1959 lecture “There’s plenty of room at the bottom” outlined some of the promise that manmade molecular machines might hold.5,6 However, Feynman’s talk came at a time before chemists had the necessary synthetic and analytical tools to make molecular machines. While interest among synthetic chemists began to grow in the 1970s and 1980s, progress accelerated in the 1990s, particularly with the invention of methods to make mechanically interlocked molecular systems (catenanes and rotaxanes) and control and switch the relative positions of their components.7−24

Here, we review triggered large-amplitude motions in molecular structures and the changes in properties these can produce. We concentrate on conformational and configurational changes in wholly covalently bonded molecules and on catenanes and rotaxanes in which switching is brought about by various stimuli (light, electrochemistry, pH, heat, solvent polarity, cation or anion binding, allosteric effects, temperature, reversible covalent bond formation, etc.). Finally, we discuss the latest generations of sophisticated synthetic molecular machine systems in which the controlled motion of subcomponents is used to perform complex tasks, paving the way to applications and the realization of a new era of “molecular nanotechnology”.

1.1. The Language Used To Describe Molecular Machines
Terminology needs to be properly and appropriately defined and these meanings used consistently to effectively convey scientific concepts. Nowhere is the need for accurate scientific language more apparent than in the field of molecular machines. Much of the terminology used to describe molecular-level machines has its origins in observations made by biologists and physicists, and their findings and descriptions have often been misinterpreted and misunderstood by chemists. In 2007 we formalized definitions of some common terms used in the field (e.g., “machine”, “switch”, “motor”, “ratchet”, etc.) so that chemists could use them in a manner consistent with the meanings understood by biologists and physicists who study molecular-level machines.14

The word “machine” implies a mechanical movement that accomplishes a useful task. This Review concentrates on systems where a stimulus triggers the controlled, relatively large amplitude (or directional) motion of one molecular or submolecular component relative to another that can potentially result in a net task being performed. Molecular machines can be further categorized into various classes such as “motors” and “switches” whose behavior differs significantly.14 For example, in a rotaxane-based “switch”, the change in position of a macrocycle on the thread of the rotaxane influences the system only as a function of state. Returning the components of a molecular switch to their original position undoes any work done, and so a switch cannot be used repetitively and progressively to do work. A “motor”, on the other hand, influences a system as a function of trajectory, meaning that when the components of a molecular motor return to their original positions, for example, after a 360° directional rotation, any work that has been done is not undone unless the motor is subsequently rotated by 360° in the reverse direction. This difference in behavior is significant; no “switch-based” molecular machine can be used to progressively perform work in the way that biological motors can, such as those from the kinesin, myosin, and dynein superfamilies, unless the switch is part of a larger ratchet mechanism.14

Artificial Molecular Machines

https://orbit.dtu.dk/files/4351774/2009%20PBI%20review%20Progress%20in%20Polymer%20Science%2034,%205,%20449-477.pdf

High temperature proton exchange membranes based on polybenzimidazoles for fuel cells

This Review summarizes recent developments in the field of responsive photonic crystal structures, including principles for design and fabrication and many strategies for applications, for example as optical switches or chemical and biological sensors. A number of fabrication methods are now available to realize responsive photonic structures, the majority of which rely on self-assembly processes to achieve ordering. Compared with microfabrication techniques, self-assembly approaches have lower processing costs and higher production efficiency, however, major efforts are still needed to further develop such approaches. In fact, some emerging techniques such as spin coating, magnetic assembly, and flow-induced self-assembly have already shown great promise in overcoming current challenges. When designing new systems with improved performance, it is always helpful to bear in mind the lessons learnt from natural photonic structures.

Responsive photonic crystals.

A series of polybenzimidazoles (PBIs) incorporating main chain pyridine groups were synthesized from the pyridine dicarboxylic acids (2,4-, 2,5-, 2,6- and 3,5-) and 3,3′,4,4′-tetraaminobiphenyl, using polyphosphoric acid (PPA) as both solvent and polycondensation reagent. A novel process, termed the PPA process, has been developed to prepare phosphoric acid (PA) doped PBI membranes by direct-casting of the PPA polymerization solution without isolation or re-dissolution of the polymers. The subsequent hydrolysis of PPA to PA by moisture absorbed from the atmosphere usually induced a transition from the solution state to a gel-like state and produced PA-doped PBI membranes with a desirable suite of physiochemical properties. The polymer structure characterization included inherent viscosity (I.V.) determination as a measurement of polymer molecular weight and thermal stability assessment via thermogravimetric analysis. Physiochemical properties of the doped membrane were studied by measurements of the PA doping level, ionic conductivity and mechanical properties. The resulting pyridine-based polybenzimidazole membranes displayed high PA doping levels, ranging from 15 to 25 mol of PA per PBI repeat unit, which contributed to their unprecedented high proton conductivities of 0.1 to 0.2 S cm–1 at 160 °C. The mechanical property measurements showed that the pyridine-based PBI membranes were thermally stable and maintained mechanical integrity even at high PA doping levels. Preliminary fuel cell tests demonstrated the feasibility of the novel pyridine-based PBI (PPBI) membranes from the PPA process for operating fuel cells at temperatures in excess of 120 °C without any external humidification.

Synthesis and Characterization of Pyridine-Based Polybenzimidazoles for High Temperature Polymer Electrolyte Membrane Fuel Cell Applications

We developed a new sensing motif for the detection and quantification of creatinine, which is an important small molecule marker of renal dysfunction. This novel sensor motif is based on our intelligent polymerized crystalline colloidal array (IPCCA) materials, in which a three-dimensional crystalline colloidal array (CCA) of monodisperse, highly charged polystyrene latex particles are polymerized within lightly cross-linked polyacrylamide hydrogels. These composite hydrogels are photonic crystals in which the embedded CCA diffracts visible light and appears intensely colored. Volume phase transitions of the hydrogel cause changes in the CCA lattice spacings which change the diffracted wavelength of light. We functionalized the hydrogel with two coupled recognition modules, a creatinine deiminase (CD) enzyme and a 2-nitrophenol (2NPh) titrating group. Creatinine within the gel is rapidly hydrolyzed by the CD enzyme in a reaction which releases OH(-). This elevates the steady-state pH within the hydrogel as compared to the exterior solution. In response, the 2NPh is deprotonated. The increased solubility of the phenolate species as compared to that of the neutral phenols causes a hydrogel swelling which red-shifts the IPCCA diffraction. This photonic crystal IPCCA senses physiologically relevant creatinine levels, with a detection limit of 6 microM, at physiological pH and salinity. This sensor also determines physiological levels of creatinine in human blood serum samples. This sensing technology platform is quite general. It may be used to fabricate photonic crystal sensors for any species for which there exists an enzyme which catalyzes it to release H(+) or OH(-).

/pdf/a-general-photonic-crystal-sensing-motif-creatinine-in-1d7va6oxt2.pdf

A general photonic crystal sensing motif: Creatinine in bodily fluids

Regioregular poly(3-hexylthiophene) (P3HT) produces thermoreversible gel in xylene. The gel is brownish-red in color. SEM and TEM studies indicate the presence of fibrillar network. WAXS and electron diffraction pattern indicate the presence of P3HT crystallites in the gel. The gels exhibit a first-order phase transition when heated in DSC. A time-dependent UV−vis study indicates that gelation in this system is probably accompanied by two different processes, e.g., (1) coil-to-rod transformation and (2) aggregation of rods to form the crystallites producing the gel. The gelation rate (tgel-1) measured from the test tube tilting method is analyzed using the equation tgel-1 = f(C) f(T), where f(c) = φn, φ being the reduced overlapping concentration and n is an exponent. The average “n” value determined is 0.52, which indicates that three-dimensional percolation is a suitable model for this gelation. The gelation rate is analyzed according to the Flory−Weaver theory of coil-to-helix transition, and the free ...

Thermoreversible Gelation of Regioregular Poly(3-hexylthiophene) in Xylene

Despite the myriad studies on polybenzimidazole based polymer electrolyte membranes for fuel cells operating above 100 °C, the development of membranes with higher proton conductivity without compromising mechanical stability has continued to be the prime challenge. In this article, organic/inorganic hybrid nanocomposites of poly (4,4′-diphenylether-5,5′-bibenzimidazole) (OPBI) were prepared with surface functionalized silica nanoparticles to address this key issue. Structural and morphological studies probed by SAXS, WAXD and TEM, respectively revealed the formation of self-assembled clusters of nanoparticles when the OPBI nanocomposites were made with amine modified silica (AMS) whereas a well dispersed structure was obtained for OPBI and the unmodified silica (UMS) composite. The OPBI/AMS nanocomposites displayed a significant enhancement in the thermal stabilities compared to the pristine OPBI and OPBI/UMS nanocomposite. The OPBI/AMS nanocomposite membranes exhibited a larger mechanical reinforcement than the pristine OPBI and OPBI/UMS nanocomposite. The formation of nanoparticle clusters in the OPBI matrix in the case of OPBI/AMS was found to be the driving force for the higher thermal and mechanical stability of OPBI/AMS than those of OPBI/UMS. The incorporation of AMS in the OPBI matrix shielded the polymer chains from the attack of oxidative radicals, resulting in a huge enhancement of oxidative stability of the nanocomposite membranes compared to the pure OPBI membrane. The OPBI/AMS nanocomposite membranes have significantly higher phosphoric acid (PA) loading compared to the pure OPBI membrane which resulted in the higher proton conductivities of the former. The self-assembled clusters of AMS in the OPBI matrix facilitated the proton transport process.

/pdf/polybenzimidazole-silica-nanocomposites-organic-inorganic-mtddg8xevf.pdf

Polybenzimidazole/silica nanocomposites: Organic-inorganic hybrid membranes for PEM fuel cell

Although increased number of reports in recent years on proton exchange membrane (PEM) developed from nanocomposites of polybenzimidazole (PBI) with inorganic fillers brought hope to end the saga of contradiction between proton conductivity and variety of stabilities, such as mechanical, thermal,chemical, etc.; it still remains a prime challenge to develop a highly conducting PEM with superior aforementioned stabilities. In fact the very limited understanding of the interactions especially interfacial interaction between PBI and inorganic filler leads to confusion over the choice of inorganic filler type and their surface functionalities. Taking clue from our earlier study based on poly(4,4′-diphenylether-5,5′-bibenzimidazole) (OPBI)/silica nanocomposites, where silica nanoparticles modified with short chain amine showed interfacial interaction-dependent properties, in this work we explored the possibility of enhanced interfacial interaction and control over the interface by optimizing the chemistry of th...

Tushar Jana

Papers

Synthesis and Characterization of Pyridine-Based Polybenzimidazoles for High Temperature Polymer Electrolyte Membrane Fuel Cell Applications

A general photonic crystal sensing motif: Creatinine in bodily fluids

Thermoreversible Gelation of Regioregular Poly(3-hexylthiophene) in Xylene

Polybenzimidazole/silica nanocomposites: Organic-inorganic hybrid membranes for PEM fuel cell

Structure and Properties of Polybenzimidazole/Silica Nanocomposite Electrolyte Membrane: Influence of Organic/Inorganic Interface