Françisco M. Raymo

Bio: Françisco M. Raymo is an academic researcher from University of Miami. The author has contributed to research in topics: Photochromism & Quantum dot. The author has an hindex of 65, co-authored 272 publications receiving 18608 citations. Previous affiliations of Françisco M. Raymo include University of California, Los Angeles & University of Messina.

Artificial Molecular Machines.

Abstract: The miniaturization of components used in the construction of working devices is being pursued currently by the large-downward (top-down) fabrication. This approach, however, which obliges solid-state physicists and electronic engineers to manipulate progressively smaller and smaller pieces of matter, has its intrinsic limitations. An alternative approach is a small-upward (bottom-up) one, starting from the smallest compositions of matter that have distinct shapes and unique properties-namely molecules. In the context of this particular challenge, chemists have been extending the concept of a macroscopic machine to the molecular level. A molecular-level machine can be defined as an assembly of a distinct number of molecular components that are designed to perform machinelike movements (output) as a result of an appropriate external stimulation (input). In common with their macroscopic counterparts, a molecular machine is characterized by 1) the kind of energy input supplied to make it work, 2) the nature of the movements of its component parts, 3) the way in which its operation can be monitored and controlled, 4) the ability to make it repeat its operation in a cyclic fashion, 5) the timescale needed to complete a full cycle of movements, and 6) the purpose of its operation. Undoubtedly, the best energy inputs to make molecular machines work are photons or electrons. Indeed, with appropriately chosen photochemically and electrochemically driven reactions, it is possible to design and synthesize molecular machines that do work. Moreover, the dramatic increase in our fundamental understanding of self-assembly and self-organizational processes in chemical synthesis has aided and abetted the construction of artificial molecular machines through the development of new methods of noncovalent synthesis and the emergence of supramolecular assistance to covalent synthesis as a uniquely powerful synthetic tool. The aim of this review is to present a unified view of the field of molecular machines by focusing on past achievements, present limitations, and future perspectives. After analyzing a few important examples of natural molecular machines, the most significant developments in the field of artificial molecular machines are highlighted. The systems reviewed include 1) chemical rotors, 2) photochemically and electrochemically induced molecular (conformational) rearrangements, and 3) chemically, photochemically, and electrochemically controllable (co-conformational) motions in interlocked molecules (catenanes and rotaxanes), as well as in coordination and supramolecular complexes, including pseudorotaxanes. Artificial molecular machines based on biomolecules and interfacing artificial molecular machines with surfaces and solid supports are amongst some of the cutting-edge topics featured in this review. The extension of the concept of a machine to the molecular level is of interest not only for the sake of basic research, but also for the growth of nanoscience and the subsequent development of nanotechnology.

Electronically Configurable Molecular-Based Logic Gates

Abstract: Logic gates were fabricated from an array of configurable switches, each consisting of a monolayer of redox-active rotaxanes sandwiched between metal electrodes. The switches were read by monitoring current flow at reducing voltages. In the “closed” state, current flow was dominated by resonant tunneling through the electronic states of the molecules. The switches were irreversibly opened by applying an oxidizing voltage across the device. Several devices were configured together to produce AND and OR logic gates. The high and low current levels of those gates were separated by factors of 15 and 30, respectively, which is a significant enhancement over that expected for wired-logic gates.

A [2]Catenane-Based Solid State Electronically Reconfigurable Switch

Abstract: A solid state, electronically addressable, bistable [2]catenane-based molecular switching device was fabricated from a single monolayer of the [2]catenane, anchored with phospholipid counterions, and sandwiched between an n-type polycrystalline silicon bottom electrode and a metallic top electrode. The device exhibits hysteretic (bistable) current/voltage characteristics. The switch is opened at +2 volts, closed at −2 volts, and read at ∼0.1 volt and may be recycled many times under ambient conditions. A mechanochemical mechanism for the action of the switch is presented and shown to be consistent with temperature-dependent measurements of the device operation.

Digital processing and communication with molecular switches

Abstract: The tremendous pace in the development of information technology is rapidly approaching a limit. Alternative materials and operating princlples for the elaboration and communication of data in electronic circults and optical networks must be identified. Organic molecules are promising candidates for the realization of future digital processors. Their attractive features are the miniaturized dimensions and the high degree of control on molecular design possible in chemical synthesis. Indeed, nanostructures with engineered properties and specific functions can be assembled relying on the power of organic synthesis. In particular, certain molecales can be designed to switch from one state to another, when addressed with chemical, electrical, or optical stimulations, and to produce a detectable signal in response to these transformations. Binary data can be enceded on the input stimulations and output signals employing logic conventions and assumptions similar to those ruting digital electronics. Thus, binary inputs can be transduced into binary outputs relying on molecular switches. Following these design principles, the three basic logic operations (AND, NOT, and OR) and more complex logic functions (EOR, INH, NOR, XNOR, and XOR) have been reproduced already at the molecular level. Presently, these simple "molecular processors" are far from any practical application. However, these encouraging results demonstrate already that chemical systems can process binary data with designed logic protocols. Further fundamental studies on the various facets of this emerging area will reveal if and how molecular switches can become the basic components of furture logic devices. After all, chemical computers are available atready. We all carry one in our head!

Synthetic supramolecular chemistry

Abstract: For many decades, the construction of organic compounds in the laboratory has relied on the remarkable abilities of the 20th century ‘alchemists’ — namely, synthetic organic chemists — to make and break covalent bonds. Careful selection of functional groups and reaction conditions, in conjunction with protection/deprotection protocols, constitute the ‘secrets’ and ‘tricks’ of their ‘art’ which is commensurate with ‘traditional’ organic synthesis [1,2]. Indeed, relying on multistep reaction sequences, the total syntheses of structurally intricate molecular compounds which are constructed entirely using covalent bonds — e.g., brevetoxin B [3], palytoxin [4], and the calichearubicins [5] — have been realized in recent times. These very elegant and successful syntheses have required enormous intellectual and hands-on effort by large teams of chemists over rather long periods of time — very often, several years. Moreover, these extremely complex, and often particularly beautiful, examples represent close to state-of-the-art as far as ‘traditional’ organic synthesis is concerned. Alas, they also highlight the difficulties and limitations associated with classical organic syntheses — specifically, that the multistep aspect of such syntheses can be extremely laborious and time-consuming. With the possible exception of some dendritic structures [6], it is becoming apparent that the construction of nanoscopic structures, of the same complexities as those found in biological systems, using these classical methods is out of the reach of even the most talented and optimistic of the 20th century chemists!

The missing memristor found

Abstract: Anyone who ever took an electronics laboratory class will be familiar with the fundamental passive circuit elements: the resistor, the capacitor and the inductor. However, in 1971 Leon Chua reasoned from symmetry arguments that there should be a fourth fundamental element, which he called a memristor (short for memory resistor). Although he showed that such an element has many interesting and valuable circuit properties, until now no one has presented either a useful physical model or an example of a memristor. Here we show, using a simple analytical example, that memristance arises naturally in nanoscale systems in which solid-state electronic and ionic transport are coupled under an external bias voltage. These results serve as the foundation for understanding a wide range of hysteretic current-voltage behaviour observed in many nanoscale electronic devices that involve the motion of charged atomic or molecular species, in particular certain titanium dioxide cross-point switches.

Nanoionics-based resistive switching memories

Abstract: Many metal–insulator–metal systems show electrically induced resistive switching effects and have therefore been proposed as the basis for future non-volatile memories. They combine the advantages of Flash and DRAM (dynamic random access memories) while avoiding their drawbacks, and they might be highly scalable. Here we propose a coarse-grained classification into primarily thermal, electrical or ion-migration-induced switching mechanisms. The ion-migration effects are coupled to redox processes which cause the change in resistance. They are subdivided into cation-migration cells, based on the electrochemical growth and dissolution of metallic filaments, and anion-migration cells, typically realized with transition metal oxides as the insulator, in which electronically conducting paths of sub-oxides are formed and removed by local redox processes. From this insight, we take a brief look into molecular switching systems. Finally, we discuss chip architecture and scaling issues.

Carbon quantum dots and their applications

Abstract: Fluorescent carbon nanoparticles or carbon quantum dots (CQDs) are a new class of carbon nanomaterials that have emerged recently and have garnered much interest as potential competitors to conventional semiconductor quantum dots. In addition to their comparable optical properties, CQDs have the desired advantages of low toxicity, environmental friendliness low cost and simple synthetic routes. Moreover, surface passivation and functionalization of CQDs allow for the control of their physicochemical properties. Since their discovery, CQDs have found many applications in the fields of chemical sensing, biosensing, bioimaging, nanomedicine, photocatalysis and electrocatalysis. This article reviews the progress in the research and development of CQDs with an emphasis on their synthesis, functionalization and technical applications along with some discussion on challenges and perspectives in this exciting and promising field.