30 results on '"Friedman DC"'
Search Results
2. Bioindustrial manufacturing readiness levels (BioMRLs) as a shared framework for measuring and communicating the maturity of bioproduct manufacturing processes.
- Author
-
Smanski MJ, Aristidou A, Carruth R, Erickson J, Gordon M, Kedia SB, Lee KH, Prather D, Schiel JE, Schultheisz H, Treynor TP, Evans SL, Friedman DC, and Tomczak M
- Subjects
- Industry, Technology
- Abstract
Readiness level (RL) frameworks such as technology readiness levels and manufacturing readiness levels describe the status of a technology/manufacturing process on its journey from initial conception to commercial deployment. More importantly, they provide a roadmap to guide technology development and scale-up from a ''totality of system'' approach. Commercialization risks associated with too narrowly focused R&D efforts are mitigated. RLs are defined abstractly so that they can apply to diverse industries and technology sectors. However, differences between technology sectors make necessary the definition of sector specific RL frameworks. Here, we describe bioindustrial manufacturing readiness levels (BioMRLs), a classification system specific to bioindustrial manufacturing. BioMRLs will give program managers, investors, scientists, and engineers a shared vocabulary for prioritizing goals and assessing risks in the development and commercialization of a bioindustrial manufacturing process., (© The Author(s) 2022. Published by Oxford University Press on behalf of Society of Industrial Microbiology and Biotechnology.)
- Published
- 2022
- Full Text
- View/download PDF
3. Making Security Viral: Shifting Engineering Biology Culture and Publishing.
- Author
-
Mackelprang R, Adamala KP, Aurand ER, Diggans JC, Ellington AD, Evans SW, Fortman JLC, Hillson NJ, Hinman AW, Isaacs FJ, Medford JI, Mamaghani S, Moon TS, Palmer MJ, Peccoud J, Vitalis EA, Hook-Barnard I, and Friedman DC
- Subjects
- Genes, Viral, SARS-CoV-2 genetics, Synthetic Biology, Bioengineering, Publishing, Security Measures organization & administration
- Abstract
The ability to construct, synthesize, and edit genes and genomes at scale and with speed enables, in synergy with other tools of engineering biology, breakthrough applications with far-reaching implications for society. As SARS-CoV-2 spread around the world in early spring of 2020, researchers rapidly mobilized, using these tools in the development of diagnostics, therapeutics, and vaccines for COVID-19. The sharing of knowledge was crucial to making rapid progress. Several publications described the use of reverse genetics for the de novo construction of SARS-CoV-2 in the laboratory, one in the form of a protocol. Given the demonstrable harm caused by the virus, the unequal distribution of mitigating vaccines and therapeutics, their unknown efficacy against variants, and the interest in this research by laboratories unaccustomed to working with highly transmissible pandemic pathogens, there are risks associated with such publications, particularly as protocols. We describe considerations and offer suggestions for enhancing security in the publication of synthetic biology research and techniques. We recommend: (1) that protocol manuscripts for the de novo synthesis of certain pathogenic viruses undergo a mandatory safety and security review; (2) that if published, such papers include descriptions of the discussions or review processes that occurred regarding security considerations in the main text; and (3) the development of a governance framework for the inclusion of basic security screening during the publication process of engineering biology/synthetic biology manuscripts to build and support a safe and secure research enterprise that is able to maximize its positive impacts and minimize any negative outcomes.
- Published
- 2022
- Full Text
- View/download PDF
4. Agricultural Crop Security: Exploring US Federal Readiness and Response Capabilities.
- Author
-
Mackelprang R and Friedman DC
- Subjects
- Agriculture, Animals, Emergencies, United States, Bioterrorism prevention & control, Crops, Agricultural
- Abstract
A large-scale agroterrorism attack on the United States would likely have severe economic and social consequences. In particular, the destruction of crops with pests or pathogens could cause substantial damage to food, economic, and social stability, with relatively little health risk to the perpetrators. The tools of engineering biology could enable a well-trained, nefarious actor to amplify their desired impacts through the development of disease-intensifying traits. In the United States, plant health emergencies are handled first at the local and state levels, then escalated to include the support and leadership of the US Department of Agriculture (USDA) and other federal agencies. We used publicly available documents and interviews across government, academia, and industry to explore the strategic and tactical approaches of the US federal government to detect and respond to plant agroterrorism. In this article, we discuss the agroterrorism preparedness and response capabilities at 3 levels of federal response: (1) within the Plant Protection and Quarantine program of the Animal and Plant Health Inspection Service at the USDA, (2) between USDA components, and (3) between federal agencies. We outline the approaches currently taken and identify opportunities to strengthen these approaches.
- Published
- 2021
- Full Text
- View/download PDF
5. Guiding Ethical Principles in Engineering Biology Research.
- Author
-
Mackelprang R, Aurand ER, Bovenberg RAL, Brink KR, Charo RA, Delborne JA, Diggans J, Ellington AD, Fortman JLC, Isaacs FJ, Medford JI, Murray RM, Noireaux V, Palmer MJ, Zoloth L, and Friedman DC
- Subjects
- Administrative Personnel ethics, Communication, Environmental Health, Humans, Medical Laboratory Personnel ethics, Public Health, Research Design, Research Personnel ethics, Social Responsibility, Bioengineering ethics, Biomedical Research ethics, Inventions ethics
- Abstract
Engineering biology is being applied toward solving or mitigating some of the greatest challenges facing society. As with many other rapidly advancing technologies, the development of these powerful tools must be considered in the context of ethical uses for personal, societal, and/or environmental advancement. Researchers have a responsibility to consider the diverse outcomes that may result from the knowledge and innovation they contribute to the field. Together, we developed a Statement of Ethics in Engineering Biology Research to guide researchers as they incorporate the consideration of long-term ethical implications of their work into every phase of the research lifecycle. Herein, we present and contextualize this Statement of Ethics and its six guiding principles. Our goal is to facilitate ongoing reflection and collaboration among technical researchers, social scientists, policy makers, and other stakeholders to support best outcomes in engineering biology innovation and development.
- Published
- 2021
- Full Text
- View/download PDF
6. Engineering Microbiomes-Looking Ahead.
- Author
-
Lee ED, Aurand ER, and Friedman DC
- Subjects
- Animals, Bacteria metabolism, Humans, Intestines microbiology, Metabolic Engineering, Microbiota
- Published
- 2020
- Full Text
- View/download PDF
7. YouTube resources for synthetic biology education.
- Author
-
Dy AJ, Aurand ER, and Friedman DC
- Abstract
Online video resources have increasingly become a common way to effectively share scientific research ideas and engage viewers at many levels of interest or expertise. While synthetic biology is a comparatively young field, it has accumulated online videos across a spectrum of content and technical depth. Such video content can be used to introduce viewers to synthetic biology, supplement college course content, teach new lab skills and entertain. Here, we compile online videos concerning synthetic biology into public YouTube playlists tailored for six different, though potentially overlapping, audiences: those wanting an introduction to synthetic biology, those wanting to get quick overviews of specific topics within synthetic biology, those wanting teaching or public lectures, those wanting more technical research lectures, those wanting to learn lab protocols and those interested in the International Genetically Engineered Machine competition., (© The Author(s) 2019. Published by Oxford University Press.)
- Published
- 2019
- Full Text
- View/download PDF
8. Author Correction: Building a global alliance of biofoundries.
- Author
-
Hillson N, Caddick M, Cai Y, Carrasco JA, Chang MW, Curach NC, Bell DJ, Feuvre RL, Friedman DC, Fu X, Gold ND, Herrgård MJ, Holowko MB, Johnson JR, Johnson RA, Keasling JD, Kitney RI, Kondo A, Liu C, Martin VJJ, Menolascina F, Ogino C, Patron NJ, Pavan M, Poh CL, Pretorius IS, Rosser SJ, Scrutton NS, Storch M, Tekotte H, Travnik E, Vickers CE, Yew WS, Yuan Y, Zhao H, and Freemont PS
- Abstract
The original version of this Comment contained errors in the legend of Figure 2, in which the locations of the fifteenth and sixteenth GBA members were incorrectly given as '(15) Australian Genome Foundry, Macquarie University; (16) Australian Foundry for Advanced Biomanufacturing, University of Queensland.'. The correct version replaces this with '(15) Australian Foundry for Advanced Biomanufacturing (AusFAB), University of Queensland and (16) Australian Genome Foundry, Macquarie University'. This has been corrected in both the PDF and HTML versions of the Comment.
- Published
- 2019
- Full Text
- View/download PDF
9. Building a global alliance of biofoundries.
- Author
-
Hillson N, Caddick M, Cai Y, Carrasco JA, Chang MW, Curach NC, Bell DJ, Le Feuvre R, Friedman DC, Fu X, Gold ND, Herrgård MJ, Holowko MB, Johnson JR, Johnson RA, Keasling JD, Kitney RI, Kondo A, Liu C, Martin VJJ, Menolascina F, Ogino C, Patron NJ, Pavan M, Poh CL, Pretorius IS, Rosser SJ, Scrutton NS, Storch M, Tekotte H, Travnik E, Vickers CE, Yew WS, Yuan Y, Zhao H, and Freemont PS
- Subjects
- Biomedical Research methods, Biotechnology instrumentation, Genetic Engineering, International Cooperation, Organisms, Genetically Modified
- Published
- 2019
- Full Text
- View/download PDF
10. Industrialization of Biology.
- Author
-
Friedman DC and Ellington AD
- Subjects
- Synthetic Biology organization & administration, Synthetic Biology methods
- Abstract
The advancement of synthetic biology over the past decade has contributed substantially to the growing bioeconomy. A recent report by the National Academies highlighted several areas of advancement that will be needed for further expansion of industrial biotechnology, including new focuses on design, feedstocks, processing, organism development, and tools for testing and measurement; more particularly, a focus on expanded chassis and end-to-end design in an effort to move beyond the use of E. coli and S. cerivisiea to organisms better suited to fermentation and production; second, continued efforts in systems biology and high-throughput screening with a focus on more rapid techniques that will provide the needed information for moving to larger scale; and finally, work to accelerate the building of a holacratic community with collaboration and engagement between the relevant government agencies, industry, academia, and the public.
- Published
- 2015
- Full Text
- View/download PDF
11. Instrument Failures for the da Vinci Surgical System: a Food and Drug Administration MAUDE Database Study.
- Author
-
Friedman DC, Lendvay TS, and Hannaford B
- Subjects
- Databases, Factual, Electric Wiring, Electrocoagulation instrumentation, Equipment Design, Equipment Failure Analysis statistics & numerical data, Humans, Product Surveillance, Postmarketing, Retrospective Studies, Risk Management, Robotics statistics & numerical data, Selection Bias, United States, United States Food and Drug Administration, Equipment Failure statistics & numerical data, Laparoscopy instrumentation, Robotics instrumentation
- Abstract
Background: Our goal was to analyze reported instances of the da Vinci robotic surgical system instrument failures using the FDA's MAUDE (Manufacturer and User Facility Device Experience) database. From these data we identified some root causes of failures as well as trends that may assist surgeons and users of the robotic technology., Methods: We conducted a survey of the MAUDE database and tallied robotic instrument failures that occurred between January 2009 and December 2010. We categorized failures into five main groups (cautery, shaft, wrist or tool tip, cable, and control housing) based on technical differences in instrument design and function., Results: A total of 565 instrument failures were documented through 528 reports. The majority of failures (285) were of the instrument's wrist or tool tip. Cautery problems comprised 174 failures, 76 were shaft failures, 29 were cable failures, and 7 were control housing failures. Of the reports, 10 had no discernible failure mode and 49 exhibited multiple failures., Conclusions: The data show that a number of robotic instrument failures occurred in a short period of time. In reality, many instrument failures may go unreported, thus a true failure rate cannot be determined from these data. However, education of hospital administrators, operating room staff, surgeons, and patients should be incorporated into discussions regarding the introduction and utilization of robotic technology. We recommend institutions incorporate standard failure reporting policies so that the community of robotic surgery companies and surgeons can improve on existing technologies for optimal patient safety and outcomes.
- Published
- 2013
- Full Text
- View/download PDF
12. Self-assembly of a [2]pseudorota[3]catenane in water.
- Author
-
Forgan RS, Gassensmith JJ, Cordes DB, Boyle MM, Hartlieb KJ, Friedman DC, Slawin AM, and Stoddart JF
- Subjects
- Models, Molecular, Anthracenes chemistry, Water chemistry
- Abstract
A donor-acceptor [3]catenane incorporating two cyclobis(paraquat-p-phenylene) rings linked together by a dinaphtho[50]crown-14 macrocycle possesses a π-electron-deficient pocket. Contrary to expectation, negligible binding of a hexaethylene glycol chain interrupted in its midriff by a π-electron-rich 1,5-dioxynaphthalene unit was observed in acetonitrile. However, a fortuitous solid-state superstructure of the expected 1:1 complex revealed its inability to embrace any stabilizing [C-H···O] interactions between the clearly unwelcome guest and the host reluctantly accommodating it. By contrast, in aqueous solution, the 1:1 complex becomes very stable thanks to the intervention of hydrophobic bonding.
- Published
- 2012
- Full Text
- View/download PDF
13. Positive cooperativity in the template-directed synthesis of monodisperse macromolecules.
- Author
-
Belowich ME, Valente C, Smaldone RA, Friedman DC, Thiel J, Cronin L, and Stoddart JF
- Abstract
Two series of oligorotaxanes R and R' that contain -CH(2)NH(2)(+)CH(2)- recognition sites in their dumbbell components have been synthesized employing template-directed protocols. [24]Crown-8 rings self-assemble by a clipping strategy around each and every recognition site using equimolar amounts of 2,6-pyridinedicarboxaldehyde and tetraethyleneglycol bis(2-aminophenyl) ether to efficiently provide up to a [20]rotaxane. In the R series, the -NH(2)(+)- recognition sites are separated by trismethylene bridges, whereas in the R' series the spacers are p-phenylene linkers. The underpinning idea here is that in the former series, the recognition sites are strategically positioned 3.5 Å apart from one another so as to facilitate efficient [π···π] stacking between the aromatic residues in contiguous rings in the rotaxanes and consequently, a discrete rigid and rod-like conformation is realized; these noncovalent interactions are absent in the latter series rendering them conformationally flexible/nondiscrete. Although in the R' series, the [3]-, [4]-, [8]-, and [12]rotaxanes were isolated after reaction times of <5-30 min in yields of 72-85%, in the R series, the [3]-, [4]-, [5]-, [8]-, [12]-, [16]-, and [20]rotaxanes were isolated in <5 min to 14 h in 88-98% yields. It follows that while in the R' series the higher order oligorotaxanes are formed in lower yields more rapidly, in the R series, the higher order oligorotaxanes are formed in higher yields more slowly. In the R series, the high percentage yields are sustained throughout, despite the fact that up to 39 components are participating in the template-directed self-assembly process. Simple arithmetic reveals that the conversion efficiency for each imine bond formation peaks at 99.9% in the R series and 99.3% in the R' series. This maintenance of reaction efficiency in the R series can be ascribed to positive cooperativity, that is, when one ring is formed it aids and abets the formation of subsequent rings presumably because of stabilizing extended [π···π] stacking interactions between the arene units. Experiments have been performed wherein the dumbbell is starved of the macrocyclic components, and up to five times more of the fully saturated rotaxane is formed than is predicted based on a purely statistical outcome, providing a clear indication that positive cooperativity is operative. Moreover, it would appear that as the R series is traversed from the [3]- to the [4]- to the [5]rotaxane, the cooperativity becomes increasingly positive. This kind of cooperative behavior is not observed for the analogous oligorotaxanes in the R' series. The conventional bevy of analytical techniques (e.g., HR-MS (ESI) and both (1)H and (13)C NMR spectroscopy) help establish the fact that all the oligorotaxanes are pure and monodisperse. Evidence of efficient [π···π] stacking between contiguous arene units in the rings in the R series is revealed by (1)H NMR spectroscopy. Ion-mobility mass spectrometry performed on the R and R' series yielded the collisional cross sections (CCSs), confirming the rigidity of the R oligorotaxanes and the flexibility of the R' ones. The extended [π···π] stacking interactions are found to be present in the solid-state structures of the [3]- and [4]rotaxanes in the R series and also on the basis of molecular mechanics calculations performed on the entire series of oligomers. The collective data presented herein supports our original design in that the extended [π···π] stacking between contiguous arene units in the rings of the R series of oligorotaxanes facilitate an essentially rigid rod-like conformation with evidence that positive cooperativity improves the efficiency of their formation. This situation stands in sharp contrast to the conformationally flexible R' series where the oligorotaxanes form with no cooperativity.
- Published
- 2012
- Full Text
- View/download PDF
14. Donor-acceptor ring-in-ring complexes.
- Author
-
Forgan RS, Wang C, Friedman DC, Spruell JM, Stern CL, Sarjeant AA, Cao D, and Stoddart JF
- Abstract
The self-assembly of three donor-acceptor ring-in-ring complexes, prepared from the π-electron-deficient tetracationic cyclophane, cyclobis(paraquat-4,4'-biphenylene), and three large π-electron-rich crown ethers (each 50-membered rings) containing dioxynaphthalene (DNP) and tetrathiafulvalene (TTF) units in pairs (DNP/DNP, DNP/TTF and TTF/TTF), is reported. (1)H NMR spectroscopic analyses are indicative of the formation of 1:1 complexes in CD(3)CN, whilst the charge-transfer interactions between the DNP and TTF units of the crown ethers and the tetracationic cyclophane have permitted the measurement of binding constants of up to 4×10(3) M(-1) in CH(3)CN to be made using UV/Vis spectroscopy. Ring-in-ring complexes are proposed as intermediates in the stepwise synthesis of molecular Borromean rings (BRs) comprised of three different rings. With the particular choice of crown ethers, the 1:1 complexes have polyether loops that protrude from the donor-acceptor recognition point above and below the mean plane of the tetracationic cyclophane, which, ideally, could conceivably bind dialkylammonium centers present in a third ring. X-ray crystallographic analyses of the solid-state superstructures of two of the three 1:1 complexes reveal, however, the presence of prodigious CH···O interactions between the polyether loops of the crown ethers and the rims of the cyclophane, no doubt stabilizing the complexes, but, at the same time, masking their potential recognition sites from further interactions that are essential to the subsequent emergence of the third ring. The solid-state superstructure of one of the crown ethers binding two dibenzylammonium ions provides some insight into the design requirements for the next generation of these systems; longer polyether loops may be required to allow optimal interactions between all components. It has become clear during a pursuit of the stepwise synthesis of the molecular BRs that, when designing complex mechanically interlocked molecules utilizing multiple recognition sites, the unsullied orthogonality of the recognition motifs is of the utmost importance., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
- Published
- 2012
- Full Text
- View/download PDF
15. Donor-acceptor molecular figures-of-eight.
- Author
-
Boyle MM, Forgan RS, Friedman DC, Gassensmith JJ, Smaldone RA, Stoddart JF, and Sauvage JP
- Abstract
The intermolecular template-directed synthesis, separation and characterisation of two constitutional isomers that are self-complexing donor-acceptor [1]rotaxanes has been achieved by click chemistry, starting from a π-electron deficient tetracationic cyclophane containing two azide functions and a π-electron rich 1,5-dioxynaphthalene-containing polyether chain terminated by propargyl groups., (This journal is © The Royal Society of Chemistry 2011)
- Published
- 2011
- Full Text
- View/download PDF
16. A neutral redox-switchable [2]rotaxane.
- Author
-
Olsen JC, Fahrenbach AC, Trabolsi A, Friedman DC, Dey SK, Gothard CM, Shveyd AK, Gasa TB, Spruell JM, Olson MA, Wang C, Jacquot de Rouville HP, Botros YY, and Stoddart JF
- Subjects
- Cyclization, Molecular Structure, Oxidation-Reduction, Rotaxanes chemistry
- Abstract
A limited range of redox-active, rotaxane-based, molecular switches exist, despite numerous potential applications for them as components of nanoscale devices. We have designed and synthesised a neutral, redox-active [2]rotaxane, which incorporates an electron-deficient pyromellitic diimide (PmI)-containing ring encircling two electron-rich recognition sites in the form of dioxynaphthalene (DNP) and tetrathiafulvalene (TTF) units positioned along the rod section of its dumbbell component. Molecular modeling using MacroModel guided the design of the mechanically interlocked molecular switch. The binding affinities in CH(2)Cl(2) at 298 K between the free ring and two electron-rich guests--one (K(a) = 5.8 × 10(2) M(-1)) containing a DNP unit and the other (K(a) = 6.3 × 10(3) M(-1)) containing a TTF unit--are strong: the one order of magnitude difference in their affinities favouring the TTF unit suggested to us the feasibility of integrating these three building blocks into a bistable [2]rotaxane switch. The [2]rotaxane was obtained in 34% yield by relying on neutral donor-acceptor templation and a double copper-catalysed azide-alkyne cycloaddition (CuAAC). Cyclic voltammetry (CV) and spectroelectrochemistry (SEC) were employed to stimulate and observe switching by this neutral bistable rotaxane in solution at 298 K, while (1)H NMR spectroscopy was enlisted to investigate switching upon chemical oxidation. The neutral [2]rotaxane is a chemically robust and functional switch with potential for applications in device settings.
- Published
- 2011
- Full Text
- View/download PDF
17. Mechanically interlocked mechanophores by living-radical polymerization from rotaxane initiators.
- Author
-
Stoll RS, Friedman DC, and Stoddart JF
- Abstract
Two [2]rotaxane initiators for single-electron-transfer living-radical-polymerization were synthesized and used for the controlled polymerization of methyl acrylate. The mechanically interlocked polymers exhibited distinct responses to mechanical activation by ultrasound. Monitoring the fate of the rotaxanes' charge transfer absorption bands provides evidence for preferential mechanical degradation of a midsection rotaxane unit as compared to a terminal rotaxane entity as a consequence of mechanical forces accumulating in the central region of the polymer chain.
- Published
- 2011
- Full Text
- View/download PDF
18. Mechanically stabilized tetrathiafulvalene radical dimers.
- Author
-
Coskun A, Spruell JM, Barin G, Fahrenbach AC, Forgan RS, Colvin MT, Carmieli R, Benítez D, Tkatchouk E, Friedman DC, Sarjeant AA, Wasielewski MR, Goddard WA 3rd, and Stoddart JF
- Subjects
- Catenanes chemistry, Dimerization, Free Radicals chemistry, Models, Molecular, Oxidation-Reduction, Heterocyclic Compounds chemistry
- Abstract
Two donor-acceptor [3]catenanes-composed of a tetracationic molecular square, cyclobis(paraquat-4,4'-biphenylene), as the π-electron deficient ring and either two tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) containing macrocycles or two TTF-butadiyne-containing macrocycles as the π-electron rich components-have been investigated in order to study their ability to form TTF radical dimers. It has been proven that the mechanically interlocked nature of the [3]catenanes facilitates the formation of the TTF radical dimers under redox control, allowing an investigation to be performed on these intermolecular interactions in a so-called "molecular flask" under ambient conditions in considerable detail. In addition, it has also been shown that the stability of the TTF radical-cation dimers can be tuned by varying the secondary binding motifs in the [3]catenanes. By replacing the DNP station with a butadiyne group, the distribution of the TTF radical-cation dimer can be changed from 60% to 100%. These findings have been established by several techniques including cyclic voltammetry, spectroelectrochemistry and UV-vis-NIR and EPR spectroscopies, as well as with X-ray diffraction analysis which has provided a range of solid-state crystal structures. The experimental data are also supported by high-level DFT calculations. The results contribute significantly to our fundamental understanding of the interactions within the TTF radical dimers.
- Published
- 2011
- Full Text
- View/download PDF
19. Donor-acceptor oligorotaxanes made to order.
- Author
-
Basu S, Coskun A, Friedman DC, Olson MA, Benítez D, Tkatchouk E, Barin G, Yang J, Fahrenbach AC, Goddard WA 3rd, and Stoddart JF
- Subjects
- Catalysis, Copper chemistry, Crystallography, X-Ray, Electrons, Hydrogen Bonding, Magnetic Resonance Spectroscopy, Models, Molecular, Molecular Conformation, Protons, Rotaxanes chemical synthesis, Rotaxanes chemistry
- Abstract
Five donor-acceptor oligorotaxanes made up of dumbbells composed of tetraethylene glycol chains, interspersed with three and five 1,5-dioxynaphthalene units, and terminated by 2,6-diisopropylphenoxy stoppers, have been prepared by the threading of discrete numbers of cyclobis(paraquat-p-phenylene) rings, followed by a kinetically controlled stoppering protocol that relies on click chemistry. The well-known copper(I)-catalyzed alkyne-azide cycloaddition between azide functions placed at the ends of the polyether chains and alkyne-bearing stopper precursors was employed during the final kinetically controlled template-directed synthesis of the five oligorotaxanes, which were characterized subsequently by (1)H NMR spectroscopy at low temperature (233 K) in deuterated acetonitrile. The secondary structures, as well as the conformations, of the five oligorotaxanes were unraveled by spectroscopic comparison with the dumbbell and ring components. By focusing attention on the changes in chemical shifts of some key probe protons, obtained from a wide range of low-temperature spectra, a picture emerges of a high degree of folding within the thread protons of the dumbbells of four of the five oligorotaxanes-the fifth oligorotaxane represents a control compound in effect-brought about by a combination of C-H···O and π-π stacking interactions between the π-electron-deficient bipyridinium units in the rings and the π-electron-rich 1,5-dioxynaphthalene units and polyether chains in the dumbbells. The secondary structures of a foldamer-like nature have received further support from a solid-state superstructure of a related [3]pseudorotaxane and density functional calculations performed thereon., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
- Published
- 2011
- Full Text
- View/download PDF
20. A multistate switchable [3]rotacatenane.
- Author
-
Barin G, Coskun A, Friedman DC, Olson MA, Colvin MT, Carmielli R, Dey SK, Bozdemir OA, Wasielewski MR, and Stoddart JF
- Abstract
Rotacatenanes are exotic molecular compounds that can be visualized as a unique combination of a [2]catenane and a [2]rotaxane, thereby combining both the circumrotation of the ring component (rotary motion) and the shuttling of the dumbbell component (translational motion) in one structure. Herein, we describe a strategy for the synthesis of a new switchable [3]rotacatenane and the investigation of its switching properties, which rely on the formation of tetrathiafulvalene (TTF) radical π-dimer interactions-namely, the mixed-valence state (TTF(2) )(+.) and the radical-cation dimer state (TTF(+.) )(2) -under ambient conditions. A template-directed approach, based on donor-acceptor interactions, has been developed, resulting in an improved yield of the key precursor [2]catenane, prior to rotacatenation. The nature of the binding between the [2]catenane and selected π-electron-rich templates has been elucidated by using X-ray crystallography and UV/Vis spectroscopy as well as isothermal titration microcalorimetry. The multistate switching mechanism of the [3]rotacatenane has been demonstrated by cyclic voltammetry and EPR spectroscopy. Most notably, the radical-cation dimer state (TTF(+.) )(2) has been shown to enter into an equilibrium by forming the co-conformation in which the two 1,5-dioxynaphthalene (DNP) units co-occupy the cavity of tetracationic cyclophane, thus enforcing the separation of TTF radical-cation dimer (TTF(+.) )(2) . The population ratio of this equilibrium state was found to be 1:1. We believe that this research demonstrates the power of constructing complex molecular machines using template-directed protocols, enabling us to make the transition from simple molecular switches to their multistate variants for enhancing information storage in molecular electronic devices., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
- Published
- 2011
- Full Text
- View/download PDF
21. Highly stable tetrathiafulvalene radical dimers in [3]catenanes.
- Author
-
Spruell JM, Coskun A, Friedman DC, Forgan RS, Sarjeant AA, Trabolsi A, Fahrenbach AC, Barin G, Paxton WF, Dey SK, Olson MA, Benítez D, Tkatchouk E, Colvin MT, Carmielli R, Caldwell ST, Rosair GM, Hewage SG, Duclairoir F, Seymour JL, Slawin AM, Goddard WA 3rd, Wasielewski MR, Cooke G, and Stoddart JF
- Subjects
- Dimerization, Catenanes chemistry
- Abstract
Two [3]catenane 'molecular flasks' have been designed to create stabilized, redox-controlled tetrathiafulvalene (TTF) dimers, enabling their spectrophotometric and structural properties to be probed in detail. The mechanically interlocked framework of the [3]catenanes creates the ideal arrangement and ultrahigh local concentration for the encircled TTF units to form stable dimers associated with their discrete oxidation states. These dimerization events represent an affinity umpolung, wherein the inversion in electronic affinity replaces the traditional TTF-bipyridinium interaction, which is over-ridden by stabilizing mixed-valence (TTF)2•+ and radical-cation (TTF•+)2 states inside the 'molecular flasks.' The experimental data, collected in the solid state as well as in solution under ambient conditions, together with supporting quantum mechanical calculations, are consistent with the formation of stabilized paramagnetic mixed-valence dimers, and then diamagnetic radical-cation dimers following subsequent one-electron oxidations of the [3]catenanes.
- Published
- 2010
- Full Text
- View/download PDF
22. Directed self-assembly of a ring-in-ring complex.
- Author
-
Forgan RS, Friedman DC, Stern CL, Bruns CJ, and Stoddart JF
- Abstract
A strategic modification to the corner ligands in Pd(II)-containing, electron-poor cyclophanes has profound repercussions for their assemblies with electron-rich aromatic crown ethers in both the solid and solution states; the formation of ring-in-ring complexes can override competing [3]catenane production on masking the hydrogen bond donor capabilities of the corner ligands.
- Published
- 2010
- Full Text
- View/download PDF
23. A tristable [2]pseudo[2]rotaxane.
- Author
-
Trabolsi A, Fahrenbach AC, Dey SK, Share AI, Friedman DC, Basu S, Gasa TB, Khashab NM, Saha S, Aprahamian I, Khatib HA, Flood AH, and Stoddart JF
- Abstract
A strategy towards increasing the lifetime of the metastable state of a [2]rotaxane incorporating tetrathiafulvalene, 1,5-dioxynaphthalene and bipyridinium (BIPY(2+)) is presented. Incorporation of BIPY(2+) served multiple roles as an electrostatic barrier to relaxation, a supramolecular recognition site for bis-1,5-dioxynaphthalene[38]crown-10 macrocycle, and upon reduction a recognition site for the mechanically bonded cyclobis(paraquat-p-phenylene) ring.
- Published
- 2010
- Full Text
- View/download PDF
24. Radically enhanced molecular recognition.
- Author
-
Trabolsi A, Khashab N, Fahrenbach AC, Friedman DC, Colvin MT, Cotí KK, Benítez D, Tkatchouk E, Olsen JC, Belowich ME, Carmielli R, Khatib HA, Goddard WA 3rd, Wasielewski MR, and Stoddart JF
- Subjects
- Dimerization, Electron Spin Resonance Spectroscopy, Oxidation-Reduction, Pyridinium Compounds chemistry, Quantum Theory, Rotaxanes chemistry, Spectrophotometry, Ultraviolet, Thermodynamics, Viologens chemistry, Free Radicals chemistry
- Abstract
The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication.
- Published
- 2010
- Full Text
- View/download PDF
25. pH-responsive mechanised nanoparticles gated by semirotaxanes.
- Author
-
Khashab NM, Belowich ME, Trabolsi A, Friedman DC, Valente C, Lau Y, Khatib HA, Zink JI, and Stoddart JF
- Subjects
- Biocompatible Materials chemistry, Bridged-Ring Compounds chemistry, Hydrogen-Ion Concentration, Imidazoles chemistry, Macrocyclic Compounds chemistry, Magnetic Resonance Spectroscopy, Rhodamines chemistry, Silicon Dioxide chemistry, Spectrometry, Fluorescence, Viologens chemistry, Drug Delivery Systems methods, Nanoparticles chemistry, Rotaxanes chemistry
- Abstract
A [2]pseudorotaxane-based mechanised nanoparticle system, which operates within an aqueous acidic environment, has been prepared and characterised; this integrated system affords both water-soluble stalk and ring components in an effort to improve the biocompatibility of these promising new drug delivery vehicles.
- Published
- 2009
- Full Text
- View/download PDF
26. A push-button molecular switch.
- Author
-
Spruell JM, Paxton WF, Olsen JC, Benítez D, Tkatchouk E, Stern CL, Trabolsi A, Friedman DC, Goddard WA 3rd, and Stoddart JF
- Abstract
The preparation, characterization, and switching mechanism of a unique single-station mechanically switchable hetero[2]catenane are reported. The facile synthesis utilizing a "threading-followed-by-clipping" protocol features Cu(2+)-catalyzed Eglinton coupling as a mild and efficient route to the tetrathiafulvalene-based catenane in high yield. The resulting mechanically interlocked molecule operates as a perfect molecular switch, most readily described as a "push-button" switch, whereby two discrete and fully occupied translational states are toggled electrochemically at incredibly high rates. This mechanical switching was probed using a wide variety of experimental techniques as well as quantum-mechanical investigations. The fundamental distinctions between this single-station [2]catenane and other more traditional bi- and multistation molecular switches are significant.
- Published
- 2009
- Full Text
- View/download PDF
27. A light-gated STOP-GO molecular shuttle.
- Author
-
Coskun A, Friedman DC, Li H, Patel K, Khatib HA, and Stoddart JF
- Abstract
Degenerate [2]rotaxanes, with their two identical binding sites, generally exhibit equilibrium dynamics with free energies of activation (DeltaG(double dagger)) for the shuttling process starting as low as 10 kcal x mol(-1). This DeltaG(double dagger) value can be raised quite dramatically by inserting "speed bumps" in the form of steric and/or electrostatic barriers into the linkers between the two identical binding sites. In our more recent research targeted toward the exploitation of the 4,4'-azobiphenyloxy unit (ABP) as a light-operated gate, we decided to introduce (i) four methyl groups on the one hand and (ii) four fluorine atoms on the other, at the 3,5,3',5'-positions of the ABP units to curtail binding by the CBPQT(4+) ring if not sterically in the case of i, then electronically in the case of ii. The first approach led to a gate (ABP-Me(4)) that remains closed all the time, whereas the second approach affords a gate (ABP-F(4)) that we can close with UV light and open with visible light. Herein, we show how light can be used, in conjunction with thermal energy, to raise and lower the free energy barrier at will and, in so doing, impart STOP and GO instructions upon the operation of a molecular shuttle.
- Published
- 2009
- Full Text
- View/download PDF
28. Teleoperation in surgical robotics--network latency effects on surgical performance.
- Author
-
Lum MJ, Rosen J, King H, Friedman DC, Lendvay TS, Wright AS, Sinanan MN, and Hannaford B
- Subjects
- Adolescent, Adult, Florida, Humans, Time Factors, Washington, Young Adult, Laparoscopy methods, Robotics methods, Telemedicine methods
- Abstract
A teleoperated surgical robotic system allows surgical procedures to be conducted across long distances while utilizing wired and wireless communication with a wide spectrum of performance that may affect the outcome. An open architecture portable surgical robotic system (Raven) was developed for both open and minimally invasive surgery. The system has been the subject of an intensive telesurgical experimental protocol aimed at exploring the boundaries of the system and surgeon performance during a series of field experiments in extreme environments (desert and underwater) teleportation between US, Europe, and Japan as well as lab experiments under synthetic fixed time delay. One standard task (block transfer emulating tissue manipulation) of the Fundamentals of Laparoscopic Surgery (FLS) training kit was used for the experimental protocol. Network characterization indicated a typical time delay in the range of 16-172 ms in field experiments. The results of the lab experiments showed that the completion time of the task as well as the length of the tool tip trajectory significantly increased (alpha< 0.02) as time delay increased in the range of 0-0.5 sec increased. For teleoperation with a time delay of 0.25s and 0.5s the task completion time was lengthened by a factor of 1.45 and 2.04 with respect to no time delay, whereas the length of the tools' trajectory was increased by a factor of 1.28 and 1.53 with respect to no time delay. There were no statistical differences between experienced surgeons and non-surgeons in the number of errors (block drooping) as well as the completion time and the tool tip path length at different time delays.
- Published
- 2009
- Full Text
- View/download PDF
29. Objective assessment of telesurgical robot systems: Telerobotic FLS.
- Author
-
Lum MJ, Friedman DC, Sankaranarayanan G, King H, Wright A, Sinanan M, Lendvay T, Rosen J, and Hannaford B
- Subjects
- Humans, Psychomotor Performance, United States, Endoscopy, Gastrointestinal, General Surgery education, Robotics instrumentation, Telemedicine
- Abstract
The Society of American Gastrointestinal Endoscopic Surgeons (SAGES) Fundamentals of Laparoscopic Surgery (FLS) program contains curriculum that includes both a cognitive and psychomotor skills. In this research the use of FLS Block Transfer task is used to evaluate the performance of surgeons' teleoperating the University of Washington Surgical robot. The use of the FLS Trainer Box and accessories kit provides a well-defined series of tasks that can be repeated by any researchers working in the field of surgical robotics so that systems can be evaluated using a common method.
- Published
- 2008
30. Telesurgery via Unmanned Aerial Vehicle (UAV) with a field deployable surgical robot.
- Author
-
Lum MJ, Rosen J, King H, Friedman DC, Donlin G, Sankaranarayanan G, Harnett B, Huffman L, Doarn C, Broderick T, and Hannaford B
- Subjects
- California, Aircraft, General Surgery, Robotics
- Abstract
Robotically assisted surgery stands to further revolutionize the medical field and provide patients with more effective healthcare. Most robotically assisted surgeries are teleoperated from the surgeon console to the patient where both ends of the system are located in the operating room. The challenge of surgical teleoperation across a long distance was already demonstrated through a wired communication network in 2001. New development has shifted towards deploying a surgical robot system in mobile settings and/or extreme environments such as the battlefield or natural disaster areas with surgeons operating wirelessly. As a collaborator in the HAPs/MRT (High Altitude Platform/Mobile Robotic Telesurgery) project, The University of Washington surgical robot was deployed in the desert of Simi Valley, CA for telesurgery experiments on an inanimate model via wireless communication through an Unmanned Aerial Vehicle (UAV). The surgical tasks were performed telerobotically with a maximum time delay between the surgeon's console (master) and the surgical robot (slave) of 20 ms for the robotic control signals and 200 ms for the video stream. This was our first experiment in the area of Mobile Robotic Telesurgery (MRT). The creation and initial testing of a deployable surgical robot system will facilitate growth in this area eventually leading to future systems saving human lives in disaster areas, on the battlefield or in other remote environments.
- Published
- 2007
Catalog
Discovery Service for Jio Institute Digital Library
For full access to our library's resources, please sign in.