bluuebunny/crossref_metadata_2025_split huggingface dataset:
Direct Electron Transfer and Oxygen Reduction Reaction on Hemoglobin with Indium Tin Oxide Synthesized with Different Metal Compositions
Authors: Ayato Yusuke , Sugimoto Wataru 
Published: February 2020

Biofuel cells (BFCs) are nature-inspired electrochemical systems. Natural bio-materials (e.g. glucose as the fuel and enzymes as the electrocatalysts) are used under mild conditions at around body temperature at near-neutral pH. We have developed BFCs with hemoglobin (Hb), [1, 2] making it possible for use as body implantable power supplies applied to medical devices such as pacemakers for cardiac resynchronization therapy and deep brain stimulation. In this study, indium tin oxide (ITO) thin films were synthesized on glass plates with different metal molar ratio by dip-coating methods and used as bio-electrodes for Hb. Electrochemical evaluation was conducted under a three-electrode system consisting of the synthesized ITO working, a platinum wire counter, and an Ag|AgCl|KCl(satd.) reference electrode. Cyclic voltammograms (CVs) in a Hb containing solution with pH 7.4 revealed a pair of well-defined redox peaks at around -0.15 V vs. Ag|AgCl|KCl(satd.) on the ITO electrode with In:Sn=19:1. The quantity of electrochemically active Hb molecules was estimated from the oxidation current of the CV curve. The estimated value of 9.1 pmol in this study corresponds well with the theoretical monolayer deposition of 8.3 pmol, assuming one Hb molecule occupies 20 nm2 [3]. On the other hand, it was found that remarkably large redox current was observed for the ITO electrode with In:Sn=1:1, 222.3 pmol of Hb was estimated to be electrochemically active. It indicates that the electrochemically active species were not only Hb molecules in monolayer deposition on the ITO electrode but also included adsorbed multilayer Hb molecules, suggesting the charge transfer through several Hb molecules in multilayer deposition. Hb molecules exhibited oxygen reduction reaction (ORR) activity on all ITO electrodes with different metal molar ratio. The ITO with In:Sn=1:1 showed the highest ORR activity. These results prove that the Hb-ITO system can be used as the BFC cathode. These findings are great advantages for practical use of the Hb-ITO system, in particular for body implantable power supplies, as the BFC ITO cathode may be inserted into blood vessels.
References
[1] Y. Ayato, K. Sakurai, S. Fukunaga, T. Suganuma, K. Yamagiwa, H. Shiroishi, J. Kuwano, Biosens Bioelectron, 55 (2014) 14.
[2] Y. Ayato, N. Matsuda, Energies, 7(1) (2014) 1.
[3] M. Revenga-Parra, E. Lorenzo, F. Pariente, Sens. Actuat. B, 107 (2005) 678.
Selective Electrochemical Sensing of Human Albumin By Semi-Covalent Imprinting
Authors: Cieplak Maciej , Szwabinska Katarzyna , KC Chandra , Borowicz Pawel , Noworyta Krzysztof R. , D'Souza Francis , Kutner Wlodzimierz 
Published: February 2020

We devised and fabricated a conducting molecularly imprinted polymer (MIP) for human albumin (HA) determination using semi-covalent imprinting (Scheme 1). The bis(2,2’-bithien-5-yl)methane units constituted the MIP backbone. This MIP was deposited as a thin film on an Au disk electrode by oxidative potentiodynamic electropolymerization. The HA template imprinting, and then its releasing from the MIP was confirmed by the XPS and PM-IRRAS measurements as well as by AFM imaging. The DPV and EIS response to the HA presence in a test solution of the MIP film coated electrode was linear in the range of 0.8 to 20 and 4 to 80 µg/mL HA, respectively, with the limit of detection of 16.6 ng/mL and 0.8 µg/mL HA, respectively. The semi-covalent imprinting provided a very well defined location of recognition functionalities in the MIP molecular cavities. Those were placed only on surface of the imprinted molecular cavities and the polymer surface. The MIP selectivity against low-molecular interferences, common for body fluids, such as blood and urea, was very high. It showed no response to their presence at concentrations encountered in natural samples. Moreover, selectivity of the MIP film coated electrode with respect to macromolecular interferences, such as myoglobin and cytochrome c, was excellent while to lysozyme was slightly lower but still high.

Figure 1
(Invited) Corona Phase Molecular Recognition (CoPhMoRe) to Enable New Nanosensor Interfaces
Authors: Strano Michael S 
Published: February 2020

Our lab at MIT has been interested in how the 1D and 2D electronic structures of carbon nanotubes and graphene respectively can be utilized to advance new concepts in molecular detection. We introduce CoPhMoRe or corona phase molecular recognition1 as a method of discovering synthetic antibodies, or nanotube-templated recognition sites from a heteropolymer library. We show that certain synthetic heteropolymers, once constrained onto a single-walled carbon nanotube by chemical adsorption, also form a new corona phase that exhibits highly selective recognition for speciﬁc molecules. To prove the generality of this phenomenon, we report three examples of heteropolymers–nanotube recognition complexes for riboﬂavin, L-thyroxine and estradiol. The platform opens new opportunities to create synthetic recognition sites for molecular detection. We have also extended this molecular recognition technique to neurotransmitters, producing the first fluorescent sensor for dopamine. Another area of advancement in biosensor development is the use of near infrared fluorescent carbon nanotube sensors for in-vivo detection2. Here, we show that PEG-ligated d(AAAT)7 DNA wrapped SWNT are selective for nitric oxide, a vasodilator of blood vessels, and can be tail vein injected into mice and localized within the viable mouse liver. We use an SJL mouse model to study liver inflammation in vivo using the spatially and spectrally resolved nIR signature of the localized SWNT sensors.

Zhang, JQ et. al. Molecular recognition using corona phase complexes made of synthetic polymers adsorbed on carbon nanotubes. Nature Nanotechnology, 8, 12, 2013, 959-968

Iverson, NM, et. al. In vivo biosensing via tissue-localizable near-infrared-fluorescent single-walled carbon nanotubes. Nature Nanotechnology, 8, 11, 2013, 873-880
Applications of Single Nanotube Imaging Spectroscopy in Live Cells
Authors: Jena Prakrit Vaibhav , Roxbury Daniel , Galassi Thomas Vito , Horoszko Christopher , Budhathoki-Uprety Januka , Heller Daniel 
Published: February 2020

The intrinsic near-infrared photoluminescence from a single nanotube can be detected within a live cell via epifluorescence. As the emission spectrum of a nanotube is exquisitely modulated by the immediate microenvironment of the nanotube, information contained in the peak emission wavelength, intensity, and full width half maximum can reflect physicochemical properties of the microenvironment. We have developed methods for detecting metabolites by employing changes in carbon nanotube emission. By spatially localizing a polymer-functionalized nanotube to a subcellular organelle, and by measuring the spectral response of the nanotube to its environment, we demonstrate the use of single nanotube spectroscopy to quantify specific metabolites in live cells.
Biomedical Applications of Diamond Nanoparticles
Authors: Mochalin Vadym N , Gogotsi Yury 
Published: February 2020

Nanomaterials hold tremendous potential in addressing the two major issues faced by our society: providing energy and improving healthcare. Nanodiamond powder produced by detonation and readily available in commercial quantities for moderate price, is one of the most promising carbon nanomaterials for theranostics [1], [2]. Made of ~5 nm diamond particles with large accessible surface and tailorable surface chemistry, it has unique optical, mechanical and thermal properties, and is non-toxic. These properties have recently started to attract a lot of interest among researchers working on different biomedical applications [3]. For tissue engineering scaffolds, the non-toxic fluorescent nanodiamond introduced into biodegradable polymers provides increased strength, visual monitoring, and enhanced biomineralization [4]. In drug delivery, the rational surface modification of nanodiamond allows for enhanced adsorption and chemical binding of the drugs for sustained or triggered drug release. In the area of biomedical imaging and diagnostics, luminescent nanodiamond with NV centers, as well as chemically modified fluorescent nanodiamond, hold tremendous potential to replace toxic semiconductor quantum dots, thus bringing this exciting potential application one step closer to the clinics [5]. The purification, characterization and surface modification of nanodiamond for biomedical applications will be discussed in detail. Recent progress in development of nanodiamond-biodegradable polymer scaffolds for tissue engineering and bone surgery will be reviewed. Surface modifications of nanodiamond for drug delivery exploiting adsorption/desorption mechanisms will be discussed, with illustrations of the use of adsorption/desorption data for rational design of nanodiamond surface for optimal drug delivery platform. Finally, an overview of surface modification of nanodiamond for biomedical imaging will be presented.

[1]. V. N. Mochalin, O. Shenderova, D. Ho, Y. Gogotsi The Properties and Applications of Nanodiamonds (Review), Nature Nanotechnology, 7 (1), p.11-23 (2012)
[2]. V. N. Mochalin, A. Pentecost, X.-M. Li, I. Neitzel, M. Nelson, C. Wei, T. He, F. Guo, Y. Gogotsi Adsorption of Drugs on Nanodiamond: Toward Development of a Drug Delivery Platform, Molecular Pharmaceutics, 10 (10), p.3728-3735 (2013)
[3]. O. Shenderova, D. Gruen, ed. Detonation Nanodiamonds: Science and Applications (2nd Edition). CRC Press, 2014
[4]. Q. Zhang, V. N. Mochalin, I. Neitzel, K. Hazeli, J. Niu, A. Kontsos, J. G. Zhou, P. I. Lelkes, Y. Gogotsi Multifunctional Nanodiamond-PLLA Scaffolds for Bone Tissue Engineering: Enhanced Mechanical Strength and Biomineralization, Biomaterials, 33 (20), p.5067-5075 (2012)
[5]. G. Balasubramanian, A. Lazariev, S. R. Arumugam, et al. "Nitrogen-Vacancy color center in diamond-emerging nanoscale applications in bioimaging and biosensing." Current Opinion in Chemical Biology 20 (2014): 69-77
Thermodynamics of Quasi-Epitaxial Assembly of Fmn Around Various (n,m)-SWNTs
Authors: Papadimitrakopoulos Fotios , Sharifi Roholah , Samaraweera Milinda , Gascon Jose 
Published: February 2020

The helical assembly of self-organized flavin mononucleotide (FMN) around single-walled carbon nanotubes (SWNTs) presents among the highest organization order in nanotube surfactants. In this contribution, we quantitatively analyze and model for the first time the cooperative hydrogen bonding of adjacent flavin moieties as well as the concentric π–π interactions between the isoalloxazine moieties and the underlying graphene lattice as a function of (n,m)-SWNT chirality. For this we use dissociation thermodynamics of FMN-wrapped (n,m)-SWNTs dispersed in both H2O and D2O as a function of FMN concentration. The binding strength of these FMN assemblies has been assessed in terms of ΔH, ΔS and ΔG. Atomistic molecular simulations were used to modeled these data and link their dependence in terms of nanotube diameter (dt
) the chiral angle (j). The findings of this study provide the first quantitative proof of the quasi-epitaxial assembly of FMN around various (n,m)-SWNTs.[1] This study demonstrates the architectural fidelity of FMN-wrapped SWNTs that closely emulates the dissociation mechanics of double-stranded DNA in its aqueous solutions.

[1] Sharifi, R.; Samaraweera, M.; Gascón, J. A.; Papadimitrakopoulos, F.; J. Am. Chem. Soc., 2014, 136(20), 7452–7463.
(Invited) Single-Walled Carbon Nanotube Spectroscopy in Complex Environments
Authors: Heller Daniel A 
Published: February 2020

The real-time and spatially-resolved detection and identification of analytes present important goals for next-generation nanoscale sensors. Low-dimensional nanomaterials are improving the detection of molecular binding phenomena. The resulting optical technologies may allow for the quantification of disease biomarkers and other bioanalytes. The photoluminescence of single-walled carbon nanotubes may facilitate quantification of analytes within complex environments. To build optical probes using these materials, we are developing new spectroscopic techniques to detect nanotube emission in biological samples and new polymers to control their optical properties.
Synthesis and Characterization of Bis-Triruthenium Cluster Derivatives of an All Equatorial [60]Fullerene Tetramalonate
Authors: Chen Chia-Hsiang , Aghabali Amineh , Olmstead Marilyn M. , Balch Alan L. , Echegoyen Luis 
Published: February 2020

Exohedral metal-C60 complexes exhibit unique physicochemical properties as a result of the metal cluster centers.1 This is important in the study of the reactivity and electrochemical properties of exohedral metal-C60 complexes, as it might result in the development of new nanomaterials.2

Kräutler et al. developed the orthogonal transposition method to synthesize C60 tetrakis-adducts with all addends located on the equatorial belt and the trans-1 positions available for further functionalizations.3 The presence of the tetrakis[di(ethoxycarbonyl)methano] groups should limit the number of possible bis-adduct regioisomers observed. We report that tetrakis[di(ethoxycarbonyl)-methano]-C60 reacts with triruthenium clusters to form the first anti-isomer C60-metal cluster complex : anti-[Ru3(CO)9]2{μ3-η2,η2,η2-C60[C(COOC2H5)2]4}. The two triruthenium groups are found in either an anti or a syn orientation, as determined by NMR. Only the anti form was characterized by X-ray crystallography, see structure below.
References
1. K. Lee, H. Song and J. T. Park, Acc. Chem. Res. 2003, 36, 78.
2. Y.-J. Cho, T. K. Ahn, H. Song, K. S. Kim, C. Y. Lee, W. S. Seo, K. Lee, S. K. Kim, D. Kim and J. T. Park, J. Am. Chem. Soc. 2005, 127, 2380.
3. R. Schwenninger, T. Müller and B. Kräutler, J. Am. Chem. Soc. 1997, 119, 9317.

Figure 1
(Invited) Graphene Plasmons: Properties and Applications
Authors: Avouris Phaedon 
Published: February 2020

After a short introduction to the single particle excitations of graphene, I will focus on the collective excitations (plasmons) of this material [1,2]. The properties of graphene plasmons, will be compared with those of the surface plasmons of conventional metals concentrating mainly on localized plasmons in lithographically patterned nano- and micro-structures (quantum dots and ribbons) [2-7]. I will discuss their optical behavior in the infrared and THz regions of the spectrum, size effects, doping effects, effects of external magnetic fields, and the hybridization of the graphene plasmons with substrate and adsorbed overlayer optical phonons and the plasmon damping mechanisms [3,6,7,11].
Applications of graphene plasmons in passive THz optical elements, the enhancement of photocurrents in graphene infrared photodetectors [8-10], and the enhancement of infrared absorption spectra of molecules and deposited thin dielectric films [11-13] will be discussed.
[1] Grigorenko, A.N.; Polini, M; Novoselov, K.S., Nat. Photonics 6, 749 (2012).
[2] Low, T.; Avouris, Ph. ACS Nano 8, 1086 (2014).
[3] Yan, H.; et al. Nat. Nanotechnol. 7, 330 (2012).
[3] Yan, H.; et al. Nat. Photonics 7, 394 (2013).
[5] Freitag, M.; Low, T.; Xia, F.; Avouris, Ph. Nat. Photonics 7, 53 (2011).
[6] Yan, H. et al. Nano Lett. 14, 4581 (2014).
[7] Low, T. et al.; Phys. Rev. Lett. 112, 116801 (2014).
[8] Freitag, M; et al. ACS Nano (2014), DOI: 10.1021/nn502822z
[9] Freitag, M.; et al. Nat. Commun. 4, 1951 (2013).
[10] Avouris, Ph., Freitag, M., IEEE J. Topics in Quantum Electronics, 20, 6000112 (2014).
[11] Li, Y. et al.; Nano Lett. 14, 1573 (2014).
[12] Freitag, M; et al. ACS Nano 8, 8350 (2014).
[13] Wang, H.; et al. to be published.
(Invited) Spectroscopic Metrics for Determining Size and Thickness of Liquid Exfoliated Nanosheets in Dispersion
Authors: Backes Claudia , Coleman Jonathan 
Published: February 2020

Over the last few years the study of 2-dimensional (2D) nanomaterials has become one of the most important areas of both materials science and nanotechnology. While this work originally focused on graphene, the palette of 2D materials currently under study includes transition metal dichalcogenides (TMDs) such as MoS2 and WSe2, layered transition metal oxides such as MoO3 and a host of other interesting structures such as GaS or phosphorene. Particularly useful is the diversity of 2D materials: depending on the combination of elements and their arrangement, they can be metals, semiconductors, insulators or superconductors.
Liquid-phase exfoliation has proven to be a powerful technique to obtain large quantities of exfoliated 2D materials in dispersion, ultimately making the materials processable. This method involves the sonication of layered crystals in certain solvents or solutions of surfactants or polymers. Even though being extremely versatile and useful, it has notable disadvantages such as the polydispersity of materials produced.
We have performed detailed spectroscopic and microscopic analysis on size-selected dispersions of exfoliated MoS2 nanosheets. This has led to the development of an in situ technique which allows nanosheet concentration, lateral size and thickness to be obtained simultaneously from an optical extinction/absorption spectrum. The combination of concentration-control, size-selection and measurement facilitates the preparation of dispersions with pre-determined properties. For example, monolayer-enriched dispersions can be produced, allowing the first measurement of direct-gap luminescence in liquid suspensions. In subsequent studies, we have developed similar metrics for other liquid-exfoliated nanosheets such as graphene, GaS and MoTe2. In the case of graphene, we propose simple metrics based on Raman spectra of size-selected graphene in restacked films to quantify size and thickness on the foundation of the G-band width or D/G ratio and changes in the 2D band shape.
C. Backes, ... J. N. Coleman, Using Edge and Confinement Effects for in situ Determination of Size and Thickness of Liquid-Exfoliated Nanosheets. Nat. Commun.
2014,
5, 4576.

Figure 1
Decorating of Graphene-Supported Palladium Nanoparticles with Nanostructured Tungsten Oxide Towards More Efficient Electrocatalytic Oxidation of Formic Acid
Authors: Ozimek Weronika , Rutkowska Iwona Agnieszka , Kulesza Pawel J 
Published: February 2020

By depositing tungsten oxide nanostructures (nanorods) over palladium nanoparticles supported onto graphene nanosheets and dispersed onto glassy carbon substrate, enhancement of the overall electrocatalytic activity towards oxidation of formic acid in acid medium was observed. The effect was particularly evident from the increase of chronoamperometric currents at a fairly low potential of 0.04 V vs. RHE. It is reasonable to expect that introduction of graphene nanosheets to the system facilitates distribution of charge at the electrocatalytic interface. Under such conditions, tungsten oxide nanorods seem to be partially and reversibly reduced not only to nonstoichiometric hydrogen tungsten(VI,V) oxide bronzes (HxWO3, 0<x<1) but also substoichiometric lower tungsten (VI,IV) oxides (WO3-y, 0<y<1). Mutual interactions between tungsten oxides or graphene and Pd nanoparticles are likely to affect electrochemical characteristics of all components. The metal-oxide interactions, as well as high population of hydroxyl groups at the electrocatalytic interface (favoring oxidative removal of passivating CO adsorbates), are presumably responsible for the overall enhancement effect. In comparison to conventional electrodeposited microporous tungsten oxides, WO3 nanorods, despite their small dimensions, are more robust and less hydrated. Electrochemical diagnostic experiments were supported with microscopic measurements aiming at monitoring morphology of catalytic surfaces with use of transmission (TEM) and scanning (SEM) electron microscopies. The palladium nanoparticles were of the sizes 10 to 20 nm, and the tungsten oxide nanorods had diameters of 50–70 nm while being approximately 5 μm long. Our ultimate goal is to minimize loading of noble metal nanoparticles while keeping the electrocatalytic activity at the high level.
A Novel Ambipolar Nonaqueous All-Organic Redox Flow Battery and Its State of Charge Detection By FTIR
Authors: Vemuri Rama Sesha , Hu Dehong , Duan Wentao , Wang Wei , Brushett Fikile R. , Wei Xiaoliang , Liu Jun 
Published: February 2020

Nonaqueous redox flow batteries (NARFB) are considered as a promising next-generation grid scale energy storage solution because of their potential higher energy densities derived from the wide voltage window of nonaqueous electrolytes. Current research of NARFB is focused on redox materials development for various flow battery chemistries. Flow battery operation involves complexity associated with solvent-salt-redox species interactions, porous electrode, flow field, material crossover, etc., making it challenging to diagnose the real-time battery status. However, there is critical knowledge and technical gaps in this aspect. Especially, fast, robust and cost-effective diagnostic techniques are lacking to monitor state of charge (SOC) in a real-time manner to maintain safe and reliable long-term flow battery operations.
In this research, we report a novel all-organic redox flow battery based on an ambipolar redox material and demonstrate Fourier Transform infrared spectroscopy (FTIR) as an effective method of detecting the SOC of this flow battery. The concentrations of the redox materials were derived from FTIR signal intensity by using the Beer-Lampert Law, which were used to calculate the SOC of the flow battery during the charge/discharge processes. The FTIR-based SOC determination agrees well with the electron spin resonance (ESR)-based measurements, demonstrating the feasibility of FTIR for online monitoring of the flow battery operation status. Also, the evolution of the FTIR spectra over repeated flow battery cycling offers a possible way to study the redox materials degradation and battery performance fading mechanism. This state of health (SOH) study can provide a direct prediction of cycle life of a NARFB.

Figure 1