Photochemical Optimization of a Silver Nanoprism/Graphene Oxide Nanocomposite's Antibacterial Properties.

Optimizing the antibacterial properties of nanocomposites is a fundamental challenge for many biomedical applications. Here, we study how we may optimize the antibacterial activity of narrow-sized anisotropically flat silver nanoprisms (S-NPs) on graphene oxide (GO) against Escherichia coli. To do so, we transformed silver nanoparticles (AgNPs) into S-NPs and anchored them to GO via a facile and low-cost photochemical reduction method by varying the irradiation wavelength during the synthesis process in the visible range (440 to 650 nm and white light). We performed a physicochemical characterization of the resulting S-NP/GO nanocomposite using a combination of UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Our results reveal a synergistic effect between the silver nanoprism and the oxygen functional groups of the GO surface. The antibacterial activity of the S-NPs/GO nanocomposite shows a significantly higher 53% inhibition efficiency after being irradiated with a 540 nm wavelength light source, compared to AgNPs with a 1% inhibition efficiency, respectively. In so doing, we have demonstrated the utility of a low-cost photoreduction method to control the structural properties of silver nanoprism on GO and, in this way, enhance the antibacterial properties of the nanocomposite. These results should be of great interest in a wide range of biomedical applications and medical devices.

Carbon Nano-onions: Potassium Intercalation and Reductive Covalent Functionalization.

Herein we report the synthesis of covalently functionalized carbon nano-onions (CNOs) via a reductive approach using unprecedented alkali-metal CNO intercalation compounds. For the first time, an in situ Raman study of the controlled intercalation process with potassium has been carried out revealing a Fano resonance in highly doped CNOs. The intercalation was further confirmed by electron energy loss spectroscopy and X-ray diffraction. Moreover, the experimental results have been rationalized with DFT calculations. Covalently functionalized CNO derivatives were synthesized by using phenyl iodide and n-hexyl iodide as electrophiles in model nucleophilic substitution reactions. The functionalized CNOs were exhaustively characterized by statistical Raman spectroscopy, thermogravimetric analysis coupled with gas chromatography and mass spectrometry, dynamic light scattering, UV-vis, and ATR-FTIR spectroscopies. This work provides important insights into the understanding of the basic principles of reductive CNOs functionalization and will pave the way for the use of CNOs in a wide range of potential applications, such as energy storage, photovoltaics, or molecular electronics.

Infra-Red Active Dirac Plasmon Serie in Potassium Doped-Graphene (KC8) Nanoribbons Array on Al2O3 Substrate.

A theoretical formulation of the electromagnetic response in graphene ribbons on dielectric substrate is derived in the framework of the ab initio method. The formulation is applied to calculate the electromagnetic energy absorption in an array of potassium-doped graphene nanoribbons (KC8-NR) deposited on a dielectric Al2O3 substrate. It is demonstrated that the replacement of the flat KC8 by an array of KC8-NR transforms the Drude tail in the absorption spectra into a series of infrared-active Dirac plasmon resonances. It is also shown that the series of Dirac plasmon resonances, when unfolded across the extended Brillouin zones, resembles the Dirac plasmon. The Dirac plasmon resonances' band structure, within the first Brillouin zone, is calculated. Finally, an excellent agreement between the theoretical absorption and recent experimental results for differential transmission through graphene on an SiO2/Si surface is presented. The theoretically predicted micrometer graphene nanoribbons intercalation compound (GNRIC) in a stage-I-like KC8 is confirmed to be synthesized for Dirac plasmon resonances.

Optimized and scalable synthesis of magnetic nanoparticles for RNA extraction in response to developing countries' needs in the detection and control of SARS-CoV-2.

Ecuador is one of the most affected countries, with the coronavirus disease 2019 (COVID-19) infection, in Latin America derived from an ongoing economic crisis. One of the most important methods for COVID-19 detection is the use of techniques such as real time RT-PCR based on a previous extraction/purification of RNA procedure from nasopharyngeal cells using functionalized magnetic nanoparticles (MNP). This technique allows the processing of ~ 10,000 tests per day in private companies and around hundreds per day at local Universities guaranteeing to reach a wide range of the population. However, the main drawback of this method is the need for specialized MNP with a strong negative charge for the viral RNA extraction to detect the existence of the SARS-CoV-2 virus. Here we present a simplified low cost method to produce 10 g of nanoparticles in 100 mL of solution that was scaled to one litter by parallelizing the process 10 times in just two days and allowing for the possibility of making ~ 50,000 COVID-19 tests. This communication helps in reducing the cost of acquiring MNP for diverse biomolecular applications supporting developing country budgets constraints and chemical availability specially during the COVID-19 International Health Emergency.

Ultralong Spin Lifetime in Light Alkali Atom Doped Graphene.

Today's great challenges of energy and informational technologies are addressed with a singular compound, Li- and Na-doped few-layer graphene. All that is impossible for graphite (homogeneous and high-level Na doping) and unstable for single-layer graphene works very well for this structure. The transformation of the Raman G line to a Fano line shape and the emergence of strong, metallic-like electron spin resonance (ESR) modes attest the high level of graphene doping in liquid ammonia for both kinds of alkali atoms. The spin-relaxation time in our materials, deduced from the ESR line width, is 6-8 ns, which is comparable to the longest values found in spin-transport experiments on ultrahigh-mobility graphene flakes. This could qualify our material as a promising candidate in spintronics devices. On the other hand, the successful sodium doping, this being a highly abundant metal, could be an encouraging alternative to lithium batteries.

Understanding the Electron-Doping Mechanism in Potassium-Intercalated Single-Walled Carbon Nanotubes.

Single-walled carbon nanotubes (SWCNTs) can be doped with potassium, similar to graphite, leading to intercalation compounds. These binary systems exhibit a clear metallic character. However, the entire picture of how electron doping (e-doping) modifies the SWCNTs' vibrational spectra as a function of their diameter, chirality, and metallicity is still elusive. Herein, we present a detailed study of the intercalation and solid state reduction of metallic and semiconducting enriched HiPco SWCNTs. We performed a combined experimental and theoretical study of the evolution of their Raman response with potassium exposure, focusing specifically on their radial breathing mode (RBM). We found the charge donated from the potassium atoms occupies antibonding π orbitals of the SWCNTs, weakening their C-C bonds, and reducing the RBM frequency. This RBM downshift with increasing doping level is quasi-linear with a steplike behavior when the Fermi level crosses a van Hove singularity for semiconducting species. Moreover, this weakening of the C-C bonds is greater with decreasing curvature, or increasing diameter. Overall, this suggests the RBM downshift with e-doping is proportional to both the SWCNT's integrated density of states (DOS) ϱ(ε) and diameter d. We have provided a precise and complete description of the complex electron doping mechanism in SWCNTs up to a charge density of -18 me/C, far beyond that achievable by standard gate voltage studies, not being the highest doping possible, but high enough to track the effects of doping in SWCNTs based on their excitation energy, diameter, band gap energy, chiral angle, and metallicity. This work is highly relevant to tuning the electronic properties of SWCNTs for applications in nanoelectronics, plasmonics, and thermoelectricity.

Characterizing the maximum number of layers in chemically exfoliated graphene.

An efficient route to synthesize macroscopic amounts of graphene is highly desired and bulk characterization of such samples, in terms of the number of layers, is equally important. We present a Raman spectroscopy-based method to determine the typical upper limit of the number of graphene layers in chemically exfoliated graphene. We utilize a controlled vapour-phase potassium intercalation technique and identify a lightly doped stage, where the Raman modes of undoped and doped few-layer graphene flakes coexist. The spectra can be unambiguously distinguished from alkali doped graphite, and modeling with the typical upper limit of the layers yields an upper limit of flake thickness of five layers with a significant single-layer graphene content. Complementary statistical AFM measurements on individual few-layer graphene flakes find a consistent distribution of the layer numbers.

Exploring the Formation of Black Phosphorus Intercalation Compounds with Alkali Metals.

Black phosphorus intercalation compounds (BPICs) with alkali metals (namely: K and Na) have been synthesized in bulk by solid-state as well as vapor-phase reactions. By means of a combination of in situ X-ray diffraction, Raman spectroscopy, and DFT calculations the structural behavior of the BPICs at different intercalation stages has been demonstrated for the first time. Our results provide a glimpse into the very first steps of a new family of intercalation compounds, with a distinct behavior as compared to its graphite analogues (GICs), showing a remarkable structural complexity and a dynamic behavior.

Precise determination of graphene functionalization by in situ Raman spectroscopy.

The verification of a successful covalent functionalization of graphene and related carbon allotropes can easily be carried out by Raman spectroscopy. Nevertheless, the unequivocal assignment and resolution of individual lattice modes associated with the covalent binding of addends was elusive up to now. Here we present an in situ Raman study of a controlled functionalization of potassium intercalated graphite, revealing several new bands appearing in the D-region of the spectrum. The evolution of these bands with increasing degree of functionalization from low to moderate levels provides a basis for the deconvolution of the different components towards quantifying the extent of functionalization. By complementary DFT calculations we were able to identify the vibrational changes in the close proximity of the addend bearing lattice carbon atoms and to assign them to specific Raman modes. The experimental in situ observation of the developing functionalization along with the reoxidation of the intercalated graphite represents an important step towards an improved understanding of the chemistry of graphene.

Manifestation of charged and strained graphene layers in the Raman response of graphite intercalation compounds.

We present detailed multifrequency resonant Raman measurements of potassium graphite intercalation compounds (GICs). From a well-controlled and consecutive in situ intercalation and high-temperature deintercalation approach the response of each stage up to stage VI is identified. The positions of the G and 2D lines as a function of staging depend on the charge transfer from K to the graphite layers and on the lattice expansion. Ab initio calculations of the density and the electronic band structure demonstrate that most (but not all) of the transferred charge remains on the graphene sheets adjacent to the intercalant layers. This leads to an electronic decoupling of these "outer" layers from the ones sandwiched between carbon layers and consequently to a decoupling of the corresponding Raman spectra. Thus, higher stage GICs offer the possibility to measure the vibrations of single, double, and multilayer graphene under conditions of biaxial strain. This strain can additionally be correlated to the in-plane lattice constants of GICs determined by X-ray diffraction. The outcome of this study demonstrates that Raman spectroscopy is a very powerful tool to identify local internal strain in pristine and weakly charged single and few-layer graphene and their composites, yielding even absolute lattice constants.