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Graphene Oxide Quantum Dots Cytotoxic and Phototoxic Activity

Research Poster Presentation by Juan Armas†

† Department of Chemistry and Biochemistry, University of California,1156 High Street, Santa Cruz, California 95064, USA.
E-mail: jarmas1@ucsc.edu Social Media: linkedin.com/in/juan-armas-4b5835149

Graphene oxide quantum dots (GOQD) and a sodium borohydride-reduced derivative (rGOQD) were synthesized using a
modified Hummer’s method and investigated as an antimicrobial agent in both dark and light-irradiation conditions. HRTEM
micrographs illustrated the resulting nanostructures with an average diameter of 7.1 ± 0.3 nm and UV-vis spectra displayed typical
absorption features of graphitic nanoparticles at 230 nm and 260 nm, with the ladder becoming enhanced after reduction. XPS revealed
a decrease in carbonyl composition and an increase in hydroxyl composition which is indicative of 𝑠𝑝2 network restoration.
Photoluminescence measurements revealed fluorescence spectra typical of graphitic structures, which blue-shifted and increased in
intensity after reduction by sodium borohydride. The nanostructures were also characterized by Raman spectroscopy, and demonstrated
characteristic D and G bands with a decrease in the D to G ratio after reduction. Escherichia coli cells were incubated with GOQD and
rGOQD solutions, and toxicity was evaluated in dark conditions, as well as under visible light irradiation. As-prepared GOQD
demonstrated apparent toxicity in the dark, likely due to redox-active phenantraquinone-moieties. Under light irradiation, only rGOQD
demonstrated phototoxicity, likely due to removal of exciton trap states after reduction which is supported by a longer excited state
lifetime as measure by fluorescence lifetime measurements. A possible correlation between the chemical structure of graphitic
nanostructures and their toxicity towards bacterial cells is established and can be extended to all carbon nanostructures.

What is graphene?
Graphene is a 𝑠𝑝2 hybridized, indefinitely singled layered, aromatic, hexagonal, 2-dimensional sheet of carbon atoms.
Graphene was first isolated/studied in 2004 won the Nobel Prize in Physics in 2010. Graphene is a wonder material because it is the
strongest material (200 times stronger than steel), and most electrically conductive charge carrier with µ = 200,000 (current density
is 1,000,000 times greater than copper and its intrinsic mobility is 1,000 times more conductive than silicon). In addition, graphene has
large specific surface area of 2630 𝑔 , a high Young’s modulus of ≈ 1Tpa (pressure inside the Earth’s inner core is 0.36Tpa), high
thermal conductivity of 5000𝑚∗𝐾, and an high optical transparency of up to 97.7%.
Mathematically, graphene is the first two-dimensional material ever created, is virtually transparent/flexible, and can pass
electrons with negligible resistance and mass. Graphene has unusual/unique optical, electronic, and mechanical properties. Scientists
and engineers throughout the globe are currently spending billions of dollars in research towards technological advancements.
Graphene will replace lithium ion batteries, silicon in computers, invent new energy storage systems (i.e. fuel and solar cells), new
electronics, communications, and aerospace craft and automotive carriers, to name a few applications.
Graphene’s amazing properties stems from its 𝑠𝑝2 hybridization network. Graphene’s carbon atom has 4 bonds: one σ bond for
each of its 3 adjacent carbon-carbon bonds and a π bond that is oriented out of a plane. The 𝑠𝑝2 orbital hybridization is attributed from
its s orbital, 𝑝𝑥 orbital, and a 𝑝𝑦 orbital that is termed a σ bond. The 𝑝𝑧 orbital constitutes the π orbital that forms double bonds which
hybridize to form π -π networks. This π and 𝜋 ∗ hybridization is attributed to graphene’s electronic properties through half-filled bands
that permit moving electrons.

While physicists and engineers studied graphene for a decade in their respective fields, cutting-edge science in biotechnology
and biomedicine recently gave birth to various applications. Graphene oxide (GO) is a graphene derivative with the same
commensurate properties but with hydrophilic functional groups and defect structures. GO nanosheets is achieved by the breakdown of
carbon pitch fibers known as acidic exfoliation. These carbon pitch fibers consist of graphite, a 3D version of graphene held together
by strong Van Der Waals forces. Interestingly, GO is toxic towards bacterial organisms and inert towards mammalian cells. GO
antibacterial properties, water solubility, and high surface area, electrical conductivity, and high tensile strength has promising
advancements in medicine and biotechnology. Scientists are studying and creating novel applications in cancer therapy, drug delivery,
tissue regeneration, water purification, and antibiotic treatments.

I am a Physical Chemist with cross interdisciplinary training as a Microbiologist and my research involves the synthesis and
characterization of GO and its usage as an antimicrobial agent. My research and training can be integrated into all of graphene’s
applications but what I am interested in is the biological applications. More specifically, I am interested in using my nanostructures and
as an agent to combat drug-resistance bacteria. Pathogenic microbial strains are increasingly gaining antibiotic resistance due to
malpractice and a transfer of resistant genes between microbial populations. Antibiotic resistance is the world’s most pressing public
health issue and it is becoming more prevalent to cure and expense to treat. Graphene nanostructures are leading candidates due to their
broad-spectrum of microbial activity and low cytotoxicity for mammalian cells. It is already established that graphene induces reactive
oxygen species (ROS), protein dysfunction, membrane damage, and transcriptional arrest and each of these specific mechanisms can
independently trigger the other with ROS being the most prevalent. My research focuses on GO’s ROS toxicity in hopes of engineering
an optimal and unambiguous antibacterial agent structure-activity correlation. One day my research will be incorporated into water
purification systems, sterilization protocols for surgical/dental equipment, and coating for wound dressings.