ABSTRACT
Measuring, recording and analyzing spectral information of materials as its unique finger print using a ubiquitous smartphone has been desired by scientists and consumers. We demonstrated it as drug classification by chemical components with smartphone Raman spectrometer. The Raman spectrometer is based on the CMOS image sensor of the smartphone with a periodic array of band pass filters, capturing 2D Raman spectral intensity map, newly defined as spectral barcode in this work. Here we show 11 major components of drugs are classified with high accuracy, 99.0%, with the aid of convolutional neural network (CNN). The beneficial of spectral barcodes is that even brand name of drug is distinguishable and major component of unknown drugs can be identified. Combining spectral barcode with information obtained by red, green and blue (RGB) imaging system or applying image recognition techniques, this inherent property based labeling system will facilitate fundamental research and business opportunities.
Subject(s)
Spectrum Analysis, Raman , Commerce , Cytoplasm , Fingers , Smartphone , Spectrum Analysis, Raman/instrumentationABSTRACT
Understanding the dynamics of colloidal nanoparticles (NPs) in a solution is the key to assembling them into solids through a solution process such as electrophoretic deposition. In this study, newly developed in situ analysis with light scattering is used to examine NP dynamics induced by a non-uniform electric field. We reveal that the symmetric directions of moving NP aggregates are due to dielectrophoresis between the cylindrical electrodes, while the actual NP deposition is based on the charge of NPs (electrophoresis). Over time, the symmetry of the dynamics becomes less evident, inducing feeble deposition as the less-ordered dynamics become stronger. Eventually, two separate deposition mechanisms emerge as the deposition rate decreases with the change in the NP dynamics. Furthermore, we identify the vortex-like NP motion between the electrodes. These in situ analyses provide insights into the electrophoretic deposition mechanism and NP behavior in a solution under an electric field for fine film construction.
ABSTRACT
This study proposes a stand-off Raman spectroscopy system using dual-wavelength in the ultraviolet (UV) region to detect hazardous chemicals. The Raman spectrum generated by the UV excitation source avoids solar background noise during daytime for chemical detection as the spectrum is in the solar blind range. Wavelengths of 213 and 266 nm by 5th and 4th harmonics are generated from Nd:YAG laser. However, Raman spectra of chemicals exhibit different signal-to-noise ratios for both the excitation wavelengths; therefore, to detect such chemicals, Raman spectra by two sources are required. Raman spectra were acquired using a dual-wavelength laser and spectrometer with a single grating and detector at the wavelengths of 213 and 266 nm simultaneously. The Raman spectra of sulfuric acid, 2-chloroethyl ethyl sulfide, and dimethyl methylphosphonate were acquired and analyzed, thus highlighting the application of dual-wavelength Raman spectroscopy. For efficient chemical detection in the field, we have ensured that the system developed in this study is robust.
Subject(s)
Hazardous Substances , Spectrum Analysis, Raman , Spectrum Analysis, Raman/methods , LasersABSTRACT
Direct messenger ribonucleic acid (mRNA) delivery to target cells or tissues has revolutionized the field of biotechnology. However, the applicability of regenerative medicine is limited by the technical difficulties of various mRNA-loaded nanocarriers. Herein, we report a new conductive hybrid film that could guide osteogenic differentiation of human adipose-derived mesenchymal stem cells (hADMSCs) via electrically controlled mRNA delivery. To find optimal electrical conductivity and mRNA-loading capacity, the polypyrrole-graphene oxide (PPy-GO) hybrid film was electropolymerized on indium tin oxide substrates. We found that the fluorescein sodium salt, a molecule partially mimicking the physical and chemical properties of mRNAs, can be effectively absorbed and released by electrical stimulation (ES). The hADMSCs cultivated on the PPy-GO hybrid film loaded with pre-osteogenic mRNAs showed the highest osteogenic differentiation under electrical stimulation. This platform can load various types of RNAs thus highly promising as a new nucleic acid delivery tool for the development of stem cell-based therapeutics. Electronic Supplementary Material: Supplementary material (electrochemical and FT-IR analysis on the film, additional SEM, AFM and C-AFM images of the film, optical and fluorescence images of cells, and the primers used for RT-qPCR analysis) is available in the online version of this article at 10.1007/s12274-022-4613-y.
ABSTRACT
Atomic-layered materials, such as high-quality bismuth oxychalcogenides, which are composed of oppositely charged alternate layers grown using chemical vapor deposition, have attracted considerable attention. Their physical properties are well-suited for high-speed, low-power-consumption optoelectronic devices, and the rapid determination of their crystallographic characteristics is crucial for scalability and integration. In this study, we introduce how the crystallographic structure and quality of such materials can be projected through Raman spectroscopy analysis. Frequency modes at â¼55, â¼78, â¼360, and â¼434 cm-1 were detected, bearing out theoretical calculations from the literature. The low-frequency modes positioned at 55 and 78 cm-1 were activated by structural defects, such as grain boundaries and O-rich edges in the Bi2O2Se crystals, accompanied by sensitivity to the excitation energy. Furthermore, the line defects at â¼55 cm-1 exhibited a strong 2-fold polarization dependence, similar to graphene/graphite edges. Our results can help illuminate the mechanism for activating the Raman-active mode from the infrared active mode by defects, as well as the electronic structures of these two-dimensional layered materials. We also suggest that the nanoscale width line defects in Bi2O2Se can be visualized using Raman spectroscopy.
ABSTRACT
2D heterostructures made of transition metal dichalcogenides (TMD) have emerged as potential building blocks for new-generation 2D electronics due to their interesting physical properties at the interfaces. The bandgap, work function, and optical constants are composition dependent, and the spectrum of applications can be expanded by producing alloy-based heterostructures. Herein, the successful synthesis of monolayer and bilayer lateral heterostructures, based on ternary alloys of MoS2(1- x ) Se2 x -WS2(1- x ) Se2 x , is reported by modifying the ratio of the source precursors; the bandgaps of both materials in the heterostructure are continuously tuned in the entire range of chalcogen compositions. Raman and photoluminescence (PL) spatial maps show good intradomain composition homogeneity. Kelvin probe measurements in different heterostructures reveal composition-dependent band alignments, which can further be affected by unintentional electronic doping during the growth. The fabrication of sequential multijunction lateral heterostructures with three layers of thickness, composed of quaternary and ternary alloys, is also reported. These results greatly expand the available tools kit for optoelectronic applications in the 2D realm.
ABSTRACT
Graphene oxide (GO) has proven to be a highly promising material across various biomedical research avenues, including cancer therapy and stem cell-based regenerative medicine. However, creating a uniform GO coating as a thin layer on desired substrates has been considered challenging owing to the intrinsic variability of the size and shape of GO. Herein, a new method is introduced that enables highly uniform GO thin film (UGTF) fabrication on various biocompatible substrates. By optimizing the composition of the GO suspension and preheating process to the substrates, the "coffee-ring effect" is significantly suppressed. After applying a special postsmoothing process referred to as the low-oxygen concentration and low electrical energy plasma (LOLP) treatment, GO is converted to small fragments with a film thickness of up to several nanometers (≈5.1 nm) and a height variation of only 0.6 nm, based on atomic force microscopy images. The uniform GO thin film can also be generated as periodic micropatterns on glass and polymer substrates, which are effective in one-step micropatterning of both antibodies and mouse melanoma cells (B16-F10). Therefore, it can be concluded that the developed UGTF is useful for various graphene-based biological applications.
Subject(s)
Graphite , Animals , Biocompatible Materials , Mice , Microscopy, Atomic Force , PolymersABSTRACT
Numerous efforts have been made to establish three-dimensional (3D) cell cultures that mimic the structure, cell composition, and functions of actual tissues and organs in vitro; however, owing to its intrinsic complexity, precise characterization of 3D differentiation remains challenging and often results in high variations in the resulting differentiated spheroids. This study reports a 3D Raman mapping-based analytical method that helps us to identify the crucial factors responsible for inducing variability in differentiated stem cell spheroids. Human dental pulp stem cell spheroids were generated at various cell densities using the hanging drop (HD) and molded parafilm-based (MP) methods and were then further subjected to odontogenic differentiation. Thereafter, the 3D cellular differentiation in these spheroids was analyzed based on three different Raman peaks, namely, 960, 1156/1528, and 2935 cm-1, which correspond to hydroxyapatite (HA, odontogenic differentiation marker), ß-carotene (precursor of HA), and proteins/cellular components (cell reference). By correlating such cell differentiation-related peaks and water/medium peaks (3400 cm-1), we discovered that the diffusion of the medium containing various nutrients and differentiation factors was crucial in determining the variations in 3D differentiation of stem cell spheroids. Odontogenic differentiation was majorly induced at the outer shell of HD spheroids (up to â¼20 µm), whereas odontogenic differentiation was markedly induced in MP spheroids (up to 40-50 µm). Considering the challenges associated with high variations in spheroid and organoid differentiation, we conclude that the proposed Raman-based 3D analysis plays a pivotal role in stem cell-based regenerative therapy and drug screening.
Subject(s)
Dental Pulp , Spectrum Analysis, Raman , Cell Differentiation , Humans , Spheroids, Cellular , Stem CellsABSTRACT
Artificial synaptic platforms are promising for next-generation semiconductor computing devices; however, state-of-the-art optoelectronic approaches remain challenging, owing to their unstable charge trap states and limited integration. We demonstrate wide-band-gap (WBG) III-V materials for photoelectronic neural networks. Our experimental analysis shows that the enhanced crystallinity of WBG synapses promotes better synaptic characteristics, such as effective multilevel states, a wider dynamic range, and linearity, allowing the better power consumption, training, and recognition accuracy of artificial neural networks. Furthermore, light-frequency-dependent memory characteristics suggest that artificial optoelectronic synapses with improved crystallinity support the transition from short-term potentiation to long-term potentiation, implying a clear emulation of the psychological multistorage model. This is attributed to the charge trapping in deep-level states and suppresses fast decay and nonradiative recombination in shallow traps. We believe that the fingerprints of these WBG synaptic characteristics provide an effective strategy for establishing an artificial optoelectronic synaptic architecture for innovative neuromorphic computing.
Subject(s)
Neural Networks, Computer , Synapses , PhotonsABSTRACT
Graphene derivatives are highly promising materials for use in stem-cell-based regenerative therapies, particularly for bone regeneration. Herein, we report a graphene oxide (GO)-based hybrid platform (GOHP) that is highly effective for guiding the osteogenesis of human adipose-derived mesenchymal stem cells (hAMSCs). A GO-coated indium tin oxide (ITO) substrate was electrochemically modified with Au nanostructures (GNSs), following which a cysteine-modified quadruple-branched arginine-glycine-aspartic acid was self-assembled on the ITO-GO-GNS hybrid via Au-S bonds. The synthesized GOHP, with the highest density of GNSs (deposition time of 120â¯s), exhibited the highest osteogenic differentiation efficiency based on the osteogenic marker expression level, osteocalcin expression, and osteoblastic mineralisation. Remarkably, although GO is known to be less efficient than the high-quality pure graphene synthesised via chemical vapour deposition (CVD), the fabricated GOHP exhibited an efficiency similar to that of CVD-grown graphene in guiding the osteogenesis of hAMSCs. The total RNA sequencing results revealed that CVD graphene and GOHP induced the osteogenesis of hAMSCs by upregulating the transcription factors related to direct osteogenesis, Wnt activation, and extracellular matrix deposition. Considering that GO is easy to produce, cost-effective, and biocompatible, the developed GOHP is highly promising for treating various diseases/disorders, including osteoporosis, rickets, and osteogenesis imperfecta.
Subject(s)
Graphite , Mesenchymal Stem Cells , Nanostructures , Cell Differentiation , Cells, Cultured , Gold , Humans , Osteogenesis , PeptidesABSTRACT
Stem cell-based therapies have recently emerged to treat various incurable diseases and disorders. Types of stem cell-derived cells and their functions should be intensively analyzed before therapy. However, current pre-treatment steps for biological analysis are mostly destructive. Here, we report a novel optical method that enables ultra-fast and label-free characterization of cells, eliminating invasive, destructive steps. The technique, referred to as "autofluorescence-Raman mapping integration (ARMI)" analysis uses cell autofluorescence (AF) to reveal cellular morphology and cytosolic microstructures, while Raman mapping allows site-specific intensive analysis of target molecules, which enables ultra-fast identification of cell types. We used human mesenchymal stem cells (MSCs) as a model and induced adipogenesis. Lipid droplets in cells appeared as "blanks" in three-dimensional AF images and site-specific Raman mapping guided by AF identified the structure and components of the CH2 stretch. Adipogenesis could be rapidly and precisely analyzed, not only for the same batch but also for different batches. Therefore, the developed tool is highly useful for the accurate screening of stem cell differentiation and implementation in biomedical and clinical applications.
Subject(s)
Adipogenesis , Biosensing Techniques , Cell Differentiation , Humans , Spectrum Analysis, Raman , Stem CellsABSTRACT
The chemical transformation from zinc oxide (ZnO) to zinc sulphide (ZnS), using di-tert-butyl disulphide (TBDS) as a highly reactive sulphur precursor, is demonstrated herein. Through anion exchange, we investigate the phase and morphological changes associated with the nanoparticle (NP) transformation of ZnO to ZnS using TBDS. The Zn-O-S alloy was not formed through the anion exchange reaction, only the ZnO and ZnS phases were detected. The NPs were transformed from a solid sphere to a hollow structure, induced by the nanoscale Kirkendall effect. Even with the dramatic shape and phase changes occurring in the NPs, the Zn oxidation state remained as 2+ throughout the 2 h anion exchange reaction. In addition, trioctylphosphine (TOP), a soft base ligand, increased the anion exchange reaction rate, facilitating the reaction with TBDS. Furthermore, anion exchange with elemental sulphur required a longer reaction time (3 h) than that with TBDS (2 h). Consequently, this study offers not only insights into phase and morphological transformations by anion exchange, but also the advantages of utilizing TBDS as a sulphur precursor.
ABSTRACT
Colloidal nanoparticles (NPs) have been recently spotlighted as building blocks for various nanostructured devices. Their collective properties have been exhibited by arranging them on a substrate to form assembled NPs. In particular, electrophoretic deposition (EPD) is an emerging fabrication method for such nanostructured films. To maximize the benefits of this method, further studies are required to fully elucidate the key parameters that influence the NP deposition. Herein, two key parameters are examined, namely: (i) the aging of colloidal NPs and (ii) the charge formation by surface ligands. The aging of Cu2-xS NPs changes the charge states, thus leading to different NP deposition behaviors. The SEM images of NP films, dynamic light scattering, and zeta potential results demonstrated that the charge control and restoration of interparticle interactions for aged NPs were achieved via simple ligand engineering. The charge control of colloidal NPs was found to be more dominant than the influence of aging, which can alter the surface charges of the NPs. The present results thus reveal that the charge formation on the colloidal NPs, which depends on the surface ligands, is an important controllable parameter in EPD.
ABSTRACT
Stimuli-responsive nanoparticles are favorable for improving the selective delivery and rational vocation that easily avoids the undesirable barriers or side effects, leading to a further improved therapeutic efficiency. Furthermore, multifunctional nanomaterials have been extensively developed as attractive candidates for theranostic reagents for cancer treatment. In this article, we developed reversibly pH-responsive gold nanoparticles (AuNPs) with an enhanced Raman scattering signal as well as an efficient photothermal effect and demonstrated their applications as a theranostic reagent for cancer treatment. Surfaces of these AuNPs were modified with mixed layers of Cy3-modified single-stranded DNA (ssDNA-Cy3) for Raman probing and a negative charge supply and cytochrome C (Cyt C) for pH-responsive charge inversion. This combination of pH-responsive ligands and Raman probes played an important role in inducing the assembly or disassembly of AuNPs corresponding to the neighboring pH, accompanied by an additional highly distinguished Raman signal intensity. An operative reversible response of the AuNPs to pH is endowed with the characteristic behavior of AuNPs with the cancerous cell's acidic microenvironment of low pH. The responsive aggregation of AuNPs in a lower pH medium provides highly amplified signals attributed to well-formed hot spots between the particle surfaces that deliver better Raman scattering signals. The acidic pH-responsive aggregation of the particles also provided efficient photothermal treatments using a long-wavelength laser light with the benefit of deeper penetration for cancer cells. In vitro experiments employing cancer cells and control normal cells well-demonstrated the specificity of the particles to cancer cells in terms of highly enhanced Raman imaging and therapeutic efficiency.
Subject(s)
Metal Nanoparticles , Neoplasms , Gold/pharmacology , Hydrogen-Ion Concentration , Metal Nanoparticles/therapeutic use , Neoplasms/diagnostic imaging , Spectrum Analysis, Raman/methods , Tumor MicroenvironmentABSTRACT
Post-growth graphene transfer to a variety of host substrates for circuitry fabrication has been among the most popular subjects since its successful development via chemical vapor deposition in the past decade. Fast and reliable evaluation tools for its morphological characteristics are essential for the development of defect-free transfer protocols. The implementation of conventional techniques, such as Raman spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy in production quality control at an industrial scale is difficult because they are limited to local areas, are time consuming, and their operation is complex. However, through a one-shot measurement within a few seconds, phase-shifting interferometry (PSI) successfully scans ≈1 mm2 of transferred graphene with a vertical resolution of ≈0.1 nm. This provides crucial morphological information, such as the surface roughness derived from polymer residues, the thickness of the graphene, and its adhesive strength with respect to the target substrates. Graphene samples transferred via four different methods are evaluated using PSI, Raman spectroscopy, and AFM. Although the thickness of the nanomaterials measured by PSI can be highly sensitive to their refractive indices, PSI is successfully demonstrated to be a powerful tool for investigating the morphological characteristics of the transferred graphene for industrial and research purposes.
ABSTRACT
Research on the 3D culturing of cancer cells that better mimic in vivo solid tumors is important for efficient drug screening. Herein, a new platform that effectively facilitates the formation of cancer spheroids for anticancer drug screening is reported. Cytophilic graphene oxide (GO), when selectively coated on the sidewalls of micro-wells fabricated from a cell-adhesion-resistive polymer, is found to efficiently initiates distinct donut-like formation of cancer cell spheroids. Scanning electron microscopy and Raman mapping are used to analyze vertically coated GO micropatterns (vGO-MPs) of different sizes (100-250 µm) on polymer platforms, and human liver cancer cells (HepG2), as a model cancer, are seeded on these platforms. Remarkably, the 150 µm-sized platform is found to easily and rapidly generate 3D spheroids in the absence of cell-adhesion proteins. In addition, owing to the unique characteristics of GO, vGO-MPs are highly stable for long periods of time (≈1 month), even under harsh conditions (>70 °C). Moreover, the anticancer effects of two drugs (hydroxyurea and cisplatin) and the potential anticancer compound (curcumin) on HepG2 cells are demonstrated by simply measuring decreases in spheroid sizes. Hence, this new platform is highly promising as a cancer spheroid-forming material for rapid drug screening.
Subject(s)
Graphite , Neoplasms , Drug Evaluation, Preclinical , Early Detection of Cancer , Humans , Spheroids, CellularABSTRACT
The enhanced growth of Cu oxides underneath graphene grown on a Cu substrate has been of great interest to many groups. In this work, the strain and doping status of graphene, based on the gradual growth of Cu oxides from underneath, were systematically studied using time evolution Raman spectroscopy. The compressive strain to graphene, due to the thermal expansion coefficient difference between graphene and the Cu substrate, was almost released by the nonuniform Cu2O growth; however, slight tensile strain was exerted. This induced p-doping in the graphene with a carrier density up to 1.7 × 1013 cm-2 when it was exposed to air for up to 30 days. With longer exposure to ambient conditions (>1 year), we observed that graphene/Cu2O hybrid structures significantly slow down the oxidation compared to that using a bare Cu substrate. The thickness of the CuO layer on the bare Cu substrate was increased to approximately 270 nm. These findings were confirmed through white light interference measurements and scanning electron microscopy.
ABSTRACT
The metal/graphene interface has been one of the most important research topics with regard to charge screening, charge transfer, contact resistance, and solar cells. Chemical bond formation of metal and graphene can be deduced from the defect induced D-band and its second-order mode, 2D band, measured by Raman spectroscopy, as a simple and nondestructive method. However, a phonon mode located at â¼1350 cm-1, which is normally known as the defect-induced D-band, is intriguing for graphene deposited with noble metals (Ag, Au, and Cu). We observe anomalous K-point phonons in nonreactive noble metal/graphene heterostructures. The intensity ratio of the midfrequency mode at â¼1350 cm-1 over G-band (â¼1590 cm-1) exhibits nonlinear but resonant behavior with the excitation laser wavelength, and more importantly, the phonon frequency-laser energy dispersion is â¼10-17 cm-1 eV-1, which is much less than the conventional range. These phonon modes of graphene at nonzero phonon wave vector (q ≠ 0) around K points are activated by localized surface plasmon resonance and not by the defects due to chemical bond formation of metal/graphene. This hypothesis is supported by density functional theory (DFT) calculations for noble metals and Cr along with the measured contact resistances.
ABSTRACT
Graphene derivatives are known to be suitable for biomedical applications, especially for stem cell-based therapies. Herein, we report the size effects of graphene oxide (GO) on differentiation of human adipose-derived mesenchymal stem cells (hADMSCs), using micro-sized (MGO) and nano-sized graphene oxide (NGO) sheets. The MGO and NGO sheets having lateral sizes of 1-10⯵m and 100-300â¯nm, respectively, are coated on glass substrates by drop casting. The hADMSCs grown on the MGO-coated substrates show enhanced cell spreading and proliferation rate when compared with those of NGO counterpart, regardless of their densities. The GO size-dependency of hADMSCs becomes more prominent when it comes to their differentiation capabilities. After 4 weeks of differentiation under the same culture conditions, the osteogenesis of hADMSCs grown on the MGO-coated substrate is particularly higher than that on the NGO-coated substrate. The difference in osteogenic differentiation of hADMSCs is found to be most dominant after 21-28â¯days of differentiation according to the calcification level of osteoblasts. These finding signify the importance of graphene size in controlling the osteogenesis of hADMSCs, which may shed new insight into the use of graphene-based materials for stem cell research and therapy.