Raman Spectroscopy Research Articles

Mineralogical Characteristics of Color-Changing Garnet and the Effect of Light Path Length on Color

The color-changing garnet displays the “alexandrite effect”, changing from green in daylight to purplish-red under incandescent light. The mineralogical characteristics of color-changing garnet is analyzed using Raman spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, an electron probe, and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The color of garnets with different thicknesses was calculated using the International Commission on Illumination (CIE 1976) L*a*b* uniform color system. The results revealed the presence of rutile inclusions in color-changing garnet. Strong absorption in both the blue-violet zone and orange-yellow zone was the main cause for the color-changing effect of garnet. The distribution pattern of rare earth elements (REE) was left-leaning, showing the enrichment of heavy rare earth elements (HREE) and depletion of light rare earth elements (LREE). As the total Cr and V concentrations increased, the area of the 574 nm absorption peak in the UV-Vis spectrum also increased, leading to a more significant variation in color ΔE*ab. The light path length of the gemstone had a significant impact on the extent of the color-changing effect. The color difference reached a maximum and the color-changing effect was most visible when the thickness of the gemstone was 5 mm.

Color Genesis and Chromatography of Yellow Silicified Corals

Color plays a vital role in revealing the formation environment and metasomatic processes of silicified coral. This study investigated the color mechanism and colorimetric characteristics of yellow silicified coral from the aspects of gemology and colorimetry. A Mako G-507C industrial camera, Raman spectroscopy, UV-Vis, EDXRF, and XRD were used for the 16 samples in this study. The results showed that the yellow color of the silicified coral was produced by Fe3+ and influenced by its degree of crystallization. The Raman peaks of all silicified corals were consistent with the standard spectral group peaks of α-quartz, where the yellow part was inferred to be goethite. The peaks at 545 and 505 nm, with a secondary peak near 435 nm in the UV-vis first-order derivative spectrum, were consistent with the presence of hematite and goethite, respectively. The band positions of the second-order derivative spectrum were shown to belong to one single-electron leap 6A1 → (4E;4A1) and one electron pair leap (6A1 +6A1) → (4T1 +4T1). The chroma and lightness were mainly affected by Fe3+. By analyzing the correlation between the Fe content and the characteristic peaks, it was found that an increase in the Fe content led to a red shift in the peak position of the main characteristic peaks, as well as an increase in the hight of the corresponding peaks in the UV-visible first-order derivative spectra. In silicified corals, an increasing crystallinity index is correlated with a decreasing phase proportion of moganite, decreasing Fe content in the bulk, and low chroma.

Identification of Cortex Cercis chinensis Decoction Pieces from Different Growth Origins Using Raman Spectroscopy

The complexity of traditional Chinese medicine (TCM) components and the time-consuming of traditional detection methods make it necessary and meaningful to establish rapid and efficient identification techniques. This study explores the potential of Raman spectroscopy, a non-destructive technique offering details of molecular structure, for rapid and accurate identification. Cortex Cercis chinensis (CCC) decoction pieces from diverse geographical origins, Anhui, Sichuan, Zhejiang, and Hubei, were collected and analyzed using Raman spectroscopy at 785 nm, and the Raman characteristic peaks were analyzed. MATLAB software was employed to analyze the similarity between the spectra of CCC decoction pieces, and the original Raman spectral data were transformed into first and second derivative spectra. The results revealed distinct Raman spectral characteristics of carbohydrates and glycosidic bonds (characteristic peaks at 480, 531, 549, 873, 946 and 1086 cm−1). The correlation coefficients of the all the four samples from different origins ranged from 0.9625 to 0.9912, while the coincidence coefficients ranged from 0.9602 to 0.9934. The first and second derivative demonstrated significantly different peaks within specific ranges, 180–200, 280–380, and 680–740 cm−1 for first derivatives, 160–300, 340–400 and 420–480 cm−1 for second derivatives. These obvious differences in first and second derivative spectra of Raman spectra of CCC decoction pieces demonstrated the different growth origins. In conclusion, the study demonstrated the ability of Raman spectroscopy to accurately differentiate CCC decoction pieces from different geographical growth origin. These findings provided a basis for further application of Raman spectra characteristic fingerprints to be used in quality control for rapid identification of the quality and origin of TCM raw materials.

Unraveling the mummy's shroud: A multi-analytical study of a rare painted textile from Roman Egypt

This article describes a multi-analytical technical study of a rare painted shroud still wrapped around a female Egyptian mummy (MCABo EG 1974) in the collection of the Museo Civico Archeologico of Bologna, Italy. Long stored in the museum's warehouses, these mummified human remains were recently rediscovered within the Bologna Mummy Project (BOmp), an interdisciplinary endeavor promoted by the Museo Civico Archeologico and the Institute for Mummy Studies of Eurac Research, Bolzano, Italy. Dating to the Roman period (1st-2nd century C.E.), as confirmed by radiocarbon dating, this mummy displays a unique series of technical features, including the exceptional finding of a colorful painted shroud still preserved in its original location around the wrapped body, to which it is secured with textile straps and resin. In this context, scientific analysis aimed to deepen our current knowledge of the artistic practices of Roman Egypt through an in-depth study of the painting technique, context of production, and possible provenance of the mummy, while promoting a science-informed, enhanced approach to the preservation of the mummified human remains. This research relied on an integrated analytical protocol based on the combined use of imaging and mapping techniques, non-invasive point analysis, and micro-invasive investigation of minute samples, each carried out at the different partnering institutions. Computed tomography (CT) highlighted varying radio-densities for some of the flesh tones and red decorations. Visible photography and multiband imaging provided information on the nature and distribution of various materials on the surface. Fiber optics reflectance spectroscopy (FORS), X-ray fluorescence (XRF) spectroscopy, and Raman spectroscopy contributed to the characterization of the shroud's color palette along with optical microscopy (OM), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM/EDS), as well as high-performance liquid chromatography coupled with diode-array detection and mass spectrometry (HPLC/DAD and HPLC/MS). Materials detected include a limited number of mineral pigments and plant-derived dyes such as red lead, red ocher, madder, an unknown yellow dye, Egyptian blue and green, and a carbon-based black. Through access to MOLAB equipment and expertise, macro-XRF (MA-XRF), as well as combined X-ray diffraction (XRD) spot analysis and mapping, enhanced pigment identification. A combination of transmission Fourier-transform infrared (FTIR) spectroscopy with gas chromatography / mass spectrometry (GC/MS) was used to identify the paint binders and any additional organic substances possibly involved in embalming practices and ritual traditions, including animal fat, plant lipid, Pinaceae resin, gum, and beeswax. Mineralogical data gathered by XRD on surface deposits and soil residues collected from within the shroud's inner folds was crucial to put forward hypotheses, in support of the stylistic study of the shroud, concerning a possible provenance from Upper Egypt, most likely West Thebes. Both the shroud and inner bandages were found to be made with linen using OM. After undergoing scientific analysis and conservation treatment, the mummy was displayed in the “Mummies. Unwrapping the past” exhibition and was featured at the 10th World Congress on Mummy Studies, both held in Bolzano in the fall of 2022.

Analysis of unknown (unlabeled/mislabeled) drug products for active pharmaceutical ingredients and related substances by an international mail facility satellite laboratory equipped with rapid screening devices.

Two chemists employed a three-device rapid screening "toolkit" consisting of a handheld Raman spectrometer, transportable mass spectrometer, and portable Fourier transform infrared (FT-IR) spectrometer at an international mail facility (IMF) satellite laboratory to examine unknown (unlabeled/mislabeled) products for the presence of active pharmaceutical ingredients (APIs). Phase I of this project previously demonstrated that this toolkit was the most effective collection of instruments for identifying APIs in product types collected at IMFs during a nationwide mail blitz and Phase II of this project previously demonstrated that results generated using the toolkit during a satellite laboratory pilot program were as reliable as those generated by a full-service library when two or more of these instruments identify an API. This study (Phase III) described the results of the satellite laboratory toolkit during production mode and encompassed the period ranging from June 2021 through December 2022. During this study, a total of 858 products were examined on-site at the IMF. The satellite laboratory yielded conclusive results for 726 (84.6%) products, which were used to support regulatory action, and identified 132 (15.4%) products that required additional full-service laboratory analyses due to inconclusive results. The satellite and full-service laboratory verified/confirmed at least one API/related substance in 617 (71.9%) products. A total of 709 APIs/related substances were found in the 617 products, and 202 of these 709 compounds were unique/different. Overall, during Phases I through III of this program, 350 different substances have been identified in products collected at IMFs.

In English

The synthesis and characterization of heterostructure por-Ga2O3/GaAs represent a crucial advancement in nanomaterials, particularly in optoelectronic applications. Employing a two-stage electrochemical etching methodology, this research has elucidated the precise conditions required to fabricate such a heterostructure. The initial stage involves etching monocrystalline gallium arsenide (GaAs) using an aqueous nitric acid solution as the electrolyte. This process is governed by the redox reactions at the crystal-electrolyte interface, where GaAs are partially oxidized and selectively etched. The second stage introduces ethanol into the electrolytic solution. This chemical addition serves a dual purpose: Firstly, it modulates the electrochemical environment, allowing for controlling pore morphology in GaAs. Secondly, it facilitates the etching of the resultant oxide layer, which predominantly consists of gallium oxide (Ga2O3). The formation of this oxide layer can be attributed to the oxidation of GaAs, driven by the electrochemical potentials and resulting in the deposition of reaction by-products on the substrate surface. The fabricated nanocomposite was comprehensively characterized using Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX), and Raman Spectroscopy. SEM imaging revealed a range of agglomerated nanostructures dispersed across the surface, with dimensions ranging from 8–25 μm, 1–1.5 μm, and 70–100 nm. These observations suggest a hierarchical pore structure indicative of a complex etching mechanism modulated by the electrolyte composition. Raman spectroscopic analysis corroborated the presence of various phases in the heterostructure. Signals corresponding to bulk GaAs, serving as the substrate, were distinguishable. In addition, peaks indicative of porous GaAs and porous Ga2O3 were observed. A cubic phase in the Ga2O3 layer was particularly noteworthy, suggesting a higher degree of crystallinity. Notably, the absence of Raman-active modes associated with internal stresses implies that the fabricated heterostructure is of high quality.

Self-Modification of Defective TiO2 under Controlled H2/Ar Gas Environment and Dynamics of Photoinduced Surface Oxygen Vacancies.

In recent years, defective TiO2 has caught considerable research attention because of its potential to overcome the limits of low visible light absorption and fast charge recombination present in pristine TiO2 photocatalysts. Among the different synthesis conditions for defective TiO2, ambient pressure hydrogenation with the addition of Ar as inert gas for safety purposes has been established as an easy method to realize the process. Whether the Ar gas might still influence the resulting photocatalytic properties and defective surface layer remains an open question. Here, we reveal that the gas flow ratio between H2 and Ar has a crucial impact on the defective structure as well as the photocatalyic activity of TiO2. In particular, transmission electron microscopy (TEM) in combination with electron energy loss spectroscopy (EELS) revealed a larger width of the defective surface layer when using a H2/Ar (50 %-50 %) gas mixture over pure H2. A possible reason could be the increase in dynamic viscosity of the gas mixture when Ar is added. Additionally, photoinduced enhanced Raman spectroscopy (PIERS) is implemented as a complementary approach to investigate the dynamics of the defective structures under ambient conditions which cannot be effortlessly realized by vacuum techniques like TEM.

Synergizing Nanomaterials and Artificial Intelligence in Advanced Optical Biosensors for Precision Antimicrobial Resistance Diagnosis.

Antimicrobial resistance (AMR) poses a critical global One Health concern, ensuing from unintentional and continuous exposure to antibiotics, as well as challenges in accurate contagion diagnostics. Addressing AMR requires a strategic approach that emphasizes early stage prevention through screening in clinical, environmental, farming, and livestock settings to identify nonvulnerable antimicrobial agents and the associated genes. Conventional AMR diagnostics, like antibiotic susceptibility testing, possess drawbacks, including high costs, time-consuming processes, and significant manpower requirements, underscoring the need for intelligent, prompt, and on-site diagnostic techniques. Nanoenabled artificial intelligence (AI)-supported smart optical biosensors present a potential solution by facilitating rapid point-of-care AMR detection with real-time, sensitive, and portable capabilities. This Review comprehensively explores various types of optical nanobiosensors, such as surface plasmon resonance sensors, whispering-gallery mode sensors, optical coherence tomography, interference reflection imaging sensors, surface-enhanced Raman spectroscopy, fluorescence spectroscopy, microring resonance sensors, and optical tweezer biosensors, for AMR diagnostics. By harnessing the unique advantages of these nanoenabled smart biosensors, a revolutionary paradigm shift in AMR diagnostics can be achieved, characterized by rapid results, high sensitivity, portability, and integration with Internet-of-Things (IoT) technologies. Moreover, nanoenabled optical biosensors enable personalized monitoring and on-site detection, significantly reducing turnaround time and eliminating the human resources needed for sample preservation and transportation. Their potential for holistic environmental surveillance further enhances monitoring capabilities in diverse settings, leading to improved modern-age healthcare practices and more effective management of antimicrobial treatments. Embracing these advanced diagnostic tools promises to bolster global healthcare capacity to combat AMR and safeguard One Health.

Structural and chemical study of complex silver patterns additively manufactured by multi-photon reduction

Multi-photon reduction (MPR) based on femtosecond laser makes rapid prototyping and molding in micro-nano scale feasible, but is limited in material selectivity due to lack of the understanding of the reaction mechanism in MPR process. In this paper, additively manufacturing of complex silver-based patterns through MPR is demonstrated. The effects of laser parameters, including laser pulse energies and scanning speeds, on the structural and chemical characteristics of the printed structures are systematically investigated. The results show that the geometric size of printed cubes deviates from the designed size further by increasing laser pulse energy or decreasing scanning speed. The reaction mechanism of MPR is revealed by studying the elemental composition and chemical structures of printed cubes. The evolution of Raman spectra upon the laser processing parameters suggests that the MPR process mainly includes two processes: reduction and decomposition. In the MPR process, silver ions are reduced and grow into particles by accepting the electrons from ethonal molecules; meanwhile carboxyl groups in polyvinylpyrrolidone are decomposed and form amorphous carbon that is attached on the surface of silver particles. The conductivity of silver wires fabricated by MPR reaches 2 × 105 S m−1 and stays relatively constant as varying their cross section area, suggesting excellent electrical conduction. The understanding of the MPR process would accelerate the development of MPR technology and the implementation of MPR in micro-electromechanical systems could therefore be envisioned.

A systematic study of solvation structure of asymmetric lithium salts in water

Aqueous electrolytes are promising in large-scale energy storage applications due to intrinsic low toxicity, non-flammability, high ion conductivity, and low cost. However, pure water’s narrow electrochemical stability window (ESW) limits the energy density of aqueous rechargeable batteries. Water-in-salt electrolytes (WiSE) proposal has expanded the ESW to over 3 V by changing electrolyte solvation structure. The limited solubility and WIS electrolyte crystallization have been persistent concerns for imide-based lithium salts. Asymmetric lithium salts compensate for the above flaws. However, studying the solvation structure of asymmetric salt aqueous electrolytes is rare. Here, we applied small-angle x-ray scattering (SAXS) and Raman spectroscope to reveal the solvation structure of imide-based asymmetric lithium salts. The SAXS spectra show the blue shifts of the lower q peak with decreased intensity as the increasing of concentration, indicating a decrease in the average distance between solvated anions. Significantly, an exponential decrease in the d-spacing as a function of concentration was observed. In addition, we also applied the Raman spectroscopy technique to study the evolutions of solvent-separated ion pairs (SSIPs), contacted ion pairs (CIPs), and aggregate ions (AGGs) in the solvation structure of asymmetric salt solutions.

High performance Pt-anchored MoS2 based chemiresistive ascorbic acid sensor

Ascorbic acid (AA), known as vitamin C, is a vital bioactive compound that plays a crucial role in several metabolic processes, including the synthesis of collagen and neurotransmitters, the removal of harmful free radicals, and the uptake of iron by cells in the human intestines. As a result, there is an absolute need for a highly selective, sensitive, and economically viable sensing platform for AA detection. Herein, we demonstrate a Pt-decorated MoS2 for efficient detection of an AA biosensor. MoS2 hollow rectangular structures were synthesized using an easy and inexpensive chemical vapor deposition approach to meet the increasing need for a reliable detection platform. The synthesized MoS2 hollow rectangular structures are characterized through field effect scanning electron microscopy (FESEM), energy-dispersive spectroscopy elemental mapping, Raman spectroscopy, and x-ray photoelectron spectroscopy. We fabricate a chemiresistive biosensor based on Pt-decorated MoS2 that measures AA with great precision and high sensitivity. The experiments were designed to evaluate the response of the Pt-decorated MoS2 biosensor in the presence and absence of AA, and selectivity was evaluated for a variety of biomolecules, and it was observed to be very selective towards AA. The Pt-MoS2 device had a higher response of 125% against 1 mM concentration of AA biomolecules, when compared to that of all other devices and 2.2 times higher than that of the pristine MoS2 device. The outcomes of this study demonstrate the efficacy of Pt-decorated MoS2 as a promising material for AA detection. This research contributes to the ongoing efforts to enhance our capabilities in monitoring and detecting AA, fostering advancements in environmental, biomedical, and industrial applications.

Investigation on specific heat and Raman spectroscopy of YbFe2As2

We hereby present a comprehensive study of polycrystalline YbFe2As2 which includes detailed investigation on the specific heat capacity and Raman spectroscopy measurements at high magnetic fields (up to 16 T) and low temperatures. Low temperature x-ray diffraction investigations at 30 K on YbFe2As2 reveal an orthorhombic unit cell structure, which indicates structural transitions from monoclinic to orthorhombic as temperature decreases. In specific heat capacity measurements, a slope change is observed around 70 K. It may be a signature of spin density wave (SDW) phase transition. The specific heat data has been fitted in the temperature ranging from 20 to 90 K. It has been found that linear coefficient of specific heat (γ) is quite enhanced suggesting the existence of quasi particles with heavy effective mass. Its value changes slowly with magnetic field below 70 K. Raman spectra have been studied in the temperature range of 4 to 300 K. It is observed that there is a trend of shifting the B1G peak position in Raman spectra on the higher side as the temperature decreases. A change of slope in shift of B1G versus temperature plot is noticed around 70 K suggesting phase transition which is consistent with specific heat and previous resistivity measurements. Overall, our results provide new insights into the physical properties and phase transitions of YbFe2As2.

Tailoring thermoelectric performance of n-type Bi2Te3 through defect engineering and conduction band convergence

Bi2Te3, an archetypical tetradymite, is recognised as a thermoelectric (TE) material of potential application around room temperature. However, large energy gap (ΔEc ) between the light and heavy conduction bands results in inferior TE performance in pristine bulk n-type Bi2Te3. Herein, we propose enhancement in TE performance of pristine n-type Bi2Te3 through purposefully manipulating defect profile and conduction band convergence mechanism. Two n-type Bi2Te3 samples, S1 and S2, are prepared by melting method under different synthesis condition. The structural as well as microstructural evidence of the samples are obtained through powder x-ray diffraction and transmission electron microscopic study. Optothermal Raman spectroscopy is utilized for comprehensive study of temperature dependent phonon vibrational modes and total thermal conductivity ( κ ) of the samples which further validates the experimentally measured thermal conductivity. The Seebeck coefficient value is significantly increased from 235 μVK−1 (sample S1) to 310 μVK−1 (sample S2). This is further justified by conduction band convergence, where ΔEc is reduced from 0.10 eV to 0.05 eV, respectively. To verify the band convergence, the double band Pisarenko model is employed. Large power factor (PF) of 2190 μWm−1K−2 and lower κ value leading to ZT of 0.56 at 300 K is gained in S2. The obtained PF and ZT value are among the highest values reported for pristine n-type bulk Bi2Te3. In addition, appreciable value of TE quality factor and compatibility factor (2.7 V−1) at room temperature are also achieved, indicating the usefulness of the material in TE module.

Coupling Nano and Atomic Electric Field Confinement for Robust Alkaline Oxygen Evolution

AbstractThe alkaline oxygen evolution reaction (OER) is a promising avenue for producing clean fuels and storing intermittent energy. However, challenges such as excessive OH− consumption and strong adsorption of oxygen‐containing intermediates hinder the development of alkaline OER. In this study, we propose a cooperative strategy by leveraging both nano‐scale and atomically local electric fields for alkaline OER, demonstrated through the synthesis of Mn single atom doped CoP nanoneedles (Mn SA‐CoP NNs). Finite element method simulations and density functional theory calculations predict that the nano‐scale local electric field enriches OH− around the catalyst surface, while the atomically local electric field improves *O desorption. Experimental validation using in situ attenuated total reflection infrared and Raman spectroscopy confirms the effectiveness of the nano‐scale and atomically electric fields. Mn SA‐CoP NNs exhibit an ultra‐low overpotential of 189 mV at 10 mA cm−2 and stable operation over 100 hours at ~100 mA cm−2 during alkaline OER. This innovative strategy provides new insights for enhancing catalyst performance in energy conversion reactions.

Coupling Nano and Atomic Electric Field Confinement for Robust Alkaline Oxygen Evolution.

The alkaline oxygen evolution reaction (OER) is a promising avenue for producing clean fuels and storing intermittent energy. However, challenges such as excessive OH- consumption and strong adsorption of oxygen-containing intermediates hinder the development of alkaline OER. In this study, we propose a cooperative strategy by leveraging both nano-scale and atomically local electric fields for alkaline OER, demonstrated through the synthesis of Mn single atom doped CoP nanoneedles (Mn SA-CoP NNs). Finite element method simulations and density functional theory calculations predict that the nano-scale local electric field enriches OH- around the catalyst surface, while the atomically local electric field improves *O desorption. Experimental validation using in situ attenuated total reflection infrared and Raman spectroscopy confirms the effectiveness of the nano-scale and atomically electric fields. Mn SA-CoP NNs exhibit an ultra-low overpotential of 189 mV at 10 mA cm-2 and stable operation over 100 hours at ~100 mA cm-2 during alkaline OER. This innovative strategy provides new insights for enhancing catalyst performance in energy conversion reactions.

Negative magnetization and magnetic ordering of rare earth and transition metal sublattices in NdFe0.5Cr0.5O3

We investigate the effect of alloying at the 3d transition metal site of a rare-earth-transition metal oxide, by considering NdFe0.5Cr0.5O3 mixed perovskite with two equal and random distribution of 3d ions, Cr and Fe, interacting with an early 4f rare earth ion, Nd. Employing temperature- and field- dependent magnetization measurements, temperature-dependent x-ray diffraction, neutron powder diffraction, and Raman spectroscopy, we characterize its structural and magnetic properties. Our study reveals bipolar magnetic switching (arising from negative magnetization) and magnetocaloric effect which underline the potential of the studied mixed perovskite in device application. The neutron diffraction study shows the absence of spin reorientation transition over the entire temperature range of 1.5–320 K, although both parent compounds exhibit spin orientation transition. We discuss the microscopic origin of this curious behavior. The neutron diffraction results also reveal the ordering of Nd spins at an unusually high temperature of about 40 K, which is corroborated by Raman measurements.

Deep autoencoder as an interpretable tool for Raman spectroscopy investigation of chemical and extracellular vesicle mixtures

Surface-enhanced Raman spectroscopy (SERS) is a powerful tool that provides valuable insight into the molecular contents of chemical and biological samples. However, interpreting Raman spectra from complex or dynamic datasets remains challenging, particularly for highly heterogeneous biological samples like extracellular vesicles (EVs). To overcome this, we developed a tunable and interpretable deep autoencoder for the analysis of several challenging Raman spectroscopy applications, including synthetic datasets, chemical mixtures, a chemical milling reaction, and mixtures of EVs. We compared the results with classical methods (PCA and UMAP) to demonstrate the superior performance of the proposed technique. Our method can handle small datasets, provide a high degree of generalization such that it can fill unknown gaps within spectral datasets, and even quantify relative ratios of cell line-derived EVs to fetal bovine serum-derived EVs within mixtures. This simple yet robust approach will greatly improve the analysis capabilities for many other Raman spectroscopy applications.

Tuning of thermoelectric performance by modulating vibrational properties in Ni-doped Sb2Te3

Sb2Te3, a binary chalcogenide-based 3D topological insulator, attracts significant attention for its exceptional thermoelectric performance. We report the vibrational properties of magnetically doped Sb2Te3 thermoelectric material. Ni doping induces defect/disorder in the system and plays a positive role in engineering the thermoelectric properties through tuning the vibrational phonon modes. Synchrotron powder x-ray diffraction study confirms good crystalline quality and single-phase nature of the synthesized samples. The change in structural parameters, including B iso and strain, further corroborate with structural disorder. Detailed modification of phonon modes with doping and temperature variation is analysed from temperature-dependent Raman spectroscopic measurement. Compressive lattice strain is observed from the blue shift of Raman peaks owing to Ni incorporation in Sb site. An attempt is made to extract the lattice thermal conductivity from total thermal conductivity estimated through optothermal Raman studies. Hall concentration data support the change in temperature-dependent resistivity and thermopower. Remarkable increase in thermopower is observed after Ni doping. Simulation of the Pisarenko model, indicating the convergence of the valence band, explains the observed enhancement of thermopower in Sb2−x Ni x Te3. The energy gap between the light and heavy valence band at Γ point is found to be 30 meV (for Sb2Te3), which is reduced to 3 meV (in Sb1.98Ni0.02Te3). A significant increase in thermoelectric power factor is obtained from 715 μWm−1K−2 for pristine Sb2Te3 to 2415 μWm−1K−2 for Ni-doped Sb2Te3 sample. Finally, the thermoelectric figure of merit, ZT is found to increase by four times in Sb1.98Ni0.02Te3 than that of its pristine counterpart.

Fabrication of a coral-like barium titanate nano-piezoelectric coating and its effect on promoting osteogenic differentiation of rat bone marrow mesenchymal stem cells in vitro

Objective: To investigate the biocompatibility of coral-like barium titanate nano-piezoelectric coatings and the influence of ultrasound-excited piezoelectric effect on the early osteogenic differentiation. Methods: The barium titanate nano-piezoelectric coating (the coating group) was prepared on the surface of titanium metal by anodic oxidation, hydrothermal reaction and high-temperature annealing, and polished titanium specimens were used as control group. The surface morphology, composition, and crystal phase and hydrophilicity of the two groups of titanium specimens were characterized using scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and contact angle meter. The piezoelectric properties of the materials were characterized by piezoresponse force microscopy. Rat bone marrow mesenchymal stem cells (BMSC) were cultured and identified and seeded the surface of titanium specimens in two groups. The cells seeded on blank culture plates were used as blank group. After low intensity pulsed ultrasound intervention, cell proliferation and live/dead staining were detected to evaluate cytocompatibility of the coatings. Alkaline phosphatase (ALP) activity of each group was detected by ALP staining kit, and the expression of osteogenesis-related genes [integrin, bone morphogenetic protein 2 (BMP-2), Runt-related transcription factor 2 (RUNX2)] was detected by real-time fluorescent quantitative PCR (RT-qPCR) to evaluate the effect of the coating on promoting the early osteogenic differentiation of BMSC. Results: The surface of titanium specimens in the coating group showed a uniform coral-like morphology, and the diameter of the coral tentacles was 70-100 nm. The main component was tetragonal barium titanate. The surface hydrophilicity of the coating group (water contact angle 10.12°± 0.93°) was significantly better than that of the control group (water contact angle 78.32°±0.71°) (F= 10 165.91, P<0.001). The coating has a stable piezoelectric property with a piezoelectric constant of about 5 pC/N. Cell experiments showed that, with or without ultrasound, the cell proliferation activity of the coating group was significantly lower than that of the blank group and the control group on the third day (P<0.05). On the fifth day, with or without ultrasound, there was no significant difference in cell proliferation activity between the three groups (P>0.05). After 7 days of culture, the ALP activity of the coating group was significantly higher than that of the blank group and the control group (P<0.05). The results of RT-qPCR showed that the mRNA expression of integrin and BMP-2 in the coating group with ultrasound was significantly higher than that in the other groups with ultrasound, and was higher than that of the coating group without ultrasound (P<0.05). The expression of integrin mRNA in the control group with ultrasound was significantly higher than that in the control group without ultrasound (P<0.05). The expression of RUNX2 mRNA in the coating group with ultrasound was significantly higher than that in the coating group without ultrasound (P<0.05). Conclusions: The coral-like barium titanate nano-piezoelectric coating exhibits favorable biocompatibility and stable piezoelectric property, and facilitates the early osteogenic differentiation of BMSC under the excitation of low-intensity pulsed ultrasound.

Thermopower and resistivity of the topological insulator Bi2Te3 in the amorphous and crystalline phase

We have, in-situ, prepared and measured the temperature dependence of thermopower S(T) and resistance R(T) of Bi2Te3 topological insulator (TI) thin films in the amorphous and crystalline phase. Samples were prepared by sequential flash-evaporation at liquid 4He temperature. The S(T) in the amorphous phase is negative and much larger compared to other known amorphous materials, while in the crystalline phase it is also negative and behaves linearly with the temperature. The resistivity ρ(T) in the amorphous phase shows a semiconducting like behavior that changes to a linear metallic behavior after crystallization. S(T) an ρ(T) results in the crystalline phase are in good agreement with results obtained both in bulk and thin films reported in the literature. Linear behavior of the ρ(T) for T > 15 K indicates the typical metallic contribution from the surface states as observed in other TI novel materials. The low temperature conductivity T < 10 K exhibits logarithmic temperature dependent positive slope κ ≈ 0.21, indicating the dominance of electron-electron interaction (EEI) over the quantum interference effect, with a clear two dimensional nature of the contribution. Raman spectroscopy showed that the sample has crystallized in the trigonal R3―m space group. Energy-dispersive x-ray spectroscopy reveales high homogeneity in the concentration and no magnetic impurities introduced during preparation or growth.