A Green Synthesis of Au-Ag Alloy Nanoparticles using Polydopamine Chemistry: Evaluation of their Anticancer Potency Towards Both MCF-7 Cells and their Cancer Stem Cells Subgroup.

BACKGROUND: Limited chemotherapy efficacy and cancer stem cells (CSCs)-induced therapeutic resistance are major difficulties for tumour treatment. Adopting more efficient therapies to eliminate bulk-sensitive cancer cells and resistant CSCs is urgently needed. METHODS: Based on the potential and functional complementarity of gold and silver nanoparticles (AuNPs or AgNPs) on tumour treatment, bimetallic NPs (alloy) have been synthesized to obtain improved or even newly emerging bioactivity from a combination effect. This study reported a facile, green and economical preparation of Au-Ag alloy NPs using biocompatible polydopamine (PDA) as a reductant, capping, stabilizing and hydrophilic agent. RESULTS: These alloy NPs were quasi-spherical with rough surfaces and recorded in diameters of 80 nm. In addition, these alloy NPs showed good water dispersity, stability and photothermal effect. Compared with monometallic counterparts, these alloy NPs demonstrated a dramatically enhanced cytotoxic/pro-apoptotic/necrotic effect towards bulk-sensitive MCF-7 and MDA-MB-231 cells. The underlying mechanism regarding the apoptotic action was associated with a mitochondria-mediated pathway, as evidenced by Au3+/Ag+ mediated Mitochondria damage, ROS generation, DNA fragmentation and upregulation of certain apoptotic-related genes (Bax, P53 and Caspase 3). Attractively, these Au-Ag alloy NPs showed a remarkably improved inhibitory effect on the mammosphere formation capacity of MCF-7 CSCs. CONCLUSION: All the positive results were attributed to incorporated properties from Au, Ag and PDA, the combination effect of chemotherapy and photothermal therapy and the nano-scaled structure of Au-Ag alloy NPs. In addition, the high biocompatibility of Au-Ag alloy NPs supported them as a good candidate in cancer therapy.

Characterisation of a casein-/whey protein concentrate-Antarctic krill oil emulsion system and improvement of its storage stability.

AIMS: To develop Antarctic krill oil emulsions with casein and whey protein concentrate (WPC) and study their physicochemical properties and storage stability. METHODS: Emulsions were prepared by homogenisation and ultrasonication. The properties of the emulsions were investigated via ultraviolet ray spectroscopy, dynamic light scattering, confocal laser scanning microscope, sodium dodecyl sulphate-polyacrylamide gel electrophoresis, Fourier transform infra-red spectrometer, and fluorescence spectrum. Shelf life was predicted by the Arrhenius model. RESULTS: Casein- and WPC-krill oil emulsions were well formed; the mean particle diameters were less than 128.19 ± 0.64 nm and 158 ± 1.56 nm, the polymer dispersity indices were less than 0.26 ± 0.01 and 0.27 ± 0.01, and the zeta potential were around -46.88 ± 5.02 mV and -33.51 ± 2.68 mV, respectively. Shelf life was predicted to be 32.67 ± 1.55 days and 29.62 ± 0.65 days (40 °C), 27.69 ± 1.15 days and 23.58 ± 0.14 days (50 °C), 24.02 ± 0.15 days and 20.1 ± 0.08 days (60 °C). CONCLUSION: The prepared krill oil emulsions have great potential to become a new krill oil supplement.

Bimetallic Gold/Silver and Bioactive Camptothecin Hybrid Nanoparticles for Eradication of Cancer Stem Cells in a Combination Manner.

The defeat of cancer is still a challenge due to the existence of cancer stem cells (CSCs) because they resist conventional chemotherapy via multifactor regulated mechanisms. Consequently, one-dimensional action toward CSCs cannot work. Herein, we used rationally designed hybrid nanoparticles as a combined cancer therapy, hoping to form a multidimensional control network. In this paper, gold/silver alloy nanoparticle decorated camptothecin nanocrystals were formulated according to complementary anti-CSC mechanisms from gold, silver, and organic drug. This smart drug formulation could combine chemotherapy and thermotherapy, target different tumor sites, and demonstrate versatile toxicity profiles from each component. Major results indicated that this nanosystem demonstrated indiscriminately effective cytotoxic/proapoptotic/necrotic activity against bulk MCF-7 cells and their CSC subpopulation, in particular under laser ablation. Moreover, this nanosystem displayed enhanced antineoplastic activity against CSC spheroids, resulting in a significant reduction in their number and size, that is, their self-renewal capacity. All the results indicated that CSCs upon treatment of these new hybrid nanoparticles underwent reduced stemness and conversion from the original quiescent state and recovered their sensitivity toward chemotherapy. The relevant anticancer mechanism was ascribed to NIR-pH dual responsive drug release, synergistic/combined thermo-chemotherapy of organic drug and inorganic alloy nanoparticles, enhanced cellular uptake mediated by alloy nanoparticles, and Ag+-induced biomembrane damage. This thermo-chemotherapy platform provides a new combinatorial strategy for inorganic and organic agents in the complete elimination of CSCs.

Potential of ultraviolet laser pulse-induced current for characterizing the grain size of table sugar.

In this work, we proposed a laser-induced current (LIC) method to investigate the grain-size dependence of the plasma of table sugar induced by a nanosecond (ns) pulsed ultraviolet laser in the size range of <180 µm->550 µm and achieve the lower power consumption in measurement. Under multiple laser irradiations and an external electric field (Vb) of 200 V, the LIC variation's (ΔIp) standard deviation and variance were 0.53 nA and 0.05 nA, respectively, indicating the relatively small systematic error during the testing process. The Vb causes a decrease in the possibility of electron-ion complexation and accelerates the separation, resulting in an increase in ΔIp with Vb. With increasing grain size (diameter D) of table sugar, ΔI demonstrate a valley-like behaviour and 250-380 µm is the critical range Dc where ΔI is very weak and considerably depends on the Vb with the slope of 0.031 nA/V. At D > 550 µm and Vb = 5 V, ΔI intensities monotonically rise by 30 % when D surpasses Dc. In this instance, the energy was the main contributor to the LIC signal during plasma generation and expansion. While D is less than Dc, ΔIp increases by 27 % at D ≤ 180 µm and Vb = 5 V. The yield stress is the main reason for the formation of plasma with high temperature and density in this situation because the sugar behaves like an elastic solid. The reason for such a LIC variation trend was discussed, which can be explained by considering the morphological, thermal and mechanical properties competing with each other. The present result suggests that the LIC method enables non-contact characterisation of sugar particle size at low-power consumption.

Green Synthesis of Gold Nanoparticles and Study of Their Inhibitory Effect on Bulk Cancer Cells and Cancer Stem Cells in Breast Carcinoma.

Chemo-resistance from cancer stem cells (CSCs) subpopulation is a current issue in cancer treatment. It is important to select alternative therapies to efficiently eradicate both bulk cancer cells and CSCs. Here, gold nanoparticles (AuNPs) have been selected regarding their biocompatibility, facile and controllable synthesis, potent anti-cancer activity and photothermal conversion performance. We reported a green synthesis of functionalized AuNPs using hyaluronic acid (HA) as a reductant, capping, stabilizing and hydrophilic substance. The resultant AuNPs were spherical-shaped with an average diameter of around 30 nm. These AuNPs displayed improved physico-chemical (yield, stability, photothermal effect) and biological properties (cellular uptake, cytotoxicity and apoptotic effect) against bulk MDA-MB-231 cells, in comparison with other organic anti-cancer drugs. The intensified bioactivity was dependent on a mitochondria-mediated cascade, reflected by the damage in mitochondria, oxidative stress, intensified Caspase 3 activity and increased/decreased expression of certain pro-apoptotic (Bax, P53, Caspase 3)/anti-apoptotic (Bcl-2) genes. Moreover, these AuNPs posed a dramatically improved inhibitory effect in cell viability and self-renewable capacity on CSC subpopulation. All the results were attributed from the nano-scaled structure of AuNPs and combined effect from NIR-induced hyperthermia. In addition, the biocompatible nature of these AuNPs supported them to be a potential candidate in the development of novel chemotherapeutic drugs.

A New Gold Nanoparticles and Paclitaxel Co-Delivery System for Enhanced Anti-Cancer Effect Through Chemo-Photothermal Combination.

Limited chemotherapeutic efficiency, drug resistance and side effect are primary obstacles for cancer treatment. The development of co-delivery system with synergistic treatment modes should be a promising strategy. Here, we fabricated a multi-functionalized nanocarrier with a combination of chemotherapeutic agent and gold nanoparticles (AuNPs), which could integrate chemo-photothermal therapy and improve entire anti-cancer index. Particularly, Paclitaxel nanocrystals (PTX NC) were first fabricated as a platform, on surface of which AuNPs were decorated and polydopamine (PDA) layer act as capping, stabilizing and hydrophilic agents for PTX NC, providing a bridge connecting AuNPs to PTX. These AuNPs decorated PTX NC exhibited good physico-chemical properties like optimal sizes, stability and photothermal efficiency. Compared to other PTX formulations, they displayed considerably improved biocompatibility, selectivity, intracellular uptake, cytotoxicity, apoptosis induction activity and P-glycoprotein (Pgp) inhibitory capability, owing to a synergistic/ cooperative effect from AuNPs, PTX and NIR treatment, photothermal-triggered drug release and nano-scaled structure. Mitochondria-mediated signaling pathway is underlying mechanism for cytotoxic and apoptotic effect from AuNPs decorated PTX NC, in terms of Mitochondria damage, a loss of Mitochondrial membrane potential, intensified oxidative stress, DNA breakage, Caspase 3 activation, up-regulated expression in pro-apoptotic genes like p53, Caspase 3 and Bax and down-regulated level in anti-apoptotic gene like Bcl-2.

Antioxidative Effect of Chlorella Pyrenoidosa Protein Hydrolysates and Their Application in Krill Oil-in-Water Emulsions.

Chlorella pyrenoidosa is an excellent source of protein, and in this research, we assessed the antioxidant and emulsifying effects of Chlorella protein hydrolysate (CPH) using neutral proteases and alkaline proteases, as well as the properties of CPH-derived krill oil-in-water (O/W) emulsions. The CPHs exhibited the ability to scavenge several kinds of free radicals, including 1,1-diphenyl-2-picrylhydrazyl (DPPH), O2-, hydroxyl, and ABTS. Additionally, the CPHs (5 mg/mL) scavenged approximately 100% of the DPPH and ABTS. The CPHs showed similar emulsifying activities to Tween 20 and excellent foaming activities (max FS 74%), which helped to stabilize the krill oil-in-water emulsion. Less than 10 mg/mL CPHs was able to form fresh krill oil-in-water emulsions; moreover, the CPHs (5 mg/mL) in a krill O/W emulsion were homogenous, opaque, and stable for at least 30 days. Based on their inhibitory effects on the peroxide value (POV) and thiobarbituric acid reactive substances (TRABS), the CPHs were found to be able to inhibit lipid oxidation in both emulsifying systems and krill O/W emulsions. Thus, the CPHs could improve superoxide dismutase (SOD) activities by 5- or 10-fold and decrease the high reactive oxygen species (ROS) level caused by the addition of H2O2 in vitro. In conclusion, health-promoting CPHs could be applied in krill oil-in-water emulsions as both emulsifiers and antioxidants, which could help to improve the oxidative and physical stability of emulsions.

Gold Nanoparticle-Decorated Drug Nanocrystals for Enhancing Anticancer Efficacy and Reversing Drug Resistance Through Chemo-/Photothermal Therapy.

Limited chemotherapeutic efficiency, drug resistance, and side effects are primary obstacles for cancer treatment. The development of co-delivery systems with synergistic treatment modes should be a promising strategy. Here, we fabricated a multifunctionalized nanocarrier with a combination of chemotherapeutic agents and gold nanoparticles (AuNPs), which could integrate chemo-photothermal therapy, thus enhancing overall anticancer efficacy, sensitizing drug-resistant cancer cells, and diminishing cancer stem cells (CSCs). To be specific, camptothecin nanocrystals (CPT NCs) were prepared as a platform, on the surface of which AuNPs were decorated and a hyaluronic acid layer acted as capping, stabilizing, targeting, and hydrophilic agents for CPT NCs, and reducing agents for AuNPs, providing a bridge connecting AuNPs to CPT. These AuNP-decorated CPT NCs exhibited good physico-chemical properties such as optimal sizes, payload, stability, and photothermal efficiency. Compared to other CPT formulations, they displayed considerably improved biocompatibility, selectivity, intracellular uptake, cytotoxicity, apoptosis induction activity, Pgp inhibitory capability, and anti-CSC activity, owing to a synergistic/cooperative effect from AuNPs, CPT, near-infrared treatment, pH/photothermal-triggered drug release, and nanoscaled structure. A mitochondrial-mediated signaling pathway is the underlying mechanism for cytotoxic and apoptotic effects from AuNP-decorated CPT NCs, in terms of mitochondrial dysfunction, intensified oxidative stress, DNA fragmentation, caspase 3 activation, upregulation of proapoptotic genes such as p53, Bax, and caspase 3, and lower levels of antiapoptotic Bcl-2.

Gibberellic acid-induced fatty acid metabolism and ABC transporters promote astaxanthin production in Phaffia rhodozyma.

AIMS: Astaxanthin is an important natural antioxidant with various biological functions; however, the production of astaxanthin does not meet the requirements for industrialization. The aim of the present study was to identify an inducer that increases astaxanthin yield and to evaluate the regulatory mechanism of the induction of astaxanthin synthesis in Phaffia rhodozyma. METHODS AND RESULTS: The effects of indole-3-acetic acid (IAA), jasmonic acid (JA) and gibberellic acid (GA) on astaxanthin synthesis were studied by fermentation kinetics analysis. Then, combined transcriptomics and metabolomics approaches were used to analyse differential metabolites and expressed genes involved in astaxanthin synthesis induced by GA. The results indicated that GA significantly increased astaxanthin production; however, IAA and JA had no significant effect on astaxanthin synthesis. The induction by GA significantly enhanced fatty acid metabolism and ABC transporters, increased the expression of fatty acid desaturase and ABC transporter genes, and elevated the contents of unsaturated fatty acids. CONCLUSIONS: These results suggested that fatty acid saturation plays an important role in astaxanthin accumulation and that ABC transporters may be the efflux pumps for astaxanthin. SIGNIFICANCE AND IMPACT OF THE STUDY: The present study reveals metabolic mechanism of GA-induced astaxanthin synthesis and proposes a new strategy of transporter engineering to improve astaxanthin production.

Ultrafast Deep-Ultraviolet Laser-Induced Voltage Response of Pyrite.

Ultrafast, high-sensitivity deep-ultraviolet (UV) photodetectors are crucial for practical applications, including optical communication, ozone layer monitoring, flame detection, etc. However, fast-response UV photodetectors based on traditional materials suffer from issues of expensive production processes. Here, we focused on pyrite with simultaneously cheap production processes and ultrafast response speed. Nanoseconds photovoltaic response was observed under UV pulsed laser irradiation without an applied bias at room temperature. In addition, the response time of the laser-induced voltage (LIV) signals was ~20 ns, which was the same as the UV laser pulse width. The maximum value of the responsivity is 0.52 V/mJ and the minimum value of detectivity was about to ~1.4 × 1013 Jones. When there exists nonuniform illumination, a process of diffusion occurs by which the carriers migrate from the region of high concentration toward the region of low concentration. The response speed is limited by a factor of the diffusion of the carriers. With an increment in laser energy, the response speed of LIV is greatly improved. The high response speed combined with low-cost fabrication makes these UV photodetectors highly attractive for applications in ultrafast detection.

Antimicrobial mechanism of 4-hydroxyphenylacetic acid on Listeria monocytogenes membrane and virulence.

4-Hydroxyphenylacetic acid (4-HPCA) is the major intestinal metabolite of kaempferol and polymeric proanthocyanidins whereas the effect of 4-HPCA on Listeria monocytogenes remains unknown. In this study, we investigated the effect and mechanism of action of 4-HPCA on the highly lethal foodborne pathogen Listeria monocytogenes. Our results indicated that 4-HPCA inhibited L. monocytogenes growth and proliferation in a dose-dependent manner. In particular, L. monocytogenes displayed negligible growth or proliferation after 4-HPCA treatment (15.61 mM) for 24 h. The impact of 4-HPCA on cell membrane structure and function was investigated in terms of fluorometric cell membrane integrity, zeta potential and relative electrical conductivity. We observed an approximately 15 % fluorescence reduction in the cell membrane after MIC treatment. The zeta potential of the bacteria shifted significantly from -49.74 to -43.70 mV, -36.65 mV and -37.97 mV after treatment with 4-HPCA at the MIC for 0 h, 3 h and 12 h, respectively. The absolute value of the relative electrical conductivities increased significantly following 3 h, 6 h, 9 h and 15 h of 4-HPCA treatment at the MIC level. The results of scanning electron microscopy (SEM) showed that cells treated with 4-HPCA displayed a wrinkled morphology and irregular shapes. Moreover, 4-HPCA obviously decreased the expression of three virulence genes (hlyA, prfA, and inlA) in L. monocytogenes after 12 h of treatment. All these results verified that 4-HPCA, as an effective antibacterial compound against L. monocytogenes, could cause cell death through cell membrane damage and decrease the expression of three virulence factors.

Novel Strategy of Mussel-Inspired Immobilization of Naringinase with High Activity Using a Polyethylenimine/Dopamine Co-deposition Method.

Mussel-inspired surface chemistry is recognized as a simple, efficient, and mild surface modification method and has become a research hotspot in many fields. In this study, polyethylenimine/dopamine was coated on the surface of SBA-15 using a co-deposition method, making it possible to immobilize naringinase with high activity and operation stability. The optimal modification and immobilization conditions as well as enzyme properties were investigated. The naringinase activity can reach up to 753.78 U/g carrier, which was much higher than those of the previous works. Besides, the residual naringinase activity still kept 78.91% of the initial activity after one month of storage and maintained 60.79% after 8 cycles. Therefore, the strategy of mussel-inspired enzyme immobilization could be recognized as a promising and universal enzyme immobilization method, with the advantages of high relative enzyme activity, enzyme carrying rate, enzyme activity recovery rate, and good reusability and storage stability.

A facile preparation of immobilized naringinase on polyethyleneimine-modified Fe3O4 magnetic nanomaterials with high activity.

Polyethyleneimine-modified Fe3O4 nanoparticles (Fe3O4-PEI) were synthesized by the one-step co-precipitation method, and the resulting material was used to immobilize naringinase from the fermentation broth of Aspergillus niger FFCC uv-11. The immobilized naringinase activity could reach up to 690.74 U per g-support at the conditions of initial naringinase activity of 406.25 U mL-1, immobilization time of 4 h, glutaraldehyde concentration of 40% (w/v), immobilization temperature of 35 °C, and pH value of 5.5, with naringinase-carrying rate and naringinase activity recovery of 92.93% and 20.89%, respectively. In addition, the immobilized naringinase exhibited good pH and temperature stability in a pH range of 3.5-6.0 and temperature range of 40-70 °C, and the optimal reaction pH and reaction temperature were optimized as 5.5 and 60 °C, respectively. Besides, the immobilized naringinase could maintain 60.58% of the original activity after 10 reuse cycles, indicating that the immobilized naringinase had good reusability. Furthermore, the immobilized naringinase also performed excellent storage stability, 87.52% of enzyme activity still remained as stored at 4 °C for one month. In conclusion, the Fe3O4-PEI could be considered as a promising support for naringinase immobilization, with the advantages of high enzyme activity loading, good reusability, storage stability and rapid recovery.

Silver nanoparticles functionalized Paclitaxel nanocrystals enhance overall anti-cancer effect on human cancer cells.

For chemotherapeutic drugs, precise tumor-targeting and high anti-cancer efficiency is equally important in order to enhance chemotherapy and reverse drug resistance. The combination of multifunctional agents to achieve synergy should be a promising strategy. In our study, we have successfully developed novel multifunctionalized drug nanocrystals to realize co-delivery of the organic drug Paclitaxel (PTX), inorganic silver nanoparticles (AgNPs) and a tumor targeting agent. To be specific, PTX nanocrystals were first prepared as a template, then coated with polydopamine (PDA). The PDA layer was utilized as the connection bridge to produce and deposit AgNPs in situ, and provide sites for tumor-targeting peptide NR1 (RGDARF) grafting. As a result, these NR1/AgNP-decorated drug nanocrystals exhibited dramatically improved cellular uptake efficiency, in vitro anti-cancer activity and an anti-migratory effect against a variety of cancer cells, which was attributable to the synergistic, or at least additive, effect of the AgNPs and PTX, enhanced cellular uptake efficiency through NR1-receptor interaction, pH-responsive drug release and the nanoscaled nature. In particular, high anti-cancer activity and low side effects from these NR1/AgNP-decorated PTX nanocrystals were well balanced in terms of good selectivity and biocompatibility. Moreover, these novel drug nanocrystals displayed strong apoptotic-inducing potency, resulting in cell membrane lysis, nuclear damage, mitochondria dysfunction, excessive ROS release and double-stranded DNA breakage. The potential acting mechanism and molecular basis of these novel drug nanocrystals is relevant to the regulation of mitochondria-mediated apoptosis with a greater Bax-to-Bcl-2 ratio and the activation of pro-apoptotic P53 and caspase 3.

Hyaluronic Acid-Coated Camptothecin Nanocrystals for Targeted Drug Delivery to Enhance Anticancer Efficacy.

Tumor-targeted drug delivery via chemotherapy is very effective on cancer treatment. For potential anticancer agent such as Camptothecin (CPT), high chemotherapeutic efficacy and accurate tumor targeting are equally crucial. Inspired by special CD44 binding capability from hyaluronic acid (HA), in this study, novel HA-coated CPT nanocrystals were successfully prepared by an antisolvent precipitation method for tumor-targeted delivery of hydrophobic drug CPT. These HA-coated CPT nanocrystals demonstrated high drug loading efficiency, improved aqueous dispersion, prolonged circulation, and enhanced stability resulting from their nanoscaled sizes and hydrophilic HA layer. Moreover, as compared to crude CPT and naked CPT nanocrystals, HA-coated CPT nanocrystals displayed dramatically enhanced in vitro anticancer activity, apoptosis-inducing potency against CD44 overexpressed cancer cells, and lower toxic effect toward normal cells due to pH-responsive drug release behavior and specific HA-CD44 mediated endocytosis. Additionally, HA-coated CPT nanocrystals performed fairly better antimigration activity and biocompatibility. The possible molecular mechanism regarding this novel drug formulation might be linked to intrinsic mitochondria-mediated apoptosis by an increase of Bax to Bcl-2 ratio and upregulation of P53. Consequently, HA-coated CPT nanocrystals are expected to be an effective nanoplatform in drug delivery for cancer therapy.

Lytic peptide-grafted beta-cyclodextrin polymer based nano-scaled drug delivery system with enhanced camptothecin anti-cancer efficacy.

The aqueous solubility of drug molecules is closely related to its bioactivity like bioavailability and subsequent therapeutic index, especially in the case of hydrophobic drugs like camptothecin (CPT), a potential broad-spectrum anti-cancer agent. Enhanced anti-cancer activity and selectivity of CPT are equally important. Inspired by host-guest effect and drug combination regimen, we developed a novel tumor lytic peptide incorporated drug delivery system by forming beta-cyclodextrin polymer (BCDp) based inclusion complex in nano-scaled size. In this study, BCDp formed inclusion complex with CPT and then a lytic-type peptide (ZH) was grafted. The resulting combinational formulation of BCDp, CPT and ZH, named as ZH-BCDp-CPT inclusion complex, demonstrated greater solubility resulting from its nano-scaled size, amorphous solid state and inclusion structure. Moreover, ZH facilitated quick internalization of conjugated drug via cell membrane lysis, leading to efficient intracellular drug delivery. This novel drug formulation was featured with prolonged circulation, enhanced anti-cancer efficacy, selectivity, anti-cell migration activity and better biocompatibility in comparison with crude CPT and binary BCDp-CPT inclusion complex, all of which were attributed to a cooperative action between ZH and BCDp-CPT inclusion complex. Our results suggested ZH-BCDp-CPT inclusion complex induced cell apoptosis by up-regulation of Bax and P53 and down-regulation of Bcl-2, primarily involved in the mitochondrial pathways.

Assessment for Less than 20-ppm Oil Leakage in Soil Using Terahertz Wave.

Although an accurate detection of trace oil leaks is of the utmost important for soil protection, the typically used techniques fail to provide rapid assessment of less than 20 parts per million (ppm) of oil in soil. Terahertz (THz) time-domain spectroscopy, an optical method with high sensitivity to polar organics, was used to characterize the content of crude oil in soils. A linear model was built between the concentration of crude oil and the THz attenuation coefficient, which predicted the limit of detection ranging from 4.11 to 16.2 ppm. Some organics, such as aromatic and aliphatic compounds, contribute to larger absorption in the THz range than minerals. Effective-medium theory was optimized to elucidate the crude oil content dependence of THz dielectric constants. Consequently, THz technology could be an effective method for detecting trace oil leakage in soil.

High Water Content Prediction of Oil-Water Emulsions Based on Terahertz Electromagnetically Induced Transparency-like Metamaterial.

This work aims to investigate the electromagnetically induced transparency-like (EIT-like) metamaterial for high water cut emulsions' detection in the terahertz band. The electromagnetic responses of the selected metamaterial covering emulsions exhibit red-shifted resonant frequency with increasing water volume from 60 to 98%. Three numerical models coinciding with theory analysis were built based on the extracted resonant frequencies at the transmission peak and dips to predict water concentration. The results show that the built models accurately predicted the water content with absolute errors less than 0.26, 0.41, and 0.24%, respectively. The EIT-like resonance is introduced by coupled bright and dark modes, making it similar to a weakened plasma resonance. Consequently, the permittivity-dependent frequency would help develop both economically feasible and socially beneficial sensors for high water content prediction.

Determining the Humidity-Dependent Ortho-to- Para Ratio of Water Vapor at Room Temperature Using Terahertz Spectroscopy.

The origin of the water spin isomers observed under various physico-chemical conditions is of great interest, including that of H2O molecules in the gas phase. Here, terahertz time-domain spectroscopy (THz-TDS) was used to study the humidity-dependent ortho-to- para (O/P) ratio of water vapor at room temperature. The relative contents of para and ortho molecules were obtained by fitting the absorption lines of water vapor showing the relationship between the spin isomer contents and humidity. Larger O/P ratios with values of ∼3.2 were observed at lower humidity (<20%) due to the stronger attractive forces of para molecules. The concentration of the ortho isomers then began to decrease at higher humidity (>20%) due to the preferential formation of dimers and clusters at increasing concentrations. Thus, the ratio gradually decreased with increasing humidity.

Layer Caused an Anisotropic Terahertz Response of a 3D-printed Simulative Shale Core.

Energy demands have motivated the development of shale formations as significant unconventional reservoirs. The anisotropy of shales plays a significant role in both the mechanical behavior and engineering activities. Alternating layers presented in shales affect the propagation of waves, causing anisotropy at various frequencies. Simplifying the complicated interior structures of shales is conducive to characterize the anisotropic properties. Therefore, simulative shale core samples were designed and fabricated using additive manufacturing processes, and layer-caused dielectric anisotropy was investigated by terahertz (THz) time-domain spectroscopy. On the basis of effective medium theory, the change of the optical length caused by refraction of rays was discussed and modeled. It is believed that the refraction of rays at the interfaces is the source of THz propagation anisotropy in the multilayered structure, and the anisotropy degree is mainly influenced by the layer thickness as well as the refractive index.