Role of Defects of Carbon Nanomaterials in the Detection of Ovarian Cancer Cells in Label-Free Electrochemical Immunosensors.

Developing label-free immunosensors to detect ovarian cancer (OC) by cancer antigen (CA125) is essential to improving diagnosis and protecting women from life-threatening diseases. Four types of carbon nanomaterials, such as multi-wall carbon nanotubes (MWCNTs), vapor-grown carbon fiber (VGCFs), graphite KS4, and carbon black super P (SP), have been treated with acids to prepare a carbon nanomaterial/gold (Au) nanocomposite. The AuNPs@carbon nanocomposite was electrochemically deposited on a glassy carbon electrode (GCE) to serve as a substrate to fabricate a label-free immunosensor for the detection of CA125. Among the four AuNPs@carbon composite, the AuNPs@MWCNTs-based sensor exhibited a high sensitivity of 0.001 µg/mL for the biomarker CA125 through the square wave voltammetry (SWV) technique. The high conductivity and surface area of MWCNTs supported the immobilization of AuNPs. Moreover, the carboxylic (COO-) functional groups in MWCNT improved to a higher quantity after the acid treatment, which served as an excellent support for the fabrication of electrochemical biosensors. The present method aims to explore an environmentally friendly synthesis of a layer-by-layer (LBL) assembly of AuNPs@carbon nanomaterials electrochemical immunoassay to CA125 in a clinical diagnosis at a low cost and proved feasible for point-of-care diagnosis.

rGO based immunosensor amplified using MWCNT and CNF nanocomposite as analytical tool for CA125 detection.

The electrochemical performance of dual layer immunosensor has been studied by employing reduced Graphene oxide (rGO) and its nanocomposites with Carbon Nanofibers (CNFs) and Carbon Nanotubes (CNTs) as supporting matrix for the detection of CA125. The immunosensor determination was based on the formation of antibody - antigen immunocomplex, a decrement in the current response was observed in accordance with the concentration of antigen. Better performance exhibited by rGO/CNF in terms of linearity (99%) and sensitivity 0.65 µA (µg mL-1)-1 can be attributed to its conductivity and surface area. The nanocomposite are employed in the detection of CA125 with linear working range of 10-32 × 10-4 µg mL-1, the limit of detection is found to be 0.28 pg mL-1 rGO nanocomposite with CNT (rGO/CNT) is studied as transducer material. rGO/CNT exhibited better linearity when compared to rGO due to its good conductivity. Thus, graphene nanocomposite transducer materials have vital application in detection of oncomarkers.

In situ electrochemical synchrotron radiation for Li-ion batteries.

Observing the electronic structure, compositional change and morphological evolution of the surface and interface of a battery during operation provides essential information for developing new electrode materials for Li-ion batteries (LIBs); this is because such observations demonstrate the fundamental reactions occurring inside the electrode materials. Moreover, obtaining detailed data on chemical phase changes and distributions by analyzing an operating LIB is the most effective method for exploring the intercalation/de-intercalation process, kinetics and the relationship between phase change or phase distribution and battery performance, as well as for further optimizing the material synthesis routes for advanced battery materials. However, most conventional in situ electrochemical techniques (other than by using synchrotron radiation) cannot clearly or precisely demonstrate structural change, electron valence change and chemical mapping information. In situ electrochemical-synchrotron radiation techniques such as X-ray absorption spectroscopy, X-ray diffraction spectroscopy and transmission X-ray microscopy can deliver accurate information regarding LIBs. This paper reviews studies regarding various applications of in situ electrochemical-synchrotron radiation such as crystallographic transformation, oxidation-state changes, characterization of the solid electrolyte interphase and Li-dendrite growth mechanism during the intercalation/de-intercalation process. The paper also presents the findings of previous review articles and the future direction of these methods.

Preventing the Distortion of CoO6 Octahedra of LiCoO2 at High-Voltage Operation of Lithium-Ion Battery: An Organic Surface Reinforcement.

Lithium cobalt oxide (LiCoO2, LCO) has been widely used in electronic markets due to its high energy density and wide voltage range applications. Recently, high-voltage (HV, >4.5 V) operation has been required to obey the requirements of high energy density and cycle life in several applications such as electric vehicles and energy storage. However, the HV operation causes structure instability due to the over de-lithiation of LCO, as well as decomposing common carbonate solvents, thereby incurring the decay of battery performance. Moreover, a distortion of the CoO6 octahedra of LCO during de-lithiation induces a rehybridization of the Co 3d and O 2p orbitals. According to above reasons, decreasing the Co-O covalent bond promptly triggers high risks that significantly limit further use of LCO. In this research, an organic surface reinforcement by using bismaleimide-uracil (BU) that electrochemically forms a cathode electrolyte interphase (CEI) on LCO was explored. The results of electrochemical impedance spectroscopy and battery performance, such as the c-rate and cyclability tests, demonstrated that the modified CEI formed from BU significantly prevents the distortion of CoO6 octahedra. X-ray photoelectronic spectroscopy and in situ XAS indicated less LiF formation and higher bond energy of Co-O improved. Finally, the differential scanning calorimetry showed the onset temperature of decomposition of LCO was extended from 245 to 270 °C at 100% state of charge, which is about a 25 °C extension. The exothermic heat of LCO decreased by approximately 30% for high-safety use. This research confirms that the BU is eligible for high voltage (>4.5 V) LCO and presents outstanding electrochemical properties and safety performances.

Enhancing the Mechanical Properties and Aging Resistance of 3D-Printed Polyurethane through Polydopamine and Graphene Coating.

Three-dimensional (3D) printing is a versatile manufacturing method widely used in various industries due to its design flexibility, rapid production, and mechanical strength. Polyurethane (PU) is a biopolymer frequently employed in 3D printing applications, but its susceptibility to UV degradation limits its durability. To address this issue, various additives, including graphene, have been explored to enhance PU properties. Graphene, a two-dimensional carbon material, possesses remarkable mechanical and electrical properties, but challenges arise in its dispersion within the polymer matrix. Surface modification techniques, like polydopamine (PDA) coating, have been introduced to improve graphene's compatibility with polymers. This study presents a method of 3D printing PU scaffolds coated with PDA and graphene for enhanced UV stability. The scaffolds were characterized through X-ray diffraction, Fourier-transform infrared spectroscopy, mechanical testing, scanning electron microscopy, and UV durability tests. Results showed successful PDA coating, graphene deposition, and improved mechanical properties. The PDA-graphene-modified scaffolds exhibited greater UV resistance over time, attributed to synergistic effects between PDA and graphene. These findings highlight the potential of combining PDA and graphene to enhance the stability and mechanical performance of 3D-printed PU scaffolds.

CT-Guided Percutaneous Cryoablation for Lung Metastasis of Colorectal Cancer: A Case Series.

PURPOSE: This study aimed to evaluate the efficacy of computed tomography (CT) guided percutaneous cryoablation (CA) for the management of lung metastases in patients with metastatic colorectal cancer (mCRC). METHODS: Retrospective analysis was performed on 38 mCRC patients with lung metastases, who underwent CT-guided percutaneous CA at our center from May 1, 2020 to November 1, 2021. The technical success rate, 1-year local control (LC) rate, recurrence-free survival (RFS) and treatment-related complications were analyzed. RESULTS: The CA procedure was successfully performed in all patients, with a technical success rate of 100%. The 1-year LC rate was 94.7% (36/38), while 16 patients experienced new distant lung metastases during the follow-up period. The median RFS was 20 months (95% CI: 13.0-27.0). The median RFS of patients with and without extrapulmonary metastasis was 15 and 23 months, respectively. Complications were reported in 18 (47.4%) patients following the CA procedure. Pneumothorax was discovered in 15 (39.5%) patients, and five of these patients (13.2%) required chest tube intubation. Two patients (5.3%) presented with hemoptysis during the CA procedure. One patient developed subcutaneous emphysema as detected in the post-procedure follow-up imaging. All patients tolerated the peri-procedural pain well under local anesthesia, and the mean visual analog scale (VAS) score was 2.8. CONCLUSION: Lung CA is a safe and well-tolerated treatment with a satisfactory local control rate for patients with lung metastases derived from mCRC.

Electrochemical immunosensing by carbon ink/carbon dot/ZnO-labeled-Ag@polypyrrole composite biomarker for CA-125 ovarian cancer detection.

In this work, we demonstrated a novel cancer antigen 125 (CA125) biomarker detection based on electrochemical immunosensor. The biomarker on conductive composite materials of carbon ink/carbon dot/zine oxide (C-ink/CD/ZnO) was employed as an electrode platform by using ITO substrate to enhance the interaction of antibodies (Ab) with supporting catalytic performance of ZnO as a labeling signal molecule. They were a scientist attention for biosensor with chemical stability, strong biocompatibility, high conductive signal, and accuracy. Moreover, the nanocomposite of silver@polypyrrole (Ag@PPy) was used as a potential redox mediator. The labeled construction with Ag@PPy was more accuracy than that of a free-labeled. The created immunosensor was a wide linear range as 1 ag·mL-1 - 100 ng·mL-1 and a low limitation of detection as 0.1 fg·mL-1 under the optimal condition. This suggested that the immunosensor is considered to be an accurate and efficient diagnostic tool for CA125 and other biomarkers detection in actual sample analysis for clinic.

Di-µ-oxido-bis-[(2-eth-oxy-6-{[2-(2-hy-droxy-ethyl-amino)-ethyl-imino]-meth-yl}phenolato-κN,N',O)oxidovanadium(V)].

In the title centrosymmetric dinuclear dioxidovanadium(V) complex, [V(2)(C(13)H(19)N(2)O(3))(2)O(4)], the V(V) ion is coordinated by an N,N',O-tridendate 2-eth-oxy-6-{[2-(2-hy-droxy-ethyl-amino)-ethyl-imino]-meth-yl}phenolate ligand and three oxide O atoms, forming a distorted cis-VN(2)O(4) octa-hedral geometry. The bridging O atoms show one short and one long bond to their two attached V(V) atoms. The dihedral angle between the benzene ring of the ligand and the V(2)O(2) plane is 75.2 (3)°. The deviation of the V(V) ion from the plane defined by the three donor atoms of the tridentate ligand and one bridging oxide O atom is 0.337 (2) Štowards the terminal oxide O atom. Two N-H⋯O hydrogen bonds help to establish the conformation of the dimer. In the crystal, the complex mol-ecules are linked by O-H⋯O hydrogen bonds, forming [100] chains.

[Preparation and luminescent properties of ZnMoO4: Tb3+].

Tb3+ doped ZnMoO4 materials were synthesized by combustion method. XRD results show that the samples completely formed single ZnMoO4 phase at 700 degrees C which belongs to Trigonal, while the incorporation of Tb3+ does not affect the basic structure of ZnMoO4. The TG-DTA results show that the samples fully formed ZnMoO4 phase due to the energy absorption at about 680 C. IR results show that there were no other organic peaks after burning at 700 C, indicating that citric acid has been completely decomposed and Tb3+ ions have been fully integrated into the lattice of ZnMoO4. SEM results show that the dispersion of particles gradually increases along with the improvement of the temperature. The best excitation wavelength was 488 nm when the monitoring wavelength was 544 nm, which corresponds to the 5D4 -->7F5 transition of Tb3+. Finally, a valuable green fluorescent powder of ZnMoO4: Tb3+ has been obtained.

State-of-the-Art Review on the Application of Membrane Bioreactors for Molecular Micro-Contaminant Removal from Aquatic Environment.

In recent years, the emergence of disparate micro-contaminants in aquatic environments such as water/wastewater sources has eventuated in serious concerns about humans' health all over the world. Membrane bioreactor (MBR) is considered a noteworthy membrane-based technology, and has been recently of great interest for the removal micro-contaminants. The prominent objective of this review paper is to provide a state-of-the-art review on the potential utilization of MBRs in the field of wastewater treatment and micro-contaminant removal from aquatic/non-aquatic environments. Moreover, the operational advantages of MBRs compared to other traditional technologies in removing disparate sorts of micro-contaminants are discussed to study the ways to increase the sustainability of a clean water supplement. Additionally, common types of micro-contaminants in water/wastewater sources are introduced and their potential detriments on humans' well-being are presented to inform expert readers about the necessity of micro-contaminant removal. Eventually, operational challenges towards the industrial application of MBRs are presented and the authors discuss feasible future perspectives and suitable solutions to overcome these challenges.

[3-Chloro-N'-(2-oxidonaphthalen-1-yl-methylidene)benzohydrazidato]methanol(methanolato)oxidovanadium(V).

In the title complex, [V(C(18)H(11)ClN(2)O(2))(CH(3)O)O(CH(3)OH)], the V(V) ion is coordinated by a tridendate 3-chloro-N'-(2-oxidonaphthalen-1-ylmethylidene)benzohydrazidate ligand, one oxido ligand and by O atoms from a methanol and a methoxide ligand, forming a distorted octa-hedral geometry. The dihedral angle between the benzene ring and the naphthyl-ene ring system is 6.4 (3)°. The deviation of the V(V) ion from the plane defined by the three donor atoms of the tridentate ligand and the meth-oxy O atom towards the oxido O atom is 0.323 (2) Å. In the crystal, pairs of inter-molecular O-H⋯N hydrogen bonds form centrosymmetric dimers.

[N'-(5-Bromo-2-oxidobenzyl-idene-κO)-2-chloro-benzohydrazidato-κN',O](methanol-κO)(methano-lato-κO)oxido-vanadium(V).

The V(V) atom in the title complex, [V(C(14)H(8)BrClN(2)O(2))(CH(3)O)O(CH(3)OH)], is six-coordinated by one phenolate O, one imine N and one enolic O atom of the hydrazone ligand, one oxide O atom, one methanol O atom and one methoxide O atom in a distorted octa-hedral geometry. The dihedral angle between the two benzene rings of the hydrazone ligand is 13.2 (3)°. The deviation of the V atom towards the oxide O atom from the plane defined by the three donor atoms of the hydrazone ligand and the meth-oxy O atom is 0.318 (2) Å. Bond lengths are comparable with those observed in similar oxidovanadium(V) complexes with hydrazone ligands. In the crystal, pairs of mol-ecules are linked through inter-molecular O-H⋯N hydrogen bonds, forming dimers.

(Acetyl-acetonato-κO,O')(2-bromo-4-chloro-6-{[2-(dimethyl-amino)-ethyl-imino]-meth-yl}phenolato-κN,N',O)oxidovanadium(IV).

The V(IV) atom in the title complex, [V(C(11)H(13)BrClN(2)O)(C(5)H(7)O(2))O], is six-coordinated by one phenolate O, one imino N and one amino N atom of the tridentate anionic Schiff base ligand, by one oxide O atom, and by two O atoms of an acetyl-acetonate anion, forming a distorted cis-VN(2)O(4) octa-hedral coordination geometry. The deviation of the V atom from the plane defined by the three donor atoms of the Schiff base ligand and one O atom of the acetyl-acetone ligand towards the oxide O atom is 0.256 (2) Å.

Synthesis, Characterization and Crystal Structures of Fluoro-Substituted Aroylhydrazones with Antimicrobial Activity.

A series of five new fluoro-substituted aroylhydrazones were prepared and structurally characterized by elemental analysis, IR, UV-Vis and 1H NMR spectroscopy, as well as single crystal X-ray diffraction. The compounds were evaluated for their antibacterial (Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and Pseudomonas fluorescence) and antifungal (Candida albicans and Aspergillus niger) activities by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) method. The biological assay indicated that the presence of the electron-withdrawing groups in the aroylhydrazones improved their antimicrobial activities.

Lithium and Potassium Cations Affect the Performance of Maleamate-Based Organic Anode Materials for Potassium- and Lithium-Ion Batteries.

In this study we prepared potassium-ion batteries (KIBs) displaying high output voltage and, in turn, a high energy density, as replacements for lithium-ion batteries (LIBs). Organic electrode materials featuring void spaces and flexible structures can facilitate the mobility of K+ to enhance the performance of KIBs. We synthesized potassium maleamate (K-MA) from maleamic acid (MA) and applied as an anode material for KIBs and LIBs, with 1 M potassium bis(fluorosulfonyl)imide (KFSI) and 1 M lithium bis(fluorosulfonyl)imide (LiFSI) in a mixture of ethylene carbonate and ethyl methyl carbonate (1:2, v/v) as respective electrolytes. The K-MA_KFSI anode underwent charging/discharging with carbonyl groups at low voltage, due to the K···O bond interaction weaker than Li···O. The K-MA_KFSI and K-MA_LiFSI anode materials delivered a capacity of 172 and 485 mA h g-1 after 200 cycles at 0.1C rate, respectively. K-MA was capable of accepting one K+ in KIB, whereas it could accept two Li+ in a LIB. The superior recoveries performance of K-MA_LiFSI, K-MA_KFSI, and Super P_KFSI at rate of 0.1C were 320, 201, and 105 mA h g-1, respectively. This implies the larger size of K+ can reversibly cycling at high rate.

In Situ Co-O Bond Reinforcement of the Artificial Cathode Electrolyte Interphase in Highly Delithiated LiCoO2 for High-Energy-Density Applications.

Highly delithiated LiCoO2 has high specific capacity (>200 mAh g-1); however, its degradation behavior causes it to have poor electrochemical performance and thermal instability. The degradation of highly delithiated LiCoO2 is mainly induced by oxygen vacancy migration and weakening of oxygen-related interactions, which result in pitting corrosion and fault formation on the surface. In this research, a coupling agent, namely, 3-aminopropyltriethoxysilane (APTES), was grafted onto the surface of LiCoO2 to form a cross-linking structure. Through the aza-Michael addition reaction, an oligomer formed from barbituric acid and bisphenol a diglycidyl ether diacrylate were reacted with the cross-linking APTES to form an artificial cathode electrolyte interphase (ACEI). The highly delithiated LiCoO2 containing the ACEI had considerably less degradation on the surface of the bulk material caused by oxygen release. The formation of the O1 phase was prevented in high delithiation and high-temperature operations. This research revealed that the ACEI reinforced the Co-O bond, which is crucial in preventing gas evolution and O1 phase formation. In addition, the ACEI prevents direct contact between the electrolyte and highly active surface of LiCoO2, thereby preventing the formation of a thick and high impedance traditional cathode electrolyte interphase. According to the present results, highly delithiated LiCoO2 containing the ACEI exhibited outstanding cycle retention and capacity at 55 °C as well as low heat capacity release in the fully delithiated state. The ACEI considerably protected and maintained the electrochemical performance of highly delithiated LiCoO2, which is suitable for high-energy-density applications, such as electric vehicles and power tools.

Effective Ru/CNT Cathode for Rechargeable Solid-State Li-CO2 Batteries.

An effective Ru/CNT electrocatalyst plays a crucial role in solid-state lithium-carbon dioxide batteries. In the present article, ruthenium metal decorated on a multi-walled carbon nanotubes (CNTs) is introduced as a cathode for the lithium-carbon dioxide batteries with Li1.5Al0.5Ge1.5(PO4)3 solid-state electrolyte. The Ru/CNT cathode exhibits a large surface area, maximum discharge capacity, excellent reversibility, and long cycle life with low overpotential. The electrocatalyst achieves improved electrocatalytic performance for the carbon dioxide reduction reaction and carbon dioxide evolution reaction, which are related to the available active sites. Using the Ru/CNT cathode, the solid-state lithium-carbon dioxide battery exhibits a maximum discharge capacity of 4541 mA h g-1 and 45 cycles of battery life with a small voltage gap of 1.24 V compared to the CNT cathode (maximum discharge capacity of 1828 mA h g-1, 25 cycles, and 1.64 V as voltage gap) at a current supply of 100 mA g-1 with a cutoff capacity of 500 mA h g-1. Solid-state lithium-carbon dioxide batteries have shown promising potential applications for future energy storage.

Catalytically Active Site Identification of Molybdenum Disulfide as Gas Cathode in a Nonaqueous Li-CO2 Battery.

Li-CO2 batteries have recently attracted attention as promising candidates for next-generation energy storage devices due to their extremely high theoretical energy density. The real application of Li-CO2 cells involves addressing several drawbacks, including high charging potential, poor coulombic efficiency, and low rechargeability. Molybdenum disulfide supported on carbon nanotubes (MoS2/CNT) with various ratios functioned as a cathode catalyst for Li-CO2 batteries. The optimal MoS2/CNT composite achieved a maximum discharge capacity of 8551 mAh g-1 with a coulombic efficiency of 96.7%. This hybrid also obtained an initial charging plateau of 3.87 V at a current density of 100 mA g-1 with a cutoff capacity of 500 mAh g-1. It provided ideal electrochemical stability of 142 cycles at the current densities of 100 mA g-1, which was comparable with that of some precious metal catalysts. This optimized MoS2/CNT was also cycled at 200 and 400 mA g-1 for 112 and 55 times, respectively. Density functional theory calculations demonstrated that the sulfided Mo-edge (s-Mo-edge) on MoS2 materials showed appropriate adsorption strengths of Li, CO2, and Li2CO3. Moreover, joint results of Raman profiles and extended X-ray absorption fine structure spectra elucidated that the catalytic efficiencies of MoS2/CNT hybrids were proportional to the quantities of exposed s-Mo-edge active sites.

Comparative Study of Li-CO2 and Na-CO2 Batteries with Ru@CNT as a Cathode Catalyst.

Alkali metal-carbon dioxide (Li/Na-CO2) batteries have generated widespread interest in the past few years owing to the attractive strategy of utilizing CO2 while still delivering high specific energy densities. Among these systems, Na-CO2 batteries are more cost effective than Li-CO2 batteries because the former uses cheaper and abundant Na. Herein, a Ru/carbon nanotube (CNT) as a cathode material was used to compare the mechanisms, stabilities, overpotentials, and energy densities of Li-CO2 and Na-CO2 batteries. The potential of Na-CO2 batteries as a viable energy storage technology was demonstrated.

Controlling Ni2+ from the Surface to the Bulk by a New Cathode Electrolyte Interphase Formation on a Ni-Rich Layered Cathode in High-Safe and High-Energy-Density Lithium-Ion Batteries.

Ni-rich high-energy-density lithium ion batteries pose great risks to safety due to internal short circuits and overcharging; they also have poor performance because of cation mixing and disordering problems. For Ni-rich layered cathodes, these factors cause gas evolution, the formation of side products, and life cycle decay. In this study, a new cathode electrolyte interphase (CEI) for Ni2+ self-oxidation is developed. By using a branched oligomer electrode additive, the new CEI is formed and prevents the reduction of Ni3+ to Ni2+ on the surface of Ni-rich layered cathode; this maintains the layered structure and the cation mixing during cycling. In addition, this new CEI ensures the stability of Ni4+ that is formed at 100% state of charge in the crystal lattice at high temperature (660 K); this prevents the rock-salt formation and the over-reduction of Ni4+ to Ni2+. These findings are obtained using in situ X-ray absorption spectroscopy, operando X-ray diffraction, operando gas chromatography-mass spectroscopy, and X-ray photoelectron spectroscopy. Transmission electron microscopy reveals that the new CEI has an elliptical shape on the material surface, which is approximately 100 nm in length and 50 nm in width, and covers selected particle surfaces. After the new CEI was formed on the surface, the Ni2+ self-oxidation gradually affects from the surface to the bulk of the material. It found that the bond energy and bond length of the Ni-O are stabilized, which dramatically inhibit gas evolution. The new CEI is successfully applied in a Ni-rich layered compound, and the 18650- and the punch-type full cells are fabricated. The energy density of the designed cells is up to 300 Wh/kg. Internal short circuit and overcharging safety tests are passed when using the standard regulations of commercial evaluation. This new CEI technology is ready and planned for future applications in electric vehicle and energy storage.