Cyclometalated complexes containing ferrocenyl Schiff base: Preparation,characterization, DFT calculations,application in cancer and biological researches and MOE studies

A series of transition metal (II/III) complexes containing organometallic Schiff base ligand (H₂L) had been synthesized and characterized by using elemental analysis (C, H, N, M), molar conductivity, IR, UV–Vis, ¹H NMR and mass spectral analysis. Also, their TG and DTG behaviors were investigated. The ligand was prepared by condensation of 4-aminosalicylic acid with 2-acetylferrocene in 1:1 M ratio. The data of elemental analysis indicated that the prepared complexes were synthesized also in a 1:1 M ratio. The ligand behaved as neutral bidentate ligand that coordinated to metal ions through protonated O-phenolic and protonated carboxylic-OH groups. All complexes had octahedral structure. DFT calculations for H₂L ligand were determined with some parameters such as HOMO-LUMO energy gab, electronegativity and chemical hardness–softness. Antimicrobial activity of both H₂L Schiff base ligand and its metal complexes was tested against different strains of bacteria and fungi species. Furthermore, all compounds had been screened for their anticancer activities against breast cancer (MCF-7) cell line. [Cu(H₂L)(H₂O)₂Cl₂]·2H₂O complex had the lowest IC₅₀ value = 47.3 µg/mL. For determining the more effective and probable binding mode between the H₂L ligand, Co(II) and Zn(II) complexes with different active sites of 4K3V, 2YLB and 3DJD receptors, so molecular docking studies were investigated.     

First germanium doped titanium disulfide polytypes: Crystal structure and metal–metal interactions

Single crystals of Ge-doped TiS₂ polytypes, 1T, (4H)₂, 12R, and their corresponding new a√3 × a√3 superstructure were grown by chemical vapor transport method. The crystals were characterized by combining X-ray diffraction and transmission electron microscopy techniques. The structures of these polytypes are all based on close packing layers of sulfur of CdI₂-type structure. Except in the 1T polytype, the germanium atoms are observed to be equally distributed over both partial and complete occupancy layers. A significant distortion of the metal–sulfur distances is observed in the superstructure polytypes, as a consequence of metal–metal corrugated layers. The 12R-a√3 × a√3 superstructure is revealed by both electron diffraction and X-ray diffraction by the presence of satellite reflections. Electron diffraction patterns from the 12R polytype show highly structured diffuse scattering surrounding the main spots. These diffuse segments, which are arranged in triangles sharing vertices, correspond to a 2a* × 2a* superstructure and are attributed to the short-range order of metal atoms in the partially filled layers.     

Synthesis,pharmacological evaluation,and molecular modeling studies of novel isatin hybrids as potential anticancer agents

A novel series of isatin hybrids 5a-g was designed, synthesized, and characterized spectroscopically. The synthesized compounds were evaluated for their cytotoxic activity against the human breast cancer cell line (MCF-7) by in vitro MTT assay. Amongst the tested compounds, 5e compound bearing benzyl moiety at N₄ piperazine was found to be the most active with the promising IC₅₀ (12.47 µM). Moreover, the active compounds 5e and 5g were subjected to antitumor evaluation (in vivo) against Dalton’s ascitic lymphoma (DAL) cell line and the results suggested that the best active compound 5e can normalize the blood picture in comparison to the standard drug. An in silico molecular docking study using the crystal structure of Hsp90 protein described the role of significant protein–ligand interactions and revealed more insights into the binding mode. The drug-likeliness of the compounds was predicted based on Lipinski's rule of five and pharmacokinetic ADME parameters. Hence, the synthesized isatin hybrids could be novel starting point anticancer lead compounds demonstrating drug-like properties which can be explored further for anticancer drug discovery.     

Production of bioactive compounds from callus of Pueraria thomsonii Benth with promising cytotoxic and antibacterial activities

For thousands of years Pueraria thomsonii Benth has been used to treat a number of diseases in traditional Chinese pharmacopeia. Despite these uses, there is still insufficient information on its biological activity and chemical composition. In this respect, the in vitro callus culture of P. thomsonii was subjected to identify anticancer and antibacterial compounds. Based on significant preliminary cytotoxicity and antibacterial activities; the chemical investigation led to the isolation of isoflavonoids, coumaric acid derivative and dihydroxyflavanone-type of compounds viz., daidzin (1), puerarin (2), biochanin A (3), daidzein (4), p-coumaric acid ethyl ester (5) and liquiritigenin (6), respectively. These compounds were tested for their cytotoxicity and antibacterial activities. Among them, p-coumaric acid ethyl ester (5) exhibited significant cytotoxicity with GI₅₀ values of 14.73, 15.64 and 20.88 μM/mL against 4T1, NC1-H1975 and A549, respectively; the other isoflavones and aflavonoid showed moderate to weak activities. Moreover, p-coumaric acid ethyl ester (5) inhibited the growth of K. pneumonia, MRSE and MRSA at very low MIC values of 6.01, 12.01 µg/mL 24.02, respectively. On the other hand compounds biochanin A (3) and liquiritigenin (6) showed moderate antibacterial activity. Because of the potential anticancer and antibacterial activities of bioactive compounds from P. thomsonii, they can be used to treat various cancer and emerging bacterial infections.     

Hydrides compounds for electrochemical applications

Hydrides have been used since a long time for solid-state hydrogen storage and electrochemical nickel-metal hydride batteries. Besides these applications, growing attention has been devoted to their development as anode materials, as well as solid electrolytes for Li-ion and other ion batteries. Herein, we review and summarize the recent advances of hydrides as negative electrodes for Ni-MH and A-ion batteries (A = Li, Na), and as electrolyte for all solid-state batteries (ASSB). Metallic hydrides such as intergrowth compounds are highlighted as the best compromise up to now for Ni-MH. Regarding anodes of Li-ion batteries, MgH₂, especially its combination with TiH₂, provides very promising results. Complex hydrides such as Li-borohydride and related closo-borates and monovalent carborate boron clusters appear to be very attractive as solid electrolytes for Li-based ASSB, whereas closo-hydroborate sodium salts and closo-carboborates are investigated for Na- and Mg-ASSB. Finally, further research directions are foreseen for hydrides in electrochemical applications.     

Chemical and pharmacological aspects of novel hetero MLB complexes derived from NO2 type Schiff base and N2 type 1,10-phenanthroline ligands

A series of hetero ligand MLB complexes (1–5) were synthesised from tridentate NO₂ type Schiff base [H₂L: (E)-2-((2-hydroxy-4-methoxyphenyl)(phenyl)methyleneamino)benzoic acid; derived from 2-hydroxy-4-methoxybenzophenone and 2-aminobenzoic acid] and bidentate N₂ type 1,10-phenanthroline (B: phen) ligands. The structural characterization of the synthesised MLB complexes were carried out via analytical as well as various spectral studies. Additionally, the low molar conductance values (Λ_m = 14–22 Ω⁻¹ cm² mol⁻¹) imply that the complexes (1–5) are non-electrolytes. The obtained results reinforce that stoichiometry of the mononuclear hetero ligand complexes can be represented as [M(II)-Schiff base(L)-phen(B)·H₂O] and both H₂L and (B) ligands can act as tri and bidentates respectively. Moreover, both the ligands bind with metal(II) ions to build a stable six, six, five membered chelate rings with octahedral geometry. The existing solvent water molecule is confirmed from thermal as well as vibrational analysis. Their microcrystalline nature and uniform surface morphology were confirmed by both powder XRD and SEM studies. 3D molecular modeling and analysis of NiLB and CuLB complexes (3 and 4) were also studied. Mn(II), Ni(II) and Cu(II) complexes (1, 3 and 4) strongly interact with DNA through intercalation binding with strong binding constant values. The obtained K_app values were 5.23, 4.98, 6.36, 7.21 and 4.86 × 10⁵ mol⁻¹ for MLB complexes (1–5) respectively and the negative Δ³G values shown that all the complexes are strongly interact with DNA in a spontaneous manner. Further, remarkable biological, antioxidant and DNA activities were remarkably exhibited by MnLB, NiLB and CuLB complexes.     

Water oxidation with inhomogeneous metal-silicon interfaces

Silicon (Si) is a prime candidate for manufacturing water-splitting photoelectrochemical cells, however, the stability of this material remains a serious bottleneck. This is particularly true for the photoanode, subject to severe deactivation mechanisms. So far, thin film homogeneity has been the paradigm in the quest for stable and efficient Si-based photoanodes, which involved the use of vapor deposition methods to produce conformal thin films ensuring Si protection and efficient catalysis during operation. Conversely, recent reports on n-Si/metal thin film junctions have highlighted the benefits of the junction heterogeneity, generated in situ. In addition, results obtained from n-Si photoanodes partially covered with discontinuous films of Co and Ni nanoparticles lately suggested that homogeneity is not a prerequisite to reach efficiency and stability. Such findings may open new protection routes for Si-based photoanodes, breaking with classical strategies and allowing the use of liquid phase modification methods such as electrodeposition.     

Photocatalytic remediation of persistent organic pollutants (POPs): A review

The release of persistent organic pollutants (POPs) into the environment is an issue of global concern, as the chemicals are stable over a prolonged period resulting in their accumulation in many animals and plants. Although POPs are banned in several countries, many chemicals have been proposed as POP candidates to be added to the existing compounds as defined by the United Nations Stockholm Convention committee. To address the safe disposal and clean-up of such chemicals, new, and especially cost-effective, remediation technologies for POPs are urgently required. This review focuses on existing POPs and the types of remediation processes available for their removal. Particular attention is paid towards photocatalysis using nanocatalysts in this review, due to their effectiveness towards POP degradation, technological feasibility, and energy and cost-efficiency. The underlying principles and the key mechanisms of the photocatalysts based on TiO₂ based materials, metal oxides, light-assisted Fenton systems, framework materials e.g. metal-organic frameworks and polyoxometalates, including metal-free and hybrid photocatalysts for POPs cleanup are described for advance applications in solving the POPs contamination in the environment. The improvements of photocatalytic performance especially the POPs removal mechanism using the conventional and modified process, the design and optimization of photoreactors, and the integration technology are the critical challenges for the emerging pollutants and require intensive research for the forthcoming future.     

Transition metal dichalcogenide thin films for solar hydrogen production

In the last three decades, transition metal dichalcogenides (TMDs) have been extensively studied for electronic, photonic, and energy applications. Different efforts are directed to find a holy grail of efficient and economically feasible materials that could be simple in production and available on a large scale. The interest in TMDs (MoS₂, WS₂, MoSe₂, WSe₂) stems from their suitable electronic structure for efficient solar light absorption and simple exfoliation technique of 2D crystallites due to the van der Waals bonding of these materials. This led to various designs and combinations of 2D single layers that could form heterojunctions and multijunctions for efficient light absorption, charge carrier generation/separation, and its transfer in optoelectronic and energy harvesting devices. Herein, TMD thin films are reviewed as photoelectrodes for solar hydrogen evolution and compared to that of other more developed materials.     

Bioelectrodes for evaluating molecular therapeutic and toxicity properties

Recent progress on material designs merged with nanotechnology and biotechnology strategies has advanced studies of complex biological samples on electrodes for cytochrome P450 (CYP)–driven biocatalytic reactions (e.g. liver membrane fractions, cells, and various organ-specific CYP extracts). In addition, protein engineering of CYP enzymes with their reductase partner in membranes (e.g. baculovirus- or Escherichia coli bacteria–expressed CYP microsomes) and other recombinant strategies (e.g. engineered CYP and reductase fusion domains and site-directed CYP mutagenesis) are promising sustainable approaches for offering abundant sources of CYP enzymes for electrocatalytic applications. The combination of in silico and experimental electroanalytical methods with hyphenated approaches and biological assays can offer early and rigorous profiling of new drugs and specialty chemicals for safe exposure and beneficial use.     

Antimycobacterial and anticancer activity of newly designed cinnamic acid hydrazides with favorable toxicity profile

A series of twelve novel hybrids of cinnamic acid and thiocarbohydrazones were designed, synthesized in high yield using a simple coupling strategy via acid chlorides, and evaluated for their impact against Mycobacterium tuberculosis (Mtb) and cancer cells survival. Among them, compound 3 demonstrated strong anti-Mtb activity by reducing bacilli survival for>90 % in all three treated Mtb isolates, whereas isoniazid and rifampicin did not. Moreover, compound 3 didn’t affect vitality of HepG-2 cells, implying on advantageous hepatotoxicity profile compared to current therapeutic options for tuberculosis. Compounds 2a and 3b displayed as strong inducers of apoptosis in A549 cells, both activating intrinsic caspase pathway and cell cycle arrest at the G0/G1 phase. Subsequent analyses disclosed differences in their activities, where 3b has ability to induce production of mitochondrial superoxide anions, while 2a significantly inhibited cellular mobility. More importantly, 3b considerably affected viability of HepG-2 and HaCaT cells, whereas 2a had moderate impact only on the later. Molecular modeling studies indicated high permeability and good absorption through the human intestine, and moderate aqueous solubility with poor blood–brain barrier permeability. In summary, our results reveal that novel compounds 3 and 2a represent promising agents for tuberculosis and cancer treatment, respectively, indicating that further investigation needs to be performed to clarify the mechanisms of their anti-Mtb and anticancer activity.     

Photocatalytic and antifouling properties of TiO2-based photocatalytic membranes

Photocatalysis has been extensively studied due to its potential ability to avoid the excessive use of chemical reagents and reduce the energy consumption by employing solar energy. Moreover, to alleviate the reduction in the membrane permeation selectivity, separation efficiency, and membrane service life caused by the emerging micro-pollutants and membrane fouling, membrane technology is often coupled with microbial, electrochemical, and catalytic processes. However, although physical/chemical cleaning and membrane module replacement can overcome the inherent limitations caused by membrane fouling and other membrane separation processes, high operating costs limit their practical applications. In this review, common preparation methods for TiO₂ photocatalytic membranes are described in detail, and the main approaches to enhancing their photocatalytic performance are discussed. More importantly, the mechanism of the TiO₂ photocatalytic membrane antifouling process is elucidated, and some applications of photocatalytic membranes in other areas are described. This review systematically outlines future research directions in the field of photocatalytic membrane modification, including metal and non-metal doping, fabrication of heterojunction structures, control over reaction conditions, increase in hydrophilicity, and increase in membrane porosity.     

Traditional uses,phytochemistry, pharmacology and other potential applications of Vitellaria paradoxa Gaertn. (Sapotaceae): A review

Vitellaria paradoxa Gaertn. is a multipurpose medicinal plant of the family Sapotaceae, and it has been widely used usually in the clinical traditional medicine as remedy for a wide range of diseases for several decades. In addition, the plant has also found applications in confectionery, cosmetics and soaps, and pharmaceuticals both locally and internationally. V. paradoxa, which has been identified with >150 phytoconstituents, is rich in oleanane-type triterpene acids and glycosides, such as paradoxosides A-E, tieghemelin A, parkiosides A-C, bassic acid, as well as flavonoids such as quercetin and catechin-type compounds. The extracts and the active constituents of V. paradoxa have been investigated for various pharmacological activities, including but not limited to anticancer, melanogenesis-inhibitory, antibacterial, anti-diabetic, antioxidant, anti-inflammatory, anti-diarrhoeal, and antifungal activities. Additionally, V. paradoxa has also been utilized in nanoparticles (NPs) synthesis. These NPs among other things have shown significant antinociceptive and antiedematogenic activities as well as environmental friendly adsorptive properties for the removal of pollutants from pharmaceutical effluents. Overall, this review comprehensively examines the traditional uses, phytochemistry, pharmacology, toxicology, clinical studies, and nanoparticles synthesized from V. paradoxa and their applications.     

Microwave-assisted extraction of high-molecular-weight hemicelluloses from spruce wood

Microwave-assisted extraction (MAE) at atmospheric pressure has been demonstrated as an efficient technology for the extraction of polymeric hemicelluloses from spruce sawdust. This technology was shown to be more efficient than conventional extraction. MAE leads to a high solubilization of wood and a selective extraction of hemicellulose polymers with high molecular weights. To optimize MAE, different treatment powers (125–573 W) of presoaked spruce sawdust in water and 1 M sodium hydroxide solution for a period of 60 min were tested. The yield of hemicellulose extraction increased with the microwave power in both mediums, but with a clear advantage for presoaked samples in basic medium. The characterization of extracted hemicelluloses has shown high extraction selectivity depending on the medium of impregnation of sawdust before MAE: High-molecular-mass acetylated galactoglucomannans (M_w ∼ 41 kDa) were isolated after presoaking in water and higher molecular mass arabinoglucoronoxylans (M_w ∼ 66 kDa) in basic medium.     

Synthesis,antifungal activity and in vitro mechanism of novel 1-substituted-5-trifluoromethyl-1H-pyrazole-4-carboxamide derivatives

Inspired by the wide application of amides in plant pathogens, a series of novel 1-substituted-5-trifluoromethyl?1H?pyrazole-4-carboxamide derivatives were designed and synthesized. Bioassay results indicated that some target compounds exhibited excellent and broad-spectrum in vitro and certain in vivo antifungal activities. Among them, the in vitro EC₅₀ values of Y₁₃ against G. zeae, B. dothidea, F. prolifeatum and F. oxysporum were 13.1, 14.4, 13.3 and 21.4 mg/L, respectively. The in vivo protective activity of Y₁₃ against G. zeae at 100 mg/L was 50.65%. SAR analysis revealed that the phenyl on the 1-position of the pyrazole ring was important for this activity. An antifungal mechanism study of Y₁₃ against G. zeae demonstrated that this compound may disrupt the cell membrane of mycelium, thus inhibiting the growth of fungi. These mechanistic study results were inconsistent with those for traditional amides and may provide a novel view for deep study of this series of pyrazole carboxamide derivatives.     

Developments on carbon dioxide reduction: Their promise,achievements, and challenges

CO₂ reduction processes continue to be developed for electrosynthesis, energy storage applications, and environmental remediation. A number of promising materials have shown high activity and selectivity to target reduction products. However, the progress has been mainly at a small laboratory scale, and the technical challenges of large scale CO₂ reduction have not been considered adequately. This review covers recent advancements in catalyst materials and cell designs. The leading materials for CO₂ reduction to a number of useful products are presented with their corresponding cell and reactor designs. The latest efforts to progress to industrially relevant scales are discussed, along with the challenges that must be met for carbon dioxide reduction to be a viable route for mass scale production.     

Eco-friendly synthesis of size-controlled silver nanoparticles by using Areca catechu nut aqueous extract and investigation of their potent antioxidant and anti-bacterial activities

Silver nanoparticles (AgNPs) have attracted considerable attention owing to their unique biological applications. AgNPs synthesized by plant extract is considered as a convenient, efficient and eco-friendly material. In this work, the aqueous extract of Areca catechu L. nut (ACN) was used as the reducing and capping agents for one-pot synthesis of AgNPs, and their antioxidant and antibacterial activities were investigated. UV (Ultra Violet)-visible spectrum and dynamic light scattering (DLS) analysis revealed that the size of AgNPs was sensitive to the synthesis conditions. The synthesized AgNPs were composed of well-dispersed particles with an small size of about 10 nm under the optimal conditions (pH value of extract was 12.0; AgNO₃ concentration was 1.0 mM; reaction time was 90 min). In addition, scanning electron microscope with energy dispersive X-ray (SEM-EDX), transmission electron microscopy (TEM) and X-ray diffraction (XRD) results further verified that the synthesized AgNPs had a stable and well-dispersed form (Zeta potential value of ?30.50 mV and polydispersity index of 0.328) and a regular spherical shape (average size of 15–20 nm). In addition, Fourier transform infrared spectrometry (FTIR) results revealed that phytochemical constituents in ACN aqueous extract accounted for Ag⁺ ion reduction, capping and stabilization of AgNPs. The possible reductants in the aqueous extract of Areca catechu L. nut were identified by high-performance liquid chromatography-electrospray ionization-quadrupole-time of flight-mass spectrometry (HPLC-ESI-qTOF/MS) method. More importantly, the synthesized AgNPs indicated excellent free radical scavenging activity of 1,1-diphenyl-2-picrylhydrazyl (DPPH, IC₅₀ = 11.75 ± 0.29 μg/mL) and 2,2-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS⁺, IC₅₀ = 44.85 ± 0.37 μg/mL), which were significant higher than that of ascorbic acid. Moreover, AgNPs exhibited an enhanced antibacterial activity against six selected common pathogens (especially Escherichia coli and Staphylococcus aureus) compared with AgNO₃ solution. In a short, this study showed that the Areca catechu L. nut aqueous extract could be applied for eco-friendly synthesis of AgNPs.     

An ultrasensitive electrochemical immunosensor for CA72-4 based on a signal amplification strategy of MoS2 nanoflower-supported Au nanoparticles

Accurate detection of cancer antigen 72-4 (CA72-4), a tumor-associated glycoprotein, is of great significance for gastric cancer diagnosis and immunotherapy monitoring. Modification of noble metal nanoparticles on transition metal dichalcogenides can significantly enhance functions, such as electron transport. Molybdenum disulfide gold nanoparticles nanocomposites (MoS₂-Au NPs) were prepared in this study and a series of characterization studies were carried out. In addition, a label-free, highly sensitive electrochemical immunosensor molybdenum disulfide -Au nanoparticles/Glassy carbon electrode (MoS₂-Au NPs/GCE) was also prepared and used for the detection of CA72-4. The electrochemical performance of the immunosensor was characterized by electrochemical techniques, such as cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). The results indicated that better MoS₂-Au NPs nanomaterials have been synthesized, and the prepared electrochemical immunosensor, MoS₂-Au NPs/GCE, showed excellent electrochemical performance. The sensor exhibited high detection sensitivity under optimal conditions, including an incubation time of 30 min, an incubation temperature of 25 °C, and a pH of 7.0. The electrochemical immunosensor also had a low detection limit of 2.0 × 10^?5 U/mL (S/N = 3) in a concentration range of 0.001–200 U/mL, with good selectivity, stability, and repeatability. In conclusion, this study provided a theoretical basis for the highly sensitive detection of tumor markers in clinical biological samples.     

Synthesis,anticancer activity and docking studies of pyrazoline and pyrimidine derivatives as potential epidermal growth factor receptor (EGFR) inhibitors

A search for anticancer agents has prompted the design and synthesis of new chalcone, pyrazoline and pyrimidine derivatives as potential epidermal growth factor receptor (EGFR) kinase inhibitors. These derivatives’ binding affinities were predicted by AutoDock, which showed that chalcone, pyrazoline and pyrimidine derivatives as EGFR-kinase inhibitors have good binding energies, ranging from ?10.91 to ?7.32 kcal/mol. These compounds were synthesized and characterized using elemental analysis (CHN analysis) and spectroscopic techniques (FTIR and NMR). Among the pyrazoline derivatives, 4Aiii has revealed a superior in vitro activity, inhibiting the EGFR kinase even at a low concentration of 0.19 μM compared to the pyrimidine derivative, 5Bii. In contrast, the cytotoxic effect of these derivatives was studied against hormonal and non-hormonal breast cancer cell lines. Most of the pyrazoline derivatives were able to express their cytotoxic effect efficiently against hormonal breast cancer but only one pyrimidine derivative managed to express its activity against hormonal breast cancer.     

Choline chloride – Urea deep eutectic solvent an efficient media for the preparation of metal nanoparticles

Metal nanoparticles are nanosized structures that have different potential applications in biological, chemical, medical, and agricultural fields because of their exotic characteristics. Their size ranges from 1 to 100 nm. Metal nanoparticles are either purer forms of metals (eg: Gold, Silver, Copper, Iron, etc.) or their compounds (eg: sulfides, hydroxides, oxides, etc.). Ionic liquids are generally used in the extraction of nanoparticles but they are challenging because of their indigent bio-degradability, bio-compatibility, and sustainability. So Deep Eutectic Solvent (DES) is reported as an alternative to ionic liquids in the formation of nanoparticles. The DESs are a complex of quaternary ammonium salts and hydrogen donors or metal salt. DESs contain higher non-symmetric ions which have lower lattice energy and hence they have a lower melting point. This research utilizes a novel DES (choline chloride – urea) as an effective solvent to produce mercuric sulfide (HgS), zirconium oxide (ZrO), manganese oxide (MnO), and copper oxide (CuO) nanoparticles. As a result, the production of these metal nanoparticles using Choline Chloride (C₅H₁₄ClNO) – Urea DES can be treated as a promising way in chemical manufacturing. The nanoparticles have been analyzed using Ultra Violet Spectroscopy, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FT-IR), X-Ray Diffraction (XRD) and Energy Dispersive X-Ray Analysis (EDAX).