Replenishment in the Family of Rhenium Chalcobromides; Synthesis and Structure of Molecular {Re4S4}Br8(TeBr2)4, Dimeric [{Re4S4}Br8(TeBr2)3]2, and Polymeric {Re4S4}Br8 Compounds Based on the {Re4S4}8+ Tetrahedral Cluster Core.

We have obtained three new rhenium(IV) chalcobromides belonging to the homologous series {Re4S4}Br8(TeBr2)n (n = 0, 3, 4): a molecular complex {Re4S4}Br8(TeBr2)4 (1), a dimeric complex [{Re4S4}(TeBr2)3Br7(µ-Br)]2 (2), and a two-dimensional (2D) polymeric compound {Re4S4}Br8 (3). Compound 1 is isotypic to the already known {Re4Te4}(TeBr2)4Br8, while 2 and 3 exhibit a new type of binding of tetrahedral clusters via µ-Br bridges. Compounds were characterized by X-ray single-crystal diffraction, X-ray powder diffraction, and thermal and elemental analyses. In compound 2, two tetrahedral cluster cores {Re4S4}8+ are linked together forming a dimer through two Re-µ-Br-Re bridges. Calculations of the electron localization function (ELF) showed that there is no covalent interaction between rhenium atoms of neighboring clusters. In compound 3, each rhenium atom of the {Re4S4}8+ core is coordinated by three Br ligands: one terminal Br and two bridging µ-Br ligands. As a result, eight bridging bromine atoms link {Re4S4}8+ cluster cores into goffered layers. {Re4S4}Br8 is the new stable rhenium(IV) thiobromide, the first discovered in the Re-S-Br system, along with the already known octahedral rhenium(III) thiobromides Re6S4+xBr10-2x (x = 0-4).

Optical and Material Characteristics of MoS2/Cu2O Sensor for Detection of Lung Cancer Cell Types in Hydroplegia.

In this study, n-type MoS2 monolayer flakes are grown through chemical vapor deposition (CVD), and a p-type Cu2O thin film is grown via electrochemical deposition. The crystal structure of the grown MoS2 flakes is analyzed through transmission electron microscopy. The monolayer structure of the MoS2 flakes is verified with Raman spectroscopy, multiphoton excitation microscopy, atomic force microscopy, and photoluminescence (PL) measurements. After the preliminary processing of the grown MoS2 flakes, the sample is then transferred onto a Cu2O thin film to complete a p-n heterogeneous structure. Data are confirmed via scanning electron microscopy, SHG, and Raman mapping measurements. The luminous energy gap between the two materials is examined through PL measurements. Results reveal that the thickness of the single-layer MoS2 film is 0.7 nm. PL mapping shows a micro signal generated at the 627 nm wavelength, which belongs to the B2 excitons of MoS2 and tends to increase gradually when it approaches 670 nm. Finally, the biosensor is used to detect lung cancer cell types in hydroplegia significantly reducing the current busy procedures and longer waiting time for detection. The results suggest that the fabricated sensor is highly sensitive to the change in the photocurrent with the number of each cell, the linear regression of the three cell types is as high as 99%. By measuring the slope of the photocurrent, we can identify the type of cells and the number of cells.

Hexamolybdenum Clusters Supported on Exfoliated h-BN Nanosheets for Photocatalytic Water Purification.

Nowadays, the development of new effective photocatalytic materials for the purification of real wastewaters and model systems containing organic molecules constitutes an important challenge. Here we present a preparation strategy for composite materials based on hexamolybdenum cluster complexes and exfoliated hexagonal boron nitride (h-BN) nanosheets. Cluster deposition on the nanosheet surface was achieved by impregnation of the matrix by a (Bu4N)2[{Mo6I8}(NO3)6]/acetone solution. Successful cluster immobilization and chemical composition of the samples were verified by inductively coupled plasma atomic emission spectroscopy, transmission electron microscopy with elemental mapping (TEM/EDS), X-ray photoelectron spectroscopy (XPS), and optical diffuse-reflectance spectroscopy. A small amount of water in acetone initiates the hydrolysis of a molybdenum cluster precursor with labile NO3- ligands, which are absent in the final composite, according to the XPS data. Intermediate hydrolyzed cluster forms anchor to the surface of h-BN nanosheets and promote growth of the insoluble compound [{Mo6I8}(H2O)2(OH)4]·yH2O as the final hydrolysis product. TEM/EDS proves that the cluster exists at the nanosheet surface in the form of an X-ray diffraction amorphous thin film. The samples obtained show high photocatalytic activity in the degradation of a model pollutant rhodamine B under UV- and visible-light irradiation. The materials retain their initial photocatalytic efficacy during at least six cycles without the need for recovery.

Theoretical and experimental comparative study of the stability and phase transformations of sesquichalcogenides M2Q3 (M = Nb, Mo; Q = S, Se).

The extensive family of transition metal chalcogenides has been comprehensively investigated owing to their diverse useful properties. However, even among them, there are ones that have received comparatively less attention; in particular, these are molybdenum and niobium sulfides and selenides with the composition of M : Q = 2 : 3 (M = Mo, Nb; Q = S, Se). Mo or Nb chalcogenides with this stoichiometry may adopt one of two structures: (i) sesquichalcogenides M2Q3, where important structural elements are infinite metal chains, or (ii) self-intercalated compounds M1.33Q2, in which extra M atoms are inserted between MQ2 layers. Depending on the M-Q combination, in practice, either none, one, or both of them may exist. The reasons for chemical dissimilarity in the series of seemingly related compounds haven't been addressed until the present work. Here, we present the first generalized comparative study of these chalcogenides by quantum-chemical computations verified by laboratory experiments. High-temperature phases of Mo2S3 and Nb2Se3 may be stably isolated at room temperature, while "Nb2S3" and "Mo2Se3" had not been obtained, nor were they expected to exist from DFT data. The structure-determining motifs of sesquichalcogenides M2Q3 are metallic chains, and thus, apparently, if metal's electron deficiency (or excess) prevents the formation of M-M chains, then the M2Q3-type structure cannot form. If the metal has an adequate electron density and the structure does form at high temperature (as it happens for Mo2S3 and Nb2Se3), then it can be kinetically stabilized by quenching, and stored under laboratory conditions for long times. However, if Nb2Se3 is left to cool down slowly, it undergoes phase transition to iso-stoichiometric intercalate Nb1.333Se2, in good agreement with DFT predictions of the close values of their free energies. Isostructural intercalate Nb1.333S2 is found to be the only experimental product in the Nb-S system, in full accordance with DFT prediction. Effective stabilization of self-intercalated phases is provided by significant charge transfer from intercalated Nb atoms to the NbQ2 layers, as confirmed by DFT. The obtained data may serve to get insight into polymorphism of some less-studied transition metal chalcogenides and to promote their use for future functional materials.

Nano-structure ZnO/Cu2O photoelectrochemical and self-powered biosensor for esophageal cancer cell detection.

The p-n heterojunction photoelectrochemical biosensor, which comprises a p-type Cu2O film formed by electrochemical deposition and n-type ZnO nanorods formed by the hydrothermal method, is prone to photoelectrochemical reactions and self-powered. Four types of human esophageal cancer cells (ECCs) were detected by this biosensor without requiring an extra bias voltage. The measured photocurrent values of high invasion capacity cancer cells was consistently 2 times higher than those measured by a slight invasion capacity cancer cells. The response time, which was about 0.5 s, allowed repeated measurement.

Solid-state reaction as a mechanism of 1T ↔ 2H transformation in MoS2 monolayers.

Monolayers of molybdenum disulfide MoS2 are considered to be prospective materials for nanoelectronics and various catalytic processes. Since in certain conditions they undergo 1T ↔ 2H phase transitions, studying these phase changes is an urgent task. We present a DFT research of these transitions to show that they can proceed as a solid-state reaction. Two transition states were discovered with energy barriers 1.03 and 1.40 eV. Sulfur atoms in the transition states are shown to be displaced relative to molybdenum atoms so that a tendency of one structural modification to transform into the other modification is seen. This kind of displacements agrees with electron microscopy data reported earlier. The energy parameters indicate that 1T → 2H reactions are exothermic for both transition states and can possibly proceed in a self-sustained manner when initially activated by some external energy impact.

Synthesis, crystal structure, and colloidal dispersions of vanadium tetrasulfide (VS4).

Although many of the layered metal chalcogenides, such as MoS2, are well-studied, some other chalcogenides have received less attention by comparison. In particular, there has been an emerging interest in vanadium tetrasulfide (VS4), which displays useful properties as a component of hybrids. However, the synthetic methods and characteristics of individual VS4 are not yet well defined, and there is no report on its solution processability. Here we have synthesized VS4 by a simple and fast direct reaction between elements. Reinvestigation of the VS4 crystal structure yielded more precise atomic coordinates and interatomic distances, thereby confirming the crystallization of VS4 in the monoclinic C2/c group and its quasi-1D chainlike structure. As the chains in VS4 are only bonded by weak van der Waals forces, we further demonstrate that bulk VS4 may be ultrasonically dispersed in appropriate solvents to form colloids, similarly to the layered chalcogenides. VS4 particles in colloids retain their phase identity and rod-shaped morphology with lengths in the range of hundreds of nanometers. Isopropanol dispersion exhibited the highest concentration and stability, which was achieved owing to the repulsion caused by high negative charges on the edges of the particles.

The first water-soluble hexarhenium cluster complexes with a heterocyclic ligand environment: synthesis, luminescence, and biological properties.

The hexarhenium cluster complexes with benzotriazolate apical ligands [{Re6(µ3-Q)8}(BTA)6](4-) (Q = S, Se; BTA = benzotriazolate ion) were obtained by the reaction of [{Re6(µ3-Q)8}(OH)6](4-) with molten 1H-BTA (1H-benzotriazole). The clusters were crystallized as potassium salts and characterized by X-ray single-crystal diffraction, elemental analyses, and UV-vis and luminescence spectroscopy. In addition, their cellular uptake and toxicity were evaluated. It was found that both clusters exhibited luminescence with high lifetimes and quantum yield values; they were taken up by the cells illuminating them under UV irradiation and, at the same time, did not exhibit acute cytotoxic effects.

Lung cancer cells detection by a photoelectrochemical MoS2 biosensing chip.

This research aims to explore the potential application of this approach in the production of biosensor chips. The biosensor chip is utilized for the identification and examination of early-stage lung cancer cells. The findings of the optical microscope were corroborated by the field emission scanning electron microscopy, which provided further evidence that the growth of MoS2 is uniform and that there is minimal disruption in the electrode, hence minimizing the likelihood of an open circuit creation. Furthermore, the bilayer structure of the produced MoS2 has been validated through the utilization of Raman spectroscopy. A research investigation was undertaken to measure the photoelectric current generated by three various types of clinical samples containing lung cancer cells, specifically the CL1, NCI-H460, and NCI-H520 cell lines. The findings from the empirical analysis indicate that the coefficient of determination (R-Square) for the linear regression model was approximately 98%. Furthermore, the integration of a double-layer MoS2 film resulted in a significant improvement of 38% in the photocurrent, as observed in the device's performance.

Large area MoS2 thin film growth by direct sulfurization.

In this study, we present the growth of monolayer MoS2 (molybdenum disulfide) film. Mo (molybdenum) film was formed on a sapphire substrate through e-beam evaporation, and triangular MoS2 film was grown by direct sulfurization. First, the growth of MoS2 was observed under an optical microscope. The number of MoS2 layers was analyzed by Raman spectrum, atomic force microscope (AFM), and photoluminescence spectroscopy (PL) measurement. Different sapphire substrate regions have different growth conditions of MoS2. The growth of MoS2 is optimized by controlling the amount and location of precursors, adjusting the appropriate growing temperature and time, and establishing proper ventilation. Experimental results show the successful growth of a large-area single-layer MoS2 on a sapphire substrate through direct sulfurization under a suitable environment. The thickness of the MoS2 film determined by AFM measurement is about 0.73 nm. The peak difference between the Raman measurement shift of 386 and 405 cm-1 is 19.1 cm-1, and the peak of PL measurement is about 677 nm, which is converted into energy of 1.83 eV, which is the size of the direct energy gap of the MoS2 thin film. The results verify the distribution of the number of grown layers. Based on the observation of the optical microscope (OM) images, MoS2 continuously grows from a single layer of discretely distributed triangular single-crystal grains into a single-layer large-area MoS2 film. This work provides a reference for growing MoS2 in a large area. We expect to apply this structure to various heterojunctions, sensors, solar cells, and thin-film transistors.

Selective two-step oxidation of µ2-S ligands in trigonal prismatic unit {Re3(µ6-C)(µ2-S)3Re3} of the bioctahedral cluster anion [Re12CS17(CN)6]6­.

An oxidation of cluster anion [Re(12)CS(17)(CN)(6)](6-) by H(2)O(2) in water has been investigated. It was shown that selective two-step oxidation of bridging µ(2)-S-ligands in trigonal prismatic unit {Re(3)(µ(6)-C)(µ(2)-S)(3)Re(3)} takes place. The first stage runs rapidly, whereas the speed of the second stage depends on intensity of ultraviolet irradiation of the reaction mixture. Each stage of the reaction is accompanied by a change in the solution's color. In the first stage of the oxidation, the cluster anion [Re(12)CS(14)(SO(2))(3)(CN)(6)](6-) is produced, in which all bridging S-ligands are turned into bridging SO(2)-ligands. The second stage of the oxidation leads to formation of the anion [Re(12)CS(14)(SO(2))(2)(SO(3))(CN)(6)](6-), in which one of the SO(2)-ligands underwent further oxidation forming the bridging SO(3)-ligand. Seven compounds containing these anions were synthesized and characterized by a set of different methods, elemental analyses, IR and UV/vis spectroscopy, and quantum-chemical calculations. Structures of some compounds based on similar cluster anions, [Cu(NH(3))(5)](3)[Re(12)CS(14)(SO(2))(3)(CN)(6)]·9.5H(2)O, [Ni(NH(3))(6)](3)[Re(12)CS(14)(SO(2))(3)(CN)(6)]·4H(2)O, and [Cu(NH(3))(5)](2.6)[Re(12)CS(14)(SO(2))(3)(CN)(6)](0.6)[{Re(12)CS(14)(SO(2))(2)(SO(3))(CN)(5)(µ-CN)}{Cu(NH(3))(4)}](0.4)·5H(2)O, were investigated by X-ray analysis of single crystals.

Nucleus-independent chemical shifts and aromaticity in hexanuclear cluster complexes [Mo6X8]n- (X = S, Se, and Te; n = 0 and 4) of Chevrel phases.

Molecular diamagnetism and multicentered X-Mo-Mo and Mo-Mo-Mo interactions in hexanuclear cluster complexes [Mo(6)X(8)](n-) (X = S, Se, and Te; n = 0 and 4) are studied using calculations of nuclear independent chemical shifts (NICS) and the methods "atoms in molecules" and electron localization function. It is shown that [Mo(6)X(8)](4-) complexes are characterized by large negative NICSs related to the aromaticity of Mo-Mo bondings and to diatropic currents in Mo(6) metallic core of the cuboctahedral clusters. The calculated currents can participate in the mechanism of nucleation of the vortex lattice of macroscopic Abrikosov's electronic whirls responsible for the magnetic high-field stability of the superconducting currents in type II superconductors.

Growth Mechanism of Periodic-Structured MoS2 by Transmission Electron Microscopy.

Molybdenum disulfide (MoS2) was grown on a laser-processed periodic-hole sapphire substrate through chemical vapor deposition. The main purpose was to investigate the mechanism of MoS2 growth in substrate with a periodic structure. By controlling the amount and position of the precursor, adjusting the growth temperature and time, and setting the flow rate of argon gas, MoS2 grew in the region of the periodic holes. A series of various growth layer analyses of MoS2 were then confirmed by Raman spectroscopy, photoluminescence spectroscopy, and atomic force microscopy. Finally, the growth mechanism was studied by transmission electron microscopy (TEM). The experimental results show that in the appropriate environment, MoS2 can be successfully grown on substrate with periodic holes, and the number of growth layers can be determined through measurements. By observing the growth mechanism, composition analysis, and selected area electron diffraction diagram by TEM, we comprehensively understand the growth phenomenon. The results of this research can serve as a reference for the large-scale periodic growth of MoS2. The production of periodic structures by laser drilling is advantageous, as it is relatively simpler than other methods.

Characteristics of P-Type and N-Type Photoelectrochemical Biosensors: A Case Study for Esophageal Cancer Detection.

P-type and N-type photoelectrochemical (PEC) biosensors were established in the laboratory to discuss the correlation between characteristic substances and photoactive material properties through the photogenerated charge carrier transport mechanism. Four types of human esophageal cancer cells (ECCs) were analyzed without requiring additional bias voltage. Photoelectrical characteristics were examined by scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-vis reflectance spectroscopy, and photocurrent response analyses. Results showed that smaller photocurrent was measured in cases with advanced cancer stages. Glutathione (L-glutathione reduced, GSH) and Glutathione disulfide (GSSG) in cancer cells carry out redox reactions during carrier separation, which changes the photocurrent. The sensor can identify ECC stages with a certain level of photoelectrochemical response. The detection error can be optimized by adjusting the number of cells, and the detection time of about 5 min allowed repeated measurement.

Intelligent Identification of MoS2 Nanostructures with Hyperspectral Imaging by 3D-CNN.

Increasing attention has been paid to two-dimensional (2D) materials because of their superior performance and wafer-level synthesis methods. However, the large-area characterization, precision, intelligent automation, and high-efficiency detection of nanostructures for 2D materials have not yet reached an industrial level. Therefore, we use big data analysis and deep learning methods to develop a set of visible-light hyperspectral imaging technologies successfully for the automatic identification of few-layers MoS2. For the classification algorithm, we propose deep neural network, one-dimensional (1D) convolutional neural network, and three-dimensional (3D) convolutional neural network (3D-CNN) models to explore the correlation between the accuracy of model recognition and the optical characteristics of few-layers MoS2. The experimental results show that the 3D-CNN has better generalization capability than other classification models, and this model is applicable to the feature input of the spatial and spectral domains. Such a difference consists in previous versions of the present study without specific substrate, and images of different dynamic ranges on a section of the sample may be administered via the automatic shutter aperture. Therefore, adjusting the imaging quality under the same color contrast conditions is unnecessary, and the process of the conventional image is not used to achieve the maximum field of view recognition range of ~1.92 mm2. The image resolution can reach ~100 nm and the detection time is 3 min per one image.

Hydrothermal Synthesis of N-Doped Graphene for Supercapacitor Electrodes.

N-doped graphene based on graphene oxide and 3,3',4,4'-tetraaminodiphenyl oxide (TADPO) was obtained using a one-step hydrothermal process. The resulting materials were fully characterized using elemental analysis, infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis, X-ray diffraction, scanning electron micrographs, and transmission electron microscopy. The findings reveal that benzimidazole rings were formed during the reaction, and the mass content of nitrogen in the obtained material varied from 12.3% to 14.7%, depending on the initial concentration of TADPO. Owing to the redox activity of benzimidazole rings, the new N-doped graphene materials demonstrated a high specific capacitance, reaching 340 F g-1 at 0.1 A g-1, which was significantly higher than that of the sample of reduced graphene oxide obtained under similar conditions without the use of TADPO (169 F g-1 at 0.1 A g-1). The resulting material also exhibited good cyclic stability after 5000 cycles.

One-step exfoliation synthesis of easily soluble graphite and transparent conducting graphene sheets.

Easily soluble expanded graphite is synthesized in a one-step exfoliation process that can be used for the lowcost mass production of graphene for various applications because of the simplicity and speed of the process. The graphene obtained is sufficiently expanded to be dispersed in aqueous solutions with an ordinary surfactant and in organic solvents.

Unusual H-bonding in novel cyano-cluster polymeric hydrates [(H){Ln(H2O)4}{Re6S8(CN)6}]*2H2O (Ln = Yb, Lu).

X-Ray studies and (1)H NMR measurements for novel cyano-bridged polymers [(H){Ln(H(2)O)(4)}{Re(6)S(8)(CN)(6)}]*2H(2)O (Ln = Yb, Lu) reveal temperature dependence of proton localization: acid protons are trapped between nitrogen atoms at low temperatures, but can be transferred to the water sublattice at higher temperatures; this transfer resulted in intermolecular proton exchange.

Self-assembly of ambivalent organic/inorganic building blocks containing Re6 metal atom cluster: formation of a luminescent honeycomb, hollow, tubular metal-organic framework.

Reactions in a sealed glass tube between melted pyrazine (pyz) and a Cs(3)Re(6)Q(i)(7)Br(i)Br(a)(6).H(2)O inorganic rhenium cluster compound (Q = S, Se; "i" for inner and "a" for apical positions) containing [Re(6)Q(i)(7)Br(i)Br(a)(6)](3-) units led to the substitution of three apical bromine ligands by three pyrazine groups with the formation of 3 CsBr as a byproduct. The resulting fac-Re(6)Q(i)(7)Br(i)(pyz)(a)(3)Br(a)(3) building unit, based on a Re(6) metal atom cluster, is neutral and noncentrosymmetric and exhibits an ambivalent organic/inorganic nature owing to the opposite disposition of the three apical pyrazine groups versus the three apical bromine atoms. These compounds were characterized by single-crystal and powder X-ray diffraction, elemental and thermal analyses, and luminescence measurements. The crystal structure of fac-Re(6)Q(i)(7)Br(i)(pyz)(a)(3)Br(a)(3).xH(2)O (Q = S (1) and Se (2)) displays an original, neutral metal-organic framework based on the self-assembling of fac-Re(6)Q(i)(7)Br(i)(pyz)(a)(3)Br(a)(3) hybrid building units. The latter are held together by supramolecular interactions: pi-pi, hydrogen bonds (C-H...N, C-H...Br(a), and C-H...Br(i)), and van der Waals contacts. It gives rise to a honeycomb porous structure of parallel hollow open-ended channels wherein the water molecules are located. Their removal does not lead to the collapsing of the structural edifice. The channel walls are constituted by hydrogen atoms from pyrazine as well as apical bromine from the cluster unit. To our knowledge, the structures of 1 and 2 constitute with that of PTMTC (perchlorotriphenylmethyl functionalized by carboxylic group radicals) one of the rare examples of stable open frameworks stabilized by supramolecular interactions between neutral molecules. Moreover, 1 is the first example of luminescent Re(6) compound built up from a noncentrosymmetric Re(6)S(i)(7)Br(i) cluster core.

The first octahedral cluster complexes with terminal formate ligands: synthesis, structure, and properties of K4[Re6S8(HCOO)6] and Cs4[Re6S8(HCOO)6].

The hexarhenium anionic cluster complex with terminal formate ligands [Re6S8(HCOO)6]4- was obtained by the room-temperature reaction between [Re6S8(OH)6]4- and formic acid in an aqueous solution. The cluster was crystallized as a potassium or cesium salt and characterized by X-ray single-crystal diffraction and elemental analyses, IR, 1H NMR, UV/vis, and luminescence spectroscopies. In particular, the emission quantum yield of the potassium salt of the Re6 cluster anion in the solid phase was determined for the first time. The electronic structures of [Re6S8(HCOO)6]4- and [Re6S8(OH)6]4- were also elucidated by DFT calculations.