Theoretical calculations and experimental verification of carbon dioxide reduction electrocatalyzed by metalloporphyrin.

Metal-functionalized porphyrin-like graphene structures are promising electrocatalysts for carbon dioxide reduction reaction (CO2RR) as their metal centers can modulate activity. Yet, the role of metal center of metalloporphyrins (MTPPs) in CO2 reaction activity is still lacking deep understanding. Here, CO2RR mechanism on MTPPs with five different metal centers (M = Fe, Co, Cu, Zn and Ni) are examined by first-principles calculations. The *COOH formation is the rate determined step on the five MTPP structures, and the CoTPP exhibits the best CO2RR activity while ZnTPP and NiTPP are the worst, which is also verified by our experiment. The CO2RR activity is controlled by adsorption states of intermediates (*CO, *COOH), i.e., chemisorption (e.g., on CoTPP) and physisorption (on ZnTPP and NiTPP) of intermediates will lead to good and poor activity, respectively. The deeper the d-band center of the porphyrin ring complexed metal atom, the weaker bonding of MTPP with CO and COOH. Theoretical calculations and experimental results indicate that MTPPs with Co and Fe centers lead to a reduction in the energy barriers for the two uphill reaction steps in the electrocatalytic CO2 reduction process, thereby enhancing CO2 reduction electrocatalytic activity. Faradaic efficiency of CO is correlated with the reaction energy barrier of the first proton-coupled electron reduction process, displaying a strong linear correlation. This work provides a fundamental understanding of MTPPs used as electrocatalysts for CO2RR.

How spin state and oxidation number of transition metal atoms determine molecular adsorption: a first-principles case study for NH3.

Understanding how the electronic state of transition metal atoms can influence molecular adsorption on a substrate is of great importance for many applications. Choosing NH3 as a model molecule, its adsorption behavior on defected SnS2 monolayers is investigated. The number of valence electrons n is controlled by decorating the monolayer with different transition metal atoms, ranging from Sc to Zn. Density-Functional Theory based calculations show that the adsorption energy of NH3 molecules oscillates with n and shows a clear odd-even pattern. There is also a mirror symmetry of the adsorption energies for large and low electron numbers. This unique behavior is mainly governed by the oxidation state of the TM ions. We trace back the observed trends of the adsorption energy to the orbital symmetries and ligand effects which affect the interaction between the 3σ orbitals (NH3) and the 3d orbitals of the transition metals. This result unravels the role which the spin state of TM ions plays in different crystal fields for the adsorption behavior of molecules. This new understanding of the role of the electronic structure on molecular adsorption can be useful for the design of high efficiency nanodevices in areas such as sensing and photocatalysis.

High-Performance Hydrogen Evolution Reaction Catalytic Electrodes by Liquid Joule-Heating Growth.

Despite the great progress in the research of integrated catalytic electrodes for hydrogen evolution reaction, the efficient preparation of high-performance catalytic electrodes with high current density remains a challenging issue. In this work, a metal (Pt)-amorphous oxide (NiO) heterostructure catalyst is successfully in situ grown on nickel foam using liquid Joule-heating. Based on the superhydrophilic surface of the electrode and its superior mechanical and chemical stability, the catalytic electrode exhibits excellent catalytic performance in alkaline electrolytes with only 100 mV overpotential to achieve 5000 mA cm-2 current density and maintains a stable performance of 500 h under a fixed current density of 1000 mA cm-2 . Further verification of the practical application of the Pt@NiO-Ni electrode in the alkaline electrolyzer is conducted. The results show that the alkaline water electrolyzer with NiFe layered double hydroxide as the anode and Pt@NiO-Ni as the cathode exhibits superior performance than the previously reported electrolyzers, with a current density of 1 A cm-2 already achieved at 1.75 V, which is even comparable to some anion exchange membrane water electrolyzers. These experimental results illustrate the strong applicability of Pt@NiO-Ni electrode at industrial scale current densities.

The unique photoelectronic properties of the two-dimensional Janus MoSSe/WSSe superlattice: a first-principles study.

Designing photocatalysts with suitable band alignment and considerable carrier mobility is extremely important. Here, by means of first-principles calculation, we systematically investigated the structural, photoelectronic, and carrier mobility behavior of the two-dimensional Janus MoSSe/WSSe superlattice. The results show that both armchair-type (AN-SL) and zigzag-type (ZN-SL) superlattices are relatively stable with negative Ef values in the range of -2.35 to -1.16 eV. Band gap and band edge position calculations demonstrate that these superlattices are completely suitable for water splitting by visible light. Particularly, the interface contact of the superlattice can be spontaneously changed from type-I to type-II when N > 4, facilitating separation of photogenerated carriers. Furthermore, the hole carrier mobility (µh) in AN-SL can be effectively regulated from 1200 to 2200 cm2 V-1 s-1, much larger than that of the isolated components. Interestingly, the disparity of hole/electron carrier mobility is remarkably large with an approximately 20-fold difference, showing the potential in prohibiting the recombination of photogenerated carriers. This unique behavior is further illustrated by the relaxation times of carriers, where the lifetime of hole carriers is about 7 times larger than that of electron carriers. These findings suggest that forming a Janus superlattice is a promising approach for regulating the photoelectronic properties of semiconductors, providing a promising way to design high efficiency photocatalysts.

Network Pharmacology and Molecular Docking Analysis Explores the Mechanisms of Cordyceps sinensis in the Treatment of Oral Lichen Planus.

Objective: Oral lichen planus (OLP) is the most common potentially malignant disorder of the oral cavity. This study aimed to investigate the mechanism of action of Cordyceps sinensis in the treatment of OLP and provides a theoretical support for improving current treatment regimens for OLP. Methods: The active components and therapeutic targets of Cordyceps sinensis were predicted and screened using the TCMSP, SymMap, PubMed, HIT 2.0, and PharmMapper databases, while the relevant OLP targets were predicted and screened using the DisGeNET and GeneCards databases. Protein-protein interactions (PPI) were examined using the String database, and Cytoscape was used to combine and illustrate the findings. GO and KEGG pathway enrichment analyses were carried out using RStudio, and AutoDock Vina and Pymol were used for molecular docking and visualization, respectively. Results: A total of 404 potential target genes were discovered after evaluating 21 active compounds from Cordyceps sinensis. Potential therapeutic targets included 67 targets that matched and overlapped with OLP, including TNF, IL-6, CD4, EGFR, and IL1B. Key targets were predominantly engaged in the PI3K-Akt signaling pathway and the MAPK signaling pathway, according to the GO and KEGG analyses. These targets have a connection to biological processes including apoptosis signaling pathway regulation, T cell activation, and oxidative stress response. The molecular docking results showed that TNF, IL-6, CD4, EGFR, and IL1B could bind to their corresponding active components. Conclusions: Cordyceps sinensis contains multiple components and acts on multiple targets and multiple pathways. Particularly, Cordyceps sinensis targets TNF, IL-6, CD4, EGFR, and IL1B, regulates PI3K-Akt and MAPK signaling pathways, as well as takes part in biological processes including apoptosis, T cell activation, and oxidative stress. Cordyceps sinensis could be a crucial choice in the therapy of OLP.

Crucial Role of Crystal Field on Determining the Evolution Process of Janus MoSSe Monolayer: A First-Principles Study.

Two-dimensional Janus MXY materials have been successfully synthesized from their parent species by CVD, SEAR, or PLD techniques. However, their detailed evolution process and underlying atomistic mechanism are far from understood conclusively, which are prompts for further research. Here, taking Janus MoSSe as a representation, the evolution process from MoS2 is systematically investigated by first-principles calculation. The simulation shows that the lowest formation energy of MoS(2-δ)Seδ increases with selenylation ratio δ. Unexpectedly, Se atoms prefer to form a pair in next-nearest neighboring state (Se-NN-Se), eventually transferred into a growth rule of (6n + 1) during the evolution process. Particularly, it is demonstrated that the stability of the intermediate is mainly governed by the Mo 4d orbitals in different distorted triangular crystal fields, rendering a different degree of orbital splitting. Both the occupied and unoccupied Mo 4d orbitals of Se-NN-Se are farther from the Fermi level than other cases, which is clearly illustrated by d-band center theory. These findings will be helpful to understand the evolution process and the underlying atomistic mechanism of Janus MXY.

The role of permanent and induced electrostatic dipole moments for Schottky barriers in Janus MXY/graphene heterostructures: a first-principles study.

The Schottky barrier height (ESBH) is a crucial factor in determining the transport properties of semiconductor materials and it directly regulates the carrier mobility in opto-electronics devices. In principle, van der Waals (vdW) Janus heterostructures offer an appealing avenue for controlling the ESBH. However, the underlying atomistic mechanisms are far from understood conclusively, which prompts further research in the topic. To this end, here we carry out an extensive first-principles study of the electronic properties and ESHB of several vdW Janus MXY/graphene (M = Mo, W; X, Y = S, Se, Te) heterostructures. The results of the simulations show that by changing the composition and geometry of the heterostructure's interface, it is possible to control its electrical contact, and thence electron transport properties, from ohmic to Schottky with up to a factor seven variation in the ESBH. Detailed analysis of the simulations enables rationalization of this highly attractive property on the basis of the interplay between the permanent dipole moment of the Janus MXY sheet and the induced one due to interfacial charge redistribution at the MXY/Gr interface. Such an interplay is shown to be highly effective in altering the electrostatic potential difference across the vdW Janus heterostructure, determining its ESBH, and thence Schottky (ohmic) contact type. These computational findings contribute guidelines to control the electrical contacts in Janus heterostructures towards the rational design of electrical contacts in nanoscale devices.

Which Is Better for Hydrogen Evolution on Metal@MoS2 Heterostructures from a Theoretical Perspective: Single Atom or Monolayer?

Single atom (SA)- and monolayer (ML)-supported catalysts are two main technical routines to increase electrochemical catalytic performance and reduce cost. To date, it is still a debate which one is better for catalysis in experiments as both routines face a puzzling problem of searching for balance between stability and catalytic activity. Here, hydrogen evolution on two-dimensional 2H-MoS2 with SA- and ML-adsorbed metal atoms (23 kinds in total) is taken as an example to solve this question by first-principles calculations. The thermodynamic stability during synthesis, in vacuum, and in electrochemical reaction conditions is determined to access the stability of MoS2 loaded with single (MS@MoS2) and monolayer metal atoms (MM@MoS2). The realistic catalytic surfaces determined by surface Pourbaix diagrams, the free energy changes of hydrogen atoms at different coverages, and the exchange current densities are applied to determine hydrogen evolution reaction (HER) activity. The results show that all MM@MoS2 are much more stable than the corresponding MS@MoS2 as the metal-metal interaction in MLs could make the former structures more stable. In general, MM@MoS2 show higher hydrogen evolution activities than those of MS@MoS2. In detail, the exchange current densities of MoS2 loaded by Pd ML and Au ML are 6.208, and 1.109 mA/cm-2, respectively, which are comparable to Pt(111). Combining with small binding energies, the Pd and Au MLs are the most promising catalysts for hydrogen evolution. The purpose of this work is to highlight the advantages and disadvantages of SA- and ML-supported surfaces as HER catalysts and provide a fundamental standard for studying them.

Metabolomics based plasma biomarkers for diagnosis of oral squamous cell carcinoma and oral erosive lichen planus.

Backgrounds: To identify diagnostic biomarkers for differentiating oral squamous cell carcinoma (OSCC) from oral erosive lichen planus (OELP) and investigate potential biomarkers associated with malignant transformation. Methods: In this study, 72 patients with OSCC, 75 patients with OELP subjects were recruited. Their plasma samples were analyzed by ultra-high-performance liquid chromatography quadrupole-Orbitrap high-resolution accurate mass spectrometry, (UHPLC/Q-Orbitrap HRMS). Principal component analysis, orthogonal partial least square discrimination analysis, t-test analysis and false discovery rate were used to identify different metabolites in patients with OSCC and OELP. The metabolic pathway analysis was performed by MetaboAnalyst. To further screen and identify the biomarkers of OSCC and establish a diagnostic panel, binary logistic regression analysis and receiver operating characteristic analysis were used. The data were then combined with blood samples from healthy individuals for mass spectrometry analysis to obtain biomarkers related to malignant transformation. Results: A total of 20 kinds of endogenous metabolites were identified from plasma samples of OSCC patients and OELP patients. Metabolic pathway analysis showed that the biomarkers associated with OSCC were closely related to cholic acid metabolism and amino acid metabolism. Finally, a diagnostic panel composed of decanoylcarnitine, cysteine and cholic acid was established. This diagnostic panel had good diagnostic efficiency with the AUC=0.998. Other metabolites including uridine, taurine, glutamate, citric acid and LysoPC(18:1) were identified to be general biomarkers for malignant transformation of OELP. Conclusion: Biomarkers based on plasma metabolomics are of great significance for the prediction of malignant transformation of OELP and early diagnosis of OSCC.

The unique carrier mobility of monolayer Janus MoSSe nanoribbons: a first-principles study.

Charge-carrier mobility is a determining factor of the transport properties of semiconductor materials and is strongly related to the optoelectronic performance of nanoscale devices. Here, we investigate the electronic properties and charge carrier mobility of monolayer Janus MoSSe nanoribbons by means of first-principles simulations coupled with deformation potential theory. These simulations indicate that zigzag nanoribbons are metallic. Conversely, armchair nanoribbons are semiconducting and show oscillations in the calculated band gap as a function of edge-width according to the 3p < 3p + 1 < 3p + 2 rule, with p being the integer number of repeat units along the non-periodic direction of the nanoribbon. Although the charge-carrier mobility of armchair nanoribbons oscillates with the edge-width, its magnitude is comparable to its two-dimensional sheet counterpart. A robust room-temperature carrier mobility is calculated for 3.5 nm armchair nanoribbons with values ranging from 50 cm2 V-1 s-1 to 250 cm2 V-1 s-1 for electrons (e) and holes (h), respectively. A comparison of these values with the results for periodic flat sheet (e: 73.8 cm2 V-1 s-1; h: 157.2 cm2 V-1 s-1) reveals enhanced (suppressed) hole (electron) mobility in the Janus MoSSe nanoribbons. This is in contrast to what was previously found for MoS2 nanoribbons, namely larger mobility for electrons in comparison with holes. These differences are rationalized on the basis of the different structures, edge electronic states and deformation potentials present in the MoSSe nanoribbons. The present results provide the guidelines for the structural and electronic engineering of MoSSe nanoribbon edges towards tailored electron transport properties.

Effects of periodontitis on postoperative pneumonia in patients with lung and esophageal cancer.

BACKGROUND: Few studies have been conducted on the relationship between chronic periodontitis and postoperative pneumonia (POP) in patients with lung and esophageal cancer. Furthermore, it remains controversial as to whether improving the periodontal condition of patients with lung and esophageal cancer before surgery reduces the incidence of POP. This retrospective study was conducted to assess the effects of periodontal therapy in patients with lung and esophageal cancer to prevent POP. METHODS: A total of 265 patients with lung or esophageal cancer complicated with chronic periodontitis who underwent open thoracotomy between July 2015 and June 2019 were selected and given the choice of being in the experimental or control group. A total of 141 participants in the experimental group received periodontal therapy, and 124 participants in the control group did not receive periodontal therapy. All clinical data of participants in both groups were retrospectively studied to determine the incidence of POP on the 30th day after discharge from hospital. RESULTS: Eight patients in the experimental and six in the control group, respectively, were excluded from the study. It was found that four of the 133 patients suffered from POP in the experimental group (incidence: 3.01%). A total of 18 of 118 patients in the control group had a pulmonary infection (incidence: 15.25%). POP incidence in the experimental group was significantly lower than that in the control group, and in the level analysis of different types of periodontitis, surgical methods, and diseases (p < 0.05). CONCLUSIONS: Periodontal treatment is associated with a lower incidence of POP following lung and esophageal cancer surgery. Improving the periodontal condition of patients helps prevent POP. The presence of periodontitis is an important predisposing factor for POP in patients after open thoracotomy. Periodontal examination and therapy are recommended before the surgical treatment of lung or esophageal cancer.

Polycrystalline Few-Layer Graphene as a Durable Anticorrosion Film for Copper.

Corrosion of metals in atmospheric environments is a worldwide problem in industry and daily life. Traditional anticorrosion methods including sacrificial anodes or protective coatings have performance limitations. Here, we report atomically thin, polycrystalline few-layer graphene (FLG) grown by chemical vapor deposition as a long-term protective coating film for copper (Cu). A six-year old, FLG-protected Cu is visually shiny and detailed material characterizations capture no sign of oxidation. The success of the durable anticorrosion film depends on the misalignment of grain boundaries between adjacent graphene layers. Theoretical calculations further found that corrosive molecules always encounter extremely high energy barrier when diffusing through the FLG layers. Therefore, the FLG is able to prevent the corrosive molecules from reaching the underlying Cu surface. This work highlights the interesting structures of polycrystalline FLG and sheds insight into the atomically thin coatings for various applications.

Activity and selectivity of CO2 photoreduction on catalytic materials.

Photoreduction of molecular CO2 by solar light into added-value fuels or chemical feedstocks is an appealing strategy to simultaneously overcome environmental problems and energy challenges. However, multiple reaction steps and a large number of possible products have significantly hindered the development of highly selective catalysts capable of delivering CO2 conversion with high efficiency. Recently, several strategies associated with different conversion mechanisms have been proposed to improve the activity and product selectivity of CO2 photocatalysts. These are based on development of low dimensional nanomaterials, defect or facet engineering, design of tailored heterostructures, and carrier conductivity enhancement. In spite of impressive progress in the field, real-world applications are yet to be delivered. To sustain further research in this promising field, here we provide a short frontier of recent advances in activity and selectivity of CO2 reduction photocatalysts, together with a critical discussion of further avenues of research in this field.

Effect of oral plaque control on postoperative pneumonia following lung cancer surgery.

BACKGROUND: There have been few studies on the relationship between oral status and postoperative pneumonia (POP) in patients with lung cancer, and whether improving their oral condition assists with a lower incidence of POP before lung cancer surgery remains controversial. This retrospective study was conducted by a stomatologist to assess the effect of controlling oral pathogenic bacteria of patients with lung cancer to prevent POP. METHODS: A total of 235 patients with lung cancer who underwent lobectomy by open thoracotomy between July 2015 and December 2018 were selected and given the choice of being in the experimental or control group. A total of 122 participants in the experimental group received professional oral plaque control, and 113 participants in the control group did not receive plaque control. All clinical data of participants in both groups were retrospectively studied to determine the incidence of POP at the thirtieth day of discharge from hospital. RESULTS: Eight in the experimental group and six in the control group were excluded from the study. It was found that four of 114 patients suffered from POP in the experimental group (incidence = 3.51%). A total of 17 of 107 patients in the control group had pulmonary infection (incidence = 15.89%). Odds ratio was 0.19. The incidence of POP in the experimental group was significantly lower than that of the control group (P < 0.05). CONCLUSIONS: Professional oral plaque control is associated with a lower incidence of POP following lung cancer surgery and is therefore a favorable factor for preventing POP, and should be carried out before the surgical treatment of lung cancer. KEY POINTS: Professional oral plaque control was associated with a lower incidence of POP following lung cancer surgery, and it is recommended this should be carried out before the surgical treatment of lung cancer.

Electrical transport in amorphous nanofilms embedded with crystalline grains at low temperatures.

Amorphous and ferromagnetic Al-Ni nanofilms have been grown by the magnetron-sputtering method with some nanosized crystalline grains embedded therein. Resistivity is demonstrated to transit from a positive temperature coefficient to a negative temperature coefficient (NTC) with increasing the fraction of Ni atoms in the Al-Ni nanofilms. The lattice disorder is deduced to induce the Anderson localization of electrons and the formation of polarons so that the NTC of the resistivity is driven in the Al-Ni nanofilms, different from that in the elemental Al and Ni nanofilms. The electron transport in the Al-Ni nanofilms is dominated by polaron hopping while it is also determined by electron-magnon and electron-phonon scatterings. The electron-magnon scatterings are further revealed to have a more important contribution to the electron transport at low temperatures than electron-phonon scatterings in the amorphous Al-Ni nanofilms. A so-called polaron-metal physical model has thus been proposed to well explain the electron transport in disorder lattices with crystalline grains embedded therein. This study may help to optimize the design of nano-engineered devices.

Electrochemical Hydrogen Evolution at the Interface of Monolayer VS2 and Water from First-Principles Calculations.

Density functional theory calculations are carried out to study the hydrogen evolution reaction (HER) at the electrochemical double-layer interface of monolayer 2H phase VS2 and water. Under typical conditions of HER, the catalyst surface is predicted to have a low hydrogen coverage of about 12%, whereas the aqueous solution side features a high hydronium concentration of about 8.3%. As a result, the HER takes place through the Volmer-Heyrovsky route, with an overall reaction barrier of about 1.0 eV, much larger than that of 1T phase VS2. This result demonstrates that 2H phase VS2 is much less reactive than its 1T phase counterpart, and the 1T-to-2H phase transformation induced by thickness reduction may deteriorate the HER activity of VS2.

Probing the properties of size dependence and correlation for tantalum clusters: geometry, stability, vibrational spectra, magnetism, and electronic structure.

A comprehensive investigation on the equilibrium geometry, relative stability, vibrational spectra, and magnetic and electronic properties of neutral tantalum clusters (Ta n , n = 2-17) was performed using density functional theory (DFT). We perform a study of the size dependence and correlations among those descriptors of parameters, and showed these could provide a novel way to confirm and predict experimental results. Some new isomer configurations that have never been reported before for tantalum clusters were found. The growth behaviors revealed that a compact geometrical growth route is preferred and develops a body-centered-cubic (BCC) structure with the cluster size increasing. The perfectly fitted functional curve, strong linear evolution, and obvious odd-even oscillation behavior proved their corresponding properties depended on the cluster size. Multiple demonstrations of the magic number were confirmed through the correlated relationships with the relative stability, including the second difference in energy, maximum hardness, and minimum polarizability. An inverse evolution trend between the energy gap and electric dipole moment and strong linear correlation between ionization potentials and polarizability indicated the strong correlation between the magnetic and electronic properties. Vibrational spectroscopy as a fingerprint was used to distinguish the ground state among the competitive geometrical isomers close in energy. The charge density difference isosurface, density of states, and molecular orbitals of selected representative clusters were analyzed to investigate the difference and evolutional trend of the relative stability and electronic structure. In addition, we first calculated the ionization potential and magnetic moment and compared these with the current available experimental data for tantalum clusters.

Doxorubicin-Loaded Dextran-Modified GoldMag Nanoparticles for Targeting Hepatocellular Carcinoma.

Doxorubicin (Dox) is one of the most widely used chemotherapeutic agents for many types of cancer, including hepatocellular carcinoma. However, clinical applications of Dox are limited due to its non-selective cytotoxicity that results in severe adverse effects. To tackle this problem targeted delivery of Dox exclusively to tumour milieu has become clinically prioritised. In this study, we first synthesized and validated Dextran coated GoldMag Nanoparticles (DGMNs) as a potential delivery vehicle for Dox. We then evaluated the cytotoxicity of Dox-DGMNs, the drug and carrier composites, under guidance of external magnetic field (EMF) in hepatocellular carcinoma cell lines and in tumour grafts. Intriguingly, DGMNs exhibited the capacity to prolong Dox release in vitro; hence, Dox-DGMNs significantly enhanced the therapeutic efficiency of the drug in vitro and in vivo, especially under EMF. However, DGMNs were able to significantly decrease systemic adverse effects and inhibit tumour growth compared to the intravenous application of free Dox. Molecular analysis revealed that tumour cells were more affected by Dox-DGMNs with EMF than Dox-DGMNs or Dox alone in terms of apoptosis and DNA damage marker expression. Overall, DGMNs exhibited a substantial potential to serve as a promising drug delivery carrier for magnetically targeted cancer therapy.

Development of novel prediction model for drug-induced mitochondrial toxicity by using naïve Bayes classifier method.

Mitochondrial dysfunction has been considered as an important contributing factor in the etiology of drug-induced organ toxicity, and even plays an important role in the pathogenesis of some diseases. The objective of this investigation was to develop a novel prediction model of drug-induced mitochondrial toxicity by using a naïve Bayes classifier. For comparison, the recursive partitioning classifier prediction model was also constructed. Among these methods, the prediction performance of naïve Bayes classifier established here showed best, which yielded average overall prediction accuracies for the internal 5-fold cross validation of the training set and external test set were 95 ± 0.6% and 81 ± 1.1%, respectively. In addition, four important molecular descriptors and some representative substructures of toxicants produced by ECFP_6 fingerprints were identified. We hope the established naïve Bayes prediction model can be employed for the mitochondrial toxicity assessment, and these obtained important information of mitochondrial toxicants can provide guidance for medicinal chemists working in drug discovery and lead optimization.

DNA binding, DNA cleavage and HSA interaction of several metal complexes containing N-(2-hydroxyethyl)-N'-benzoylthiourea and 1,10-phenanthroline ligands.

Four novel ternary metal complexes of the type [M(Phen)(L1)2)] [phen = 1,10-phenanthroline, L1 = N-(2-hydroxyethyl)-N'-benzoylthiourea, M = Ni(II)(1), Co(II) (2), Cu(II) (3), Pd(II) (4)] were synthesized. The organic ligands and their corresponding organometallic complexes have been characterized using UV-vis absorption spectroscopy, element analysis, infrared radiation spectroscopy and fluorescence spectra. DNA binding and cleavage studies of these complexes were conducted in detail. In vitro DNA-binding properties were studied by electronic absorption spectra and fluorescence spectra methods. The results indicate that all of the ternary metal complexes can efficiently bind to DNA via intercalation mode. The DNA-binding constants for all ternary compounds are around 4 × 10(6) M(-1). The binding propensity of the complexes to human serum albumin (HSA) was also investigated. Agarose gel electrophoresis study revealed that the metal complexes could cleave super-coiled pBR322 DNA to a nicked form in the absence of external agents. In vitro anti bacterial studies show that copper complex has weak antibacterial activities. Copper complex exhibits a better biological activity among all complexes. This study provides a new perspective and evaluation on the role and importance of the effect factors on the medicinal properties of benzoylthiourea compounds. Synchronous fluorescence spectra of HSA (10 µM) as a function of concentration of the complexes 1-4.