Monocarboxylate-protected two-electron superatomic silver nanoclusters with high photothermal conversion performance.

The first series of monocarboxylate-protected superatomic silver nanoclusters was synthesized and fully characterized by X-ray diffraction, fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and electrospray ionization mass spectrometry (ESI-MS). Specifically, compounds [Ag16(L)8(9-AnCO2)12]2+ (L = Ph3P (I), (4-ClPh)3P (II), (2-furyl)3P (III), and Ph3As (IV)) were prepared by a solvent-thermal method under alkaline conditions. These clusters exhibit a similar unprecedented structure containing a [Ag8@Ag8]6+ metal kernel, of which the 2-electron superatomic [Ag8]6+ inner core shows a flattened and puckered hexagonal bipyramid of S6 symmetry. Density functional theory calculations provide a rationalization of the structure and stability of these 2-electron superatoms. Results indicate that the 2 superatomic electrons occupy a superatomic molecular orbital 1S that has a substantial localization on the top and bottom vertices of the bipyramid. The π systems of the anthracenyl groups, as well as the 1S HOMO, are significantly involved in the optical and photothermal behavior of the clusters. The four characterized nanoclusters show high photothermal conversion performance in sunlight. These results show that the unprecedented use of mono-carboxylates in the stabilization of Ag nanoclusters is possible, opening the door for the introduction of various functional groups on their cluster surface.

Nanoscale Metal-Organic Frameworks: Recent developments in synthesis, modifications and bioimaging applications.

Porous Metal-Organic Frameworks (MOFs) have emerged as eye-catching materials in recent years. They are widely used in numerous fields of chemistry thanks to their desirable properties. MOFs have a key role in the development of bioimaging platforms that are hopefully expected to effectually pave the way for accurate and selective detection and diagnosis of abnormalities. Recently, many types of MOFs have been employed for detection of RNA, DNA, enzyme activity and small-biomolecules, as well as for magnetic resonance imaging (MRI) and computed tomography (CT), which are valuable methods for clinical analysis. The optimal performance of the MOF in the bio-imaging field depends on the core structure, synthesis method and modifications processes. In this review, we have attempted to present crucial parameters for designing and achieving an efficient MOF as bioimaging platforms, and provide a roadmap for researchers in this field. Moreover, the influence of modifications/fractionalizations on MOFs performance has been thoroughly discussed and challenging problems have been extensively addressed. Consideration is mainly focused on the principal concepts and applications that have been achieved to modify and synthesize advanced MOFs for future applications.

Radiochromic Hydrogen-Bonded Organic Frameworks for X-ray Detection.

Porous materials have been investigated as efficient photochromic platforms for detecting hazardous radiation, while the utilization of hydrogen bonded organic frameworks (HOFs) in this field has remained intact. Herein, two HOFs were synthesized through self-assembly of tetratopic viologen ligand and formic acid (PFC-25, PFC-26), as a new class of "all-organic" radiochromic smart material, opening a gate for HOFs in this field. PFC-26 is active upon both X-ray and UV irradiation, while PFC-25 is only active upon X-ray irradiation. The same building block yet different radiochromic behaviors of PFC-25 and PFC-26 allow us to gain a deep mechanistic understanding of the factors that control the detection specificity. Theoretical and experimental studies reveal that the degree of π-conjugation of viologen ligand is highly related to the threshold energy of triggering a charge transfer, therefore being a vital factor for the particularity of radiochromic materials. Thanks to its convenient processibility, nanoparticle size, and UV silence, PFC-25 can be further fabricated into a portable naked-eye sensor for X-ray detection, which shows obvious color change with the merits of high transmittance contrast, good sensitivity (reproducible dose threshold of 3.5 Gy), and excellent stability. The work exhibits the promising practical potentials of HOF materials in photochromic technology.

Stable supercapacitor electrode based on two-dimensional high nucleus silver nano-clusters as a green energy source.

Atomically precise silver nanoclusters (Ag-NCs) are known as a hot research area owing to their brilliant features and they have attracted an immense amount of research attention over the last year. There is a lack of sufficient understanding about the Ag-NC synthesis mechanisms that result in optimal silver nanoclusters with an appropriate size, shape, and morphology. In addition, the coexisting flexible coordination of silver ions, the argentophilic interactions, and coordination bonds result in a high level of sophistication in the self-assembly process. Furthermore, the expansion of clusters by the organic ligand to form a high dimensional structure could be very interesting and useful for novel applications in particular. In this study, a novel two-dimensional 14-nucleus silver poly-cluster was designed and synthesized by the combination of two synthetic methods. The high nucleus silver cluster units are connected together via tetradecafluoroazelaic acid (CF2) and this leads to the high stability of the polymer. This highly stable conductive poly-cluster, with bridging groups of difluoromethylene, displays a high energy density (372 F g-1 at 4.5 A g-1), excellent cycling stability, and great capacity. This nanocluster shows a high power density and long cycle life over 6000 cycles (95%) and can also tolerate a wide range of scan rates (5 mV s-1 to 1 V s-1), meaning it could act as a green energy source.

New 3D Porous Silver Nanopolycluster as a Highly Effective Supercapacitor Electrode: Synthesis and Study of the Optical and Electrochemical Properties.

A high-nucleus silver nanopolycluster as a new type of silver-based polymer supercapacitor (SSc) by a simple and single-step synthesis process was designed and synthesized. The structural, optical, and electrochemical properties of SSc-2 were determined. This highly stable conductive 3D nanopolycluster shows great cycling stability, large capacity, and high energy density without any modification or doping process and so acts as an excellent SSc (412 F g-1 at 1.5 A g-1). In addition, there was a stable cycling performance (94% capacitance) following 7000 cycles at 3 A g-1 current density. The presence of fluorinated groups, 3D expansion of high-nucleus metallic clusters, and porosity are the advantages of SSc-2 that lead to stability, conductivity, and high capacity, respectively. These results lead to the development of a novel kind of SSc by overcoming the low conductivity and limited capacity challenges without any modification.

Electrochemical Applications of Ferrocene-Based Coordination Polymers.

Ferrocene and its derivatives, especially ferrocene-based coordination polymers (Fc-CPs), offer the benefits of high thermal stability, two stable redox states, fast electron transfer, and excellent charge/discharge efficiency, thus holding great promise for electrochemical applications. Herein, we describe the synthesis and electrochemical applications of Fc-CPs and reveal how the incorporation of ferrocene units into coordination polymers containing other metals results in unprecedented properties. Moreover, we discuss the usage of Fc-CPs in supercapacitors, batteries, and sensors as well as further applications of these polymers, for example in electrocatalysts, water purification systems, adsorption/storage systems.

Comparative Study of the Supercapacitive Performance of Three Ferrocene-Based Structures: Targeted Design of a Conductive Ferrocene-Functionalized Coordination Polymer as a Supercapacitor Electrode.

As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH)2 ) clusters based on coinage metals, [(PPh3 )2 AgO2 CFcCO2 Ag(PPh3 )2 ]2 ⋅7 CH3 OH (SC1 : super capacitor) and [(PPh3 )3 CuO2 CFcCO2 Cu(PPh3 )3 ]⋅3 CH3 OH (SC2 ), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g-1 and 210 F g-1 specific capacitance at 1.5 A g-1 in Na2 SO4 electrolyte, respectively. The obtained results show that the presence of CuI instead of AgI improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC2 ([(PPh3 )2 CuO2 CFcCO2 ]∞ ), a polymeric structure of SC2 , was synthesized and used as an energy storage electrode. PSC2 displays high conductivity and gives 455 F g-1 capacitance at 3 A g-1 . The PSC2 as a supercapacitor electrode presents a high power density (2416 W kg-1 ), high energy density (161 Wh kg-1 ), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high-performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials.

Size and function influence study on enhanced catalytic performance of a cooperative MOF for mild, green and fast C-C bond formation.

Tuning of pore function and size (surface area) are two key factors that play important roles in the performance of metal-organic-frameworks (MOFs) as catalysts. The catalytic performance of two bulk and nanosized MOFs with different functional groups such as a Brønsted base and Lewis acid was studied in line with the sustainable development of catalysts and green chemistry principles. Bifunctional imine decorated TMU-33, ([Cd3(BDC)3(OPP)(DMF)2]·2DMA)n (TMU-33), (OPP: N,N'-(oxybis(4,1-phenylene))bis(1-(pyridin-4yl)methanimine)), with an adjustable structure and amine functionalized TMU-40, [Zn(BDC)(L*)]·DMF, (L*: N1,N2-bis(pyridin-4-ylmethylene)ethane-1,2-diamine), were evaluated in the C-C bond forming reaction under mild and green conditions. The results show that the nanosized samples of bifunctional TMU-33 which simultaneously have an imine and open metal site exhibit higher performance as Knoevenagel catalysts. Furthermore, among the nanosized samples, the nanoplate TMU-33 with more access to open metal sites shows the highest catalytic activity without any side product in water, at room temperature for 5 min, which confirms that the Lewis acid is the effective catalyst for this reaction. The catalyst could be reused for at least three cycles without any significant loss of its activity. The performance of the structure indicates that the tuning of functionality of MOFs can be a very promising route for the extension of green catalysts.

The Prevalence of Genu Varum and Genu Valgum in Overweight and Obese Patients: Assessing the Relationship between Body Mass Index and Knee Angular Deformities.

BACKGROUND: Recent studies have shown evidence of a relationship between overweight and obesity with skeletal abnormalities, especially angular knee disorders. AIM OF THE STUDY: To reveal causal relationship between obesity and skeletal abnormalities. METHODS: This study was performed on 280 overweight or obese patients (with BMI > 25kg/m2) who referred to Rasoul Akram hospital in Tehran between 2017 and 2018. Several non-radiographic methods including measuring Q angle, inter-malleoli distance and distance between two knees were used to determine genu varum and genu valgum.  BMI was also calculated by dividing the weight by the square of the height. RESULTS: The prevalence of genu varumand genu valgum was 8.6% and 10.0% respectively. There was a significant adverse correlation between the Q angle and BMI. The mean BMI in patients with and without genu varum was 39.07 ± 6.41 kg/m2 and 42.1 ± 2.26 kg/m2, respectively, which was significantly lower in the genuvarum group (P = 0.008). Also, the mean BMI in patients with and without genu valgum was 43.39 ± 3.33 kg/m2 and 41.58 ± 4.61  kg/m2, respectively, which was significantly higher in the genuvalgum group (P = 0.044). Also, there was a direct correlation between BMI of patients with inter-malleoli distance and inverse correlation between BMI and two knees distance. CONCLUSION: There is a strong and significant relationship between incidence of obesity and genu valgum; therefore, the prevalence of this deformity in obese individuals is predictable. Also, the lower incidence of genu varum in obese people is predictable in our society.

Ultrasonic-assisted synthesis of the nanostructures of a Co(II) metal organic framework as a highly sensitive fluorescence probe of phenol derivatives.

Nanostructures of a metal-organic framework with chemical formula, [Co(BDC)(L*)]n.DMF (TMU-40), BDC = 1,4-benzendicarboxylate, L* = 5,6-dipyridin-4-yl-1,2,3,4-tetrahydropyrazine, under ultrasonic irradiation at ambient temperature and atmospheric pressure were prepared and characterized by Fourier-transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). Sonication time, concentration of initial reagents and ultrasonic generator power effects on the size and morphology of nano-structured compounds were studied. TMU-40 (for Tarbiat Modares University) displayed a good potential as a luminescent sensor against phenol derivatives consist of phenol, 4-aminophenol, 4-methylphenol and 4-chlorophenol. Nano-sized TMU-40 showed the better sensing performance in comparison to its bulk phase. The nano TMU-40 displayed very selective and sensitive in detection of phenol derivatives. The detection limit amounts of 15 nM and 63 nM were achieved for 4-aminophenol in nano TMU-40 and bulk TMU-40, respectively. The special structure and fluorescent character of L* ligand and high surface area of nano MOF provide an effective interaction between MOF and phenolic analytes to selectively and sensitively detect of the analyte molecules.

Highly Electroconductive Metal-Organic Framework: Tunable by Metal Ion Sorption Quantity.

This study has developed a simple and innovative approach to design a metal-organic framework (MOF) with tunable conductivity. The in situ amine functionalized TMU-60 [Zn(OBA)(L*)·DMF] has the potential of converting to a conductor due to the selective and fast sorption of cadmium ion. In order to precisely monitor the cadmium penetration to the framework pores, in addition to full kinetic and thermodynamic studies of sorption, the time-dependent effects of Cd(II) penetration to MOF pores was taken by fluorescence and electrochemical methods. The results obviously prove that the conductivity of the structure can be adjusted by changing the Cd exposure time and the quantity of ion sorption. The presence of cadmium ions can enhance the ability of the framework to pass electrons through its constituents. Even though the porosity of the structure remains to a certain extent, the achieved tunable and highly stable electrical conductivity is provided by sorption of metal ions. More importantly, the conductivity has been improved from 53 × 10-6 to 1.8 × 10-2 S·cm-1 for TMU-60 and TMU-60-Cd compressed pellet (room temperature), respectively. The mechanism of charge transport through the pellet is proposed to be a hopping mechanism between metal nodes and localized Cd(II) after sorption, which is supported by chronoamperometry measurement. A fit of the time-dependent data to the Cottrell equation gave a charge-transport diffusion coefficient of 1.6 × 10-10 cm2/s throughout the structure. This novel approach not only enhances the conductivity of the MOF but also allows adjusting the conductivity according to the desired applications.

Ultrasonic-assisted fabrication of thin-film electrochemical detector of H2O2 based on ferrocene-functionalized silver cluster.

A novel ferrocene-functionalized silver cluster (FcAgCs) has been designed and synthesized with the assistant of ultrasound treatment and fully characterized by single crystal spectroscopy, IR, UV-Vis, XRD, TGA, NMR, CV and elemental analyses. Ultrasound synthesis method facilitates and accelerates synthesis of this amazing structure and plays a vital role in the synthesis of this special cluster. Single-crystal X-ray analysis reveal that the cluster can be described as a cationic [(dppf)2Ag4(CCtBu)2(CH3OH)2]2+ (dppf = 1,1'-bis(diphenylphosphino)ferrocene) species consisted of four rhombic silver atom and two isolated BF4- counter anions. Thermal stability greater than 200 °C and solution CV results show that the title cluster is sufficiently stable and suitable for the fabricating of FcAgCs/ITO thin-films and exploring as electrochemical responding materials. Based on its properties, we use it to prepare thin-films on ITO substrate by spin coating method. Verification of synthesis, thickness, uniformity and stability of the fabricated FcAgCs/ITO thin-films were characterized and confirmed by UV, XRD, SEM and the scotch tape adhesion peel test. Moreover, we use this FcAgCs/ITO thin-film electrode as thin-film electrochemical detector which shows sensitive and quick response in the detection of H2O2.

Simple One-Pot Preparation of a Rapid Response AIE Fluorescent Metal-Organic Framework.

Luminogenic materials, particularly those that have turn-on response by sensing the analytes, are highly regarded as optical instruments, sensing material, fluorescent probes, etc. However, most of these materials are only usable in dilute form and often show the self-quenching effect at high concentrations. The use of light-emitting AIE-based materials (aggregation-induced emission) is the solution of this problem. The rigid structure of these active fluorescence ligands, which contains several aromatic rings attached to each other, does not lose its fluorescence properties by increasing the concentration. Unlike other AIE ligands, which have a complex or multistep synthetic route, here, we present a simple one-pot method for in situ synthesis of the AIE ligand and the metal-organic framework (MOF) contained therein. Presence of metal nodes having varied outer-shell electron configurations affects the fluorescence intensity of these materials and, thus, both high and low emissive "turn on" MOFs were readily acquired. Based on the possible interactions between the free nitrogens on the ligand and the phenolic compounds, the MOFs enable highly selective and sensitive detection of phenol derivatives in several seconds with low detection limits (less than 65 nM for 4-aminophenol and 120 nM for phenol) through turn-on emission fluorescence.

Goal-Directed Design of Metal-Organic Frameworks for HgII and PbII Adsorption from Aqueous Solutions.

Metal-organic frameworks (MOFs), which are inorganic-organic hybrid porous materials prepared from metal ion/clusters and multidentate organic ligands, have evolved to be next-generation utility materials because of their usability in diverse applications. These porous materials, with excellent chemical stability and a wide variety of functional groups, have demonstrated their utility to the area of capturing various types of hazardous metal ion pollutants. This conceptual review focuses on recent progress in reported MOFs as HgII and PbII adsorbents emphasizing the general concepts that have guided important developments in these area and their implications for future research. Also, we suggest our personal insights into future research opportunities in the area and we hope to encourage more researchers to engage in this new field of MOF-based materials with the goal of environmental pollution management.

Fast and Selective Heavy Metal Removal by a Novel Metal-Organic Framework Designed with In-Situ Ligand Building Block Fabrication Bearing Free Nitrogen.

Fast and effective adsorbents for the selective removal of HgII and PbII ions were prepared by the reaction of Zn(NO3 )2 ⋅6H2 O, H2 BDC, and N1 ,N2 -bis(pyridin-4-ylmethylene) ethane-1,2-diamine (L) that yields an unprecedented two-dimensional layer-based supramolecular framework, {Zn(BDC)(L*)}⋅DMF (TMU-40), by solvothermal reaction. The formation of this framework involved an in situ C=C coupling of L to L* [L*=5,6-di(pyridin-4-yl)-1,2,3,4-tetrahydropyrazine]. As L* contains free nitrogen atoms, direct reaction of L* and metals led to metallated products. Post-synthetic modification of this novel MOF (TMU-40) with H2 O2 gives a new framework (O-TMU-40) by same structure and different ligand, which also bears free nitrogen atoms. FTIR spectra, TGA analysis, X-ray diffraction, Zeta Potential analysis and 1 H NMR spectroscopy were used to characterize the prepared frameworks. The TMU-40 and O-TMU-40 frameworks were used for heavy-metal removal from aqueous solutions. Maximum adsorption values of 269 mg g-1 for HgII with TMU-40 and 215 mg g-1 for PbII with O-TMU-40 were achieved in 10 min at 298 Kwithout changes in the pH of the adsorption medium with pseudo-second order kinetics based on the Langmuir model. The extremely fast kinetics of TMU-40 means this adsorbent can reduce heavily contaminated water containing HgII concentrations of 40 ppm down to the acceptable limit of 2 ppb.