A novel nano‐size lanthanum metal–organic framework based on 5‐amino‐isophthalic acid and phenylenediamine: Photoluminescence study and sensing applications

In this paper, a novel lanthanum metal–organic framework La‐MOF was prepared via hydrothermal and reflux methods. The La‐MOF was achieved through the reaction of a 5‐amino‐isophthalic acid with 1, 2‐phenylenediamine and lanthanum chloride. The prepared La‐MOF structure was confirmed by XRD, mass spectrometry, IR, UV–Vis and elemental analysis, whereas the size, and morphology was examined by FE‐SEM/EDX and HR‐TEM. The results indicated that the La‐MOF prepared via both methods have the same structure and composition. Meanwhile, the MOF yield, reaction time, morphology, physiochemical and sensing properties were highly depended on the used preparation method. The photoluminescence (PL) study was carried out for the La‐MOF, and the results showed that La‐MOF exhibits strong emission at 558 nm after excitation at 369 nm. Moreover, the PL data indicating that the La‐MOF has highly selective sensing properties for iron (III) competing with different metal ions. The Stern‐Völmer graph shows a linear calibration curve which achieved over a concentration range 1.0–500 μM of Fe³⁺ with a correlation coefficient, detection, and quantitation limits 0.998, 1.35 μM and 4.08 μM, respectively. According to the remarkable quenching of the PL intensity of La‐MOF using various concentrations of Fe³⁺, it was successfully used as a sensor for Fe³⁺detecting in different water resources (pure and waste) samples. The quenching mechanism was studied and it has a dynamic type and due to efficient energy transfer between the La‐MOF and Fe³⁺.     

Engineering a Cu‐MOF Nano‐Catalyst by using Post‐Synthetic Modification for the Preparation of 5‐Substituted 1H‐Tetrazoles

A new nano scale Cu‐MOF has been obtained via post‐synthetic metalation by immersing a Zn‐MOF as a template in DMF solutions of copper(II) salts. The Cu‐MOF serves as recyclable nano‐catalyst for the preparation of 5‐substituted 1H‐tetrazoles via [3 + 2] cycloaddition reaction of various nitriles and sodium azide in a green medium (PEG). The post‐synthetic metalated MOF were characterized by FT‐IR spectroscopy, powder X‐ray diffraction (PXRD), atomic absorption spectroscopy (AAS), and energy dispersive X‐ray spectroscopy (EDX) techniques. The morphology and size of the nano‐catalyst were determined by field emission scanning electron microscopy (FE‐SEM).     

Organometallic assembling of chitosan‐Iron oxide nanoparticles with their antifungal evaluation against Rhizopus oryzae

The ever‐increasing resistance of plant microbes towards fungicides and bactericides has been causing serious threat to plant production in recent years. For the development of an effective antifungal agent, we introduce a novel hydrothermal protocol for synthesis of chitosan iron oxide nanoparticles (CH‐Fe₂O₃ NPs) using acetate buffer of low pH 5.0 for intermolecular interaction of Fe₂O₃ NPs and CH. The composite structure and elemental elucidation were carried out by using X‐ray power diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X‐ray (EDX), Transmission Electron Microscopy (TEM), Fourier Transformed Infrared Spectroscopy (FTIR) and Ultraviolet Visible Absorption Spectroscopy (UV–vis spectroscopy). Additionally, antifungal activity was evaluated both In vitro and In vivo against Rhizopus oryzae which is causing fruit rot disease of strawberry. We compared different concentrations (0.25%, 0.50%, 075% and 1%) of CH‐Fe₂O₃ NPs and 50% synthetic fungicide (Matalyxal Mancozab) to figure out suitable concentration for application in the field. XRD analysis showed a high crystalline nature of the NPs with average size of 52 nanometer (nm). SEM images revealed spherical shape with size range of 50–70 nm, whereas, TEM also revealed spherical shape, size ranging from 0 nm to 80 nm. EDX and FTIR results revealed presence of CH on surface of Fe₂O₃ NPs. The band gap measurement showed peak 317–318 nm for bare Fe₂O₃ NPs and CH‐Fe₂O₃ NPs respectively. Antifungal activity in both In vitro and In vivo significantly increased with increase in concentration. The overall results revealed high synergetic antifungal potential of organometallic CH‐Fe₂O₃ NPs against Rhizopus oryzae and suggest the use of CH‐Fe₂O₃ NPs against other Phyto‐pathological diseases due to biodegradable nature.     

Fabrication of carboxymethylated cellulose fibers supporting Ag NPs@MOF‐199s nanocatalysts for catalytic reduction of 4‐nitrophenol

In this work, we prepared high‐performance and recyclable nanocatalysts that consist of small and well‐dispersed silver nanoparticles (Ag NPs) immobilized onto Cu‐ based metal–organic framework (MOF‐199 s) supported by carboxymethylated cellulose fibers (CCFs). The as‐prepared green nanohybrid catalysts, namely Ag NPs@ MOF‐199 s/CCFs, were characterized using SEM, TEM, XRD and FT‐IR techniques. The catalytic performances showed that Ag NPs@ MOF‐199 s/CCFs catalysts exhibited a very high catalytic efficiency towards the reduction of 4‐nitrophenol to 4‐aminophenol. The enhanced catalytic performances are attributed to the improved dispersity, small particles of Ag NPs stabilized by the MOF‐199 s, and the porous catalyst structures. The introduction of cellulose fiber further facilitates the reuse and sustainability of the nanohybrid catalysts, showing a stable and high reusability (more than 91% of catalytic activity) even after five runs.     

Copper nanoparticles supported on polyethylene glycol-modified magnetic Fe3O4 nanoparticles: Its anti-human gastric cancer investigation

In that work, we have described the synthesis of novel Cu NPs decorated polyethylene glycol (PEG₂₀₀₀) coated magnetic nanoparticles (Fe₃O₄/PEG2000/Cu NPs) in an eco-friendly pathway applying Green Tea extract as reducing/stabilizing agent. The morphological and physicochemical features of the prepared nanocomposite were determined using several advanced techniques like ICP-OES, FE-SEM, EDX, atomic mapping, TEM, VSM, and XRD studies. In the antioxidant test, the IC50 of Fe₃O₄/PEG₂₀₀₀/Cu nanocomposite and BHT against DPPH free radicals were 198 and 85 µg/mL, respectively. In the cellular and molecular part of the recent study, the treated cells with Fe₃O₄/PEG₂₀₀₀/Cu nanocomposite were assessed by MTT assay for 48 h about the cytotoxicity and anti-human gastric cancer properties on normal (HUVEC) and gastric cancer cell lines i.e. NCI-N87 and MKN45. The IC50 of Fe₃O₄/PEG₂₀₀₀/Cu nanocomposite were 316 and 131 µg/mL against NCI-N87 and MKN45 cell lines, respectively. The viability of malignant gastric cell line reduced dose-dependently in the presence of Fe₃O₄/PEG₂₀₀₀/Cu nanocomposite. It seems that the anti-human gastric cancer effect of recent nanoparticles is due to their antioxidant effects.     

In vitro curcumin delivery and antibacterial activity of RuS2 and RuO2 nanoparticles loaded chitosan biopolymer

In this work, RuS₂ and RuO₂ nanoparticles loaded chitosan (Chitosan was extracted from Lobsters shells of Persian Gulf, IR. Iran) was prepared and characterized via FE‐SEM, EDS and FT‐IR analysis. FESEM showed the formation of spherical nanoparticles in size ranging of 20 to 100 mm. Subsequently, the role of these new materials as curcumin drug carrier and in vitro release of curcumin in simulated body fluid (SBF) solution (pH 7.4) were studied. RuS₂‐NPs‐CS than to RuO₂‐NPs‐CS showed higher drug loading efficiency (>91%) and rapid (<90 min) curcumin drug release in SBF solution. Also, antibacterial activity of RuS₂‐NPs‐CS and RuO₂‐NPs‐CS in presens and absence of Rosemary extracts against the gram negative bacteria Pseudomonas aeruginosa (PAO 1) was evaluated by detection of minimal inhibition concentration (MIC) and minimal bactericidal concentration (MBC). MIC of RuS₂‐NPs‐CS, RuO₂‐NPs‐CS and Rosemary extracts on Pseudomonas aeruginosa strains were found to be 50 mg/ml, 50 mg/ml and 1250 mg/ml, respectively. The synergistic effect of these materials for inhibition of PAO 1 growth showed that mixture of RuS₂‐NPs‐CS and Rosemary extracts has a better efficiency than to other mixture materials.     

Design Rules for Self‐Assembly of 2D Nanocrystal/Metal–Organic Framework Superstructures

We demonstrate the guiding principles behind simple two dimensional self‐assembly of MOF nanoparticles (NPs) and oleic acid capped iron oxide (Fe₃O₄) NCs into a uniform two‐dimensional bi‐layered superstructure. This self‐assembly process can be controlled by the energy of ligand–ligand interactions between surface ligands on Fe₃O₄ NCs and Zr₆O₄(OH)₄(fumarate)₆ MOF NPs. Scanning transmission electron microscopy (TEM)/energy‐dispersive X‐ray spectroscopy and TEM tomography confirm the hierarchical co‐assembly of Fe₃O₄ NCs with MOF NPs as ligand energies are manipulated to promote facile diffusion of the smaller NCs. First‐principles calculations and event‐driven molecular dynamics simulations indicate that the observed patterns are dictated by combination of ligand–surface and ligand–ligand interactions. This study opens a new avenue for design and self‐assembly of MOFs and NCs into high surface area assemblies, mimicking the structure of supported catalyst architectures, and provides a thorough fundamental understanding of the self‐assembly process, which could be a guide for designing functional materials with desired structure.     

Size Selectivity of a Copper Metal–Organic Framework and Origin of Catalytic Activity in Epoxide Alcoholysis

{Cu(bpy)(H₂O)₂(BF₄)₂(bpy)} (Cu‐MOF; MOF=metal–organic framework; bpy=4,4′‐bipyridine), with a 3D‐interpenetrated structure and saturated Cu coordination sites in the framework, possesses unexpectedly high activity in the ring‐opening reaction of epoxides with MeOH, although the reaction rate drops remarkably with more bulky alcohols. This (apparent) size selection and the single Cu²⁺ sites in an identical environment of the crystalline matrix resemble zeolites. The real nature of active sites was investigated by attenuated total reflection infrared (ATR‐IR), Raman, EPR, and UV/Vis spectroscopies. Cu‐MOF has highly dynamic structural properties that respond to MeOH; its framework dimensions change from 3D to 2D by restructuring to a symmetric coordination of four bpy units to Cu. This interaction is accompanied by the partial dissolution of Cu‐MOF as multi‐Cu clusters, in which Cu²⁺ ions are connected with bpy ligands. Although both molecular and surface catalysis contribute to the high rate of alcoholysis, the soluble oligomeric species (Cu_mbpy_n) are far more active. Finally, addition of diethyl ether to the reaction mixture induces the reconstruction of dissolved and solid Cu‐MOF to the original framework structure, thereby allowing excellent recyclability of Cu‐MOF as an apparent heterogeneous catalyst. In contrast, the original Cu‐MOF structure is maintained upon contact with larger alcohols, such as iPrOH and tBuOH, thus leading to poor activity in epoxide ring opening.     

Surface Modification of TiO2 Nanoparticles with Vitamin B12: Relationships between Vitamin B12 Content and Its Optical Properties

Anatase TiO₂ nanoparticles (NPs) with particle size of 10–20 nm were prepared via sol gel technique. The as‐synthesized NPs were immerged in vitamin B₁₂ (VB₁₂) solutions with different concentrations. The in‐ fluences of the solution concentration on photoluminescence and photocatalytic activity of the modified NPs were studied. Fourier transform infrared spectroscopy (FTIR) results demonstrated that TiO₂ NPs adsorb VB₁₂ molecules and that a new band is formed at ～2300 cm^?1. The VB₁₂ loading process led to dimin‐ ishing of the aggregation of NPs and formation of a fibre shape structure. The best photoactivity and PL effect among the modified samples was related to sample ‘d’. The optimum processing conditions to achieve this sample was found to be VB₁₂ concentration of 5 g/L.     

Dendrimer‐encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe3O4@SiO2 nanoparticles as a novel recyclable catalyst for N‐arylation of nitrogen heterocycles and green synthesis of 5‐substituted 1H‐tetrazoles

In this study, dendrimer‐encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe₃O₄@SiO₂ nanoparticles were prepared via a multistep‐synthesis. Then, the synthesized composite was fully characterized by various techniques such as fourier transform infrared (FT‐IR) spectroscopy, X‐ray diffraction (XRD), dynamic light scattering (DLS), UV‐vis spectroscopy, energy dispersive X‐ray analysis (EDX), thermogravimetric analysis (TGA) and vibration sample magnetometer (VSM). From the information gained by FE‐SEM and TEM studies it can be inferred that the particles are mostly spherical in shape and have an average size of 50 nm. Also, the amount of Cu is determined to be 0.51 mmol/g in the catalyst by inductively coupled plasma (ICP) analyzer. This magnetic nano‐compound has been successfully applied as a highly efficient, magnetically recoverable and stable catalyst for N‐arylation of nitrogen heterocycles with aryl halides (I, Br) and arylboronic acids without using external ligands or additives. The catalyst was also employed in a one‐pot, three‐component reaction for the efficient and green synthesis of 5‐substituted 1H‐tetrazoles using various aldehydes, hydroxylamine hydrochloride and sodium azide in water. The magnetic catalyst can be easily separated by an external magnet bar and is recycled seven times without significant loss of its activity.     

Temperature Dependent Spectroscopic Properties of Cu+ and Dy3+ Co-Doped Phosphate Glass: Band Gap Analysis and Cu Nanocluster-Enhanced Dy3+ Luminescence

This paper reports on the effects of temperature on light absorption and emission in Cu⁺ and Dy³⁺ co-doped phosphate glass, which is of interest for photonic applications. First, the temperature dependence of the absorption edge of the glass in connection with Cu⁺ ions absorption was assessed. A thermally-induced red shift attributed to Cu⁺ ion-lattice interactions was observed and analyzed through optical band gap determinations in the context of indirect-allowed transitions. Application of the Varshni model for the dependence of the energy gaps with temperature allowed to estimate the 0 K energy gap at 2.87 (±0.01) eV. Furthermore, Dy³⁺ photoluminescence (PL) along with Cu nanoparticles (NPs) absorption was monitored in real-time during an isothermal treatment by the in situ concurrent PL and absorption microspectroscopy technique. Periods of enhancement and quenching of Dy³⁺ emission linked to bidirectional energy transfer processes involving non-plasmonic Cu clusters and plasmonic Cu NPs were revealed. The formation of Cu NPs was promoted by tin(II) used as reductant. It is the first time to the author's knowledge that the 0 K energy gap is estimated for a highly Cu⁺-doped glass and that the enhancement of Dy³⁺ PL by Cu clusters is exposed.     

Preparation of chitosan functionalized end‐capped Ag‐NPs and composited with Fe3O4‐NPs: Controlled release to pH‐responsive delivery of progesterone and antibacterial activity against pseudomonas aeruginosa (PAO‐1)

In this work, functionalized chitosan end‐capped Ag nanoparticles (NPs) and composited with Fe₃O₄‐NPs was prepared as pH‐responsive controlled release carrier for gastric‐specific drug delivery. The structure of prepared material was characterized by FE‐SEM, XRD, EDS and FT‐IR analysis. The loading behavior of the progesterone onto this novel material was studied in aqueous medium at 25°C and their release was followed spectrophotometrically at 37°C in seven different buffer solutions (pH 1.2, 2.2, 3.2, 4.2, 5.2, 6.2 and 7.2) to simulate intestine and gastric media which experimental results reveal more release rate in pH 1.2 (gastric medium) with respect to other buffers. This observation is attributed to dependency of the CS‐IMBDO‐Ag‐Fe₃O₄‐NPs and progesterone structure with buffer pH that candidate this new material as prospective pH‐sensitive carrier for gastric‐targeted drug delivery. On the other hand, the antibacterial properties of this material against gram‐negative bacterium pseudomonas aeruginosa (PAO‐1) in agar plates was studied and accordingly based on broth micro dilution the minimum bactericidal concentration (MBC) and minimum inhibitory concentration (MIC) with respect to standard CLSI in different concentrations of CS‐IMBDO‐Ag‐Fe₃O₄‐NPs was calculated. The results reveal that MIC and MBC values are 50 and 1250 μg/mL, respectively. In addition, extracts of Portulaca oleracea leaves was prepared and its antibacterial activity in single and binary system with CS‐IMBDO‐Ag‐Fe₃O₄‐NPs as synergies effect against PAO‐1 was tested and results shown that these materials have significant synergistic effect for each other.     

Novel symmetrical coralloid Cu 3D superstructures: Solid-state synthesis from a Cu-carboxylate MOF and their in-situ thermal conversion

We describe here a one-step solid-state process for the synthesis of metal three-dimensional (3D) superstructures from a metal-organic framework (MOF). Novel symmetrical coralloid Cu 3D superstructures with surface interspersed with clusters of Cu nanoparticles were successfully synthesized by thermolysis of the [Cu₃(btc)₂] (btc=benzene-1,3,5-tricarboxylato) MOF in a one-end closed horizontal tube furnace (OCTF). The obtained products were characterized by TGA, FT-IR, XRD, EDX, SEM, TEM, HRTEM and SAED. Different reaction conditions were discussed. Furthermore, the synthesized Cu samples were converted into CuO microstructures by in-situ calcination in the air. In addition, the possible formation mechanism was also proposed. This method is a simple and facile route, which builds a direct linkage between metal-carboxylate MOF crystals and metal nano- or microstructures and also opens a new application field of MOFs.     

Influence of the Base on Pd@MIL‐101‐NH2(Cr) as Catalyst for the Suzuki–Miyaura Cross‐Coupling Reaction

The chemical stability of metal–organic frameworks (MOFs) is a major factor preventing their use in industrial processes. Herein, it is shown that judicious choice of the base for the Suzuki–Miyaura cross‐coupling reaction can avoid decomposition of the MOF catalyst Pd@MIL‐101‐NH₂(Cr). Four bases were compared for the reaction: K₂CO₃, KF, Cs₂CO₃ and CsF. The carbonates were the most active and achieved excellent yields in shorter reaction times than the fluorides. However, powder XRD and N₂ sorption measurements showed that the MOF catalyst was degraded when carbonates were used but remained crystalline and porous with the fluorides. XANES measurements revealed that the trimeric chromium cluster of Pd@MIL‐101‐NH₂(Cr) is still present in the degraded MOF. In addition, the different countercations of the base significantly affected the catalytic activity of the material. TEM revealed that after several catalytic runs many of the Pd nanoparticles (NPs) had migrated to the external surface of the MOF particles and formed larger aggregates. The Pd NPs were larger after catalysis with caesium bases compared to potassium bases.     

Synthesis of Fe3O4@SiO2-Au/Cu magnetic nanoparticles and its efficient catalytic performance for the Ullmann coupling reaction of bromamine acid

Over bimetallic Au/Cu catalyst supported on magnetic Fe₃O₄ nanoparticles, water-mediated bromamine acid could be selectively converted into 4,4'-diamino-1,1'-dianthraquinonyl-3,3'-disulfonic acid (DAS) with a yield of 88.67%. The magnetic catalyst could be readily separated and reused.     

MOF‐on‐MOF: Oriented Growth of Multiple Layered Thin Films of Metal–Organic Frameworks

The precise alignment of multiple layers of metal–organic framework (MOF) thin films, or MOF‐on‐MOF films, over macroscopic length scales is presented. The MOF‐on‐MOF films are fabricated by epitaxially matching the interface. The first MOF layer (Cu₂(BPDC)₂, BPDC=biphenyl‐4,4′‐dicarboxylate) is grown on an oriented Cu(OH)₂ film by a “one‐pot” approach. Aligned second (Cu₂(BDC)₂, BDC=benzene 1,4‐dicarboxylate, or Cu₂(BPYDC)₂, BPYDC=2,2′‐bipyridine‐5,5′‐dicarboxylate) MOF layers can be deposited using liquid‐phase epitaxy. The co‐orientation of the MOF films is confirmed by X‐ray diffraction. Importantly, our strategy allows for the synthesis of aligned MOF films, for example, Cu₂(BPYDC)₂, that cannot be grown on a Cu(OH)₂ surface. We show that aligned MOF films furnished with Ag nanoparticles show a unique anisotropic plasmon resonance. Our MOF‐on‐MOF approach expands the chemistry of heteroepitaxially oriented MOF films and provides a new toolbox for multifunctional porous coatings.     

Near‐Infrared Emission from Tin–Lead (Sn–Pb) Alloyed Perovskite Quantum Dots by Sodium Doping

Phase‐stable CsSn_xPb_1?xI₃ perovskite quantum dots (QDs) hold great promise for optoelectronic applications owing to their strong response in the near‐infrared region. Unfortunately, optimal utilization of their potential is limited by the severe photoluminescence (PL) quenching, leading to extremely low quantum yields (QYs) of approximately 0.3 %. The ultra‐low sodium (Na) doping presented herein is found to be effective in improving PL QYs of these alloyed QDs without alerting their favourable electronic structure. X‐ray photoelectron spectroscopy (XPS) studies suggest the formation of a stronger chemical interaction between I^? and Sn²⁺ ions upon Na doping, which potentially helps to stabilize Sn²⁺ and suppresses the formation of I vacancy defects. The optimized PL QY of the Na‐doped QDs reaches up to around 28 %, almost two orders of magnitude enhancement compared with the pristine one.     

Single‐microemulsion‐based Hydrothermal Approach to In(OH)3 and In2O3 Nanocubes

Well‐defined indium hydroxide [In(OH)₃] nanocubes have been successfully prepared through a facile single‐microemulsion‐mediated hydrothermal process at a relatively low temperature. Calcination of the In(OH)₃ precursor at 400°C in a furnace yielded In₂O₃ crystals with the same morphology. X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FE‐SEM), and transmission electron microscopy (TEM) were used to characterize the samples. The effects of reaction parameters on the formation of nanostructures were also discussed, and the nucleation, aggregation and anisotropic growth mechanism was proposed. Room temperature photoluminescence (PL) spectra as well as the ultraviolet‐visible (UV‐vis) absorbance spectra were carried out on the In₂O₃ crystals to investigate their optical properties.     

超细氧化铜纳米颗粒修饰二维金属有机框架协同增强二氧化碳电化学还原生成乙烯

为了促进CO2电化学还原(ECR)制备燃料和高值化学品,开发高活性、低成本和高选择性催化剂至关重要.本文通过简单的溶剂热法一步合成超细氧化铜(CuO)纳米颗粒修饰的二维Cu基金属有机框架(CuO/Cu-MOF)复合催化剂.并采用X射线衍射、X射线光电子能谱、傅里叶变换红外光谱、高角环形暗场像-扫描透射电镜、N2吸附/脱...     

Synthesis of ω‐fluorenyl‐functionalized soluble polyphenylene: influence of polymer chain structure on photoluminescence quenching

The influence of the polymer chain structure of soluble polyphenylene (SPP) on the photoluminescence (PL) quenching of fluorene is strongly affected by the 1,2‐phenylene (1,2‐Ph)/1,4‐phenylene (1,4‐Ph) unit molar ratios of SPP, and the amount of 1,4‐Ph units is a major factor for PL quenching. The addition of the fluorenyl group by the formation of carbon–carbon bond at the polymer chain end of SPP is also an important factor for PL quenching of fluorene. Charge (electron) transfer from the fluorenyl end‐group to the main chain of ω‐fluorenyl‐functionalized SPP (FL‐SPP) was very efficient. UV/Vis and PL spectra suggested that this FL‐SPP may be useful for preparing an effective polymer photocell. Copyright © 2008 John Wiley & Sons, Ltd.