A review of metal-organic framework (MOF) materials as an effective photocatalyst for degradation of organic pollutants.

Water plays a vital role in all aspects of life. Recently, water pollution has increased exponentially due to various organic and inorganic pollutants. Organic pollutants are hard to degrade; therefore, cost-effective and sustainable approaches are needed to degrade these pollutants. Organic dyes are the major source of organic pollutants from coloring industries. The photoactive metal-organic frameworks (MOFs) offer an ultimate strategy for constructing photocatalysts to degrade pollutants present in wastewater. Therefore, tuning the metal ions/clusters and organic ligands for the better photocatalytic activity of MOFs is a tremendous approach for wastewater treatment. This review comprehensively reports various MOFs and their composites, especially POM-based MOF composites, for the enhanced photocatalytic degradation of organic pollutants in the aqueous phase. A brief discussion on various theoretical aspects such as density functional theory (DFT) and machine learning (ML) related to MOF and MOF composite-based photocatalysts has been presented. Thus, this article may eventually pave the way for applying different structural features to modulate novel porous materials for enhanced photodegradation properties toward organic pollutants.

A mini review on metal-organic framework-based electrode materials for capacitive deionization.

Capacitive deionization (CDI) is an electrochemical method of extracting ions from solution at potentials below electrolysis. It has various applications ranging from water remediation and desalination to heavy metal removal and selective resource recovery. A CDI device applies an electrical charge across two porous electrodes to attract and remove ions without producing waste products. It is generally considered environmentally friendly and promising for sustainability, yet ion removal efficiency still falls short of more established filtration methods. Commercially available activated carbon is typically used for CDI, and its ion adsorption capacity is low at approximately 20-30 mg g-1. Recently, much interest has been in the highly porous and well-structured family of materials known as metal-organic frameworks (MOFs). Most MOFs are poor conductors of electricity and cannot be directly used to make electrodes. A common workaround is to pyrolyze the MOF to convert its organic components to carbon while maintaining its underlying microstructure. However, most MOF-derived materials only retain partial microstructure after pyrolysis and cannot inherit the robust porosity of the parent MOFs. This review provides a systematic breakdown of structure-performance relationships between a MOF-derived material and its CDI performance based on recent works. This review also serves as a starting point for researchers interested in developing MOF-derived materials for CDI applications.

Metal-Organic-Framework-Derived 3D Hierarchical Matrixes for High-Performance Flexible Li-S Batteries.

Lithium-sulfur (Li-S) batteries have shown exceptional theoretical energy densities, making them a promising candidate for next-generation energy storage systems. However, their practical application is limited by several challenging issues, such as uncontrollable Li dendrite growth, sluggish electrochemical kinetics, and the shuttling effect of lithium polysulfides (LiPSs). To overcome these issues, we designed and synthesized hierarchical matrixes on carbon cloth (CC) by using metal-organic frameworks (MOFs). ZnO nanosheet arrays were used as anode hosts (CC-ZnO) to enable stable Li plating and stripping. The symmetric cell with CC-ZnO@Li was demonstrated to have enhanced cycling stability, with a voltage hysteresis of ∼25 mV for over 800 h at 1 mA cm-2 and 1 mAh cm-2. To address the cathode challenges, we developed a multifunctional CC-NC-Co cathode host with physical confinement, chemical anchoring, and excellent electrocatalysis. The full cells with CC-ZnO@Li anodes and CC-NC-Co@S cathodes exhibited excellent electrochemical performance, with long cycling life (0.02% and 0.03% capacity decay per cycle when cycling 900 times at 0.5 C and 600 times at 1 C, respectively) and outstanding rate performance (793 mAh g-1 at 4 C). Additionally, the pouch cell based on the flexible CC-ZnO@Li anode and CC-NC-Co@S cathode showed good stability in different bending states. Overall, our study presents an effective strategy for preparing flexible Li and S hosts with hierarchical structures derived from MOF, which can pave the way for high-performance Li-S batteries.

A bifunctionalised Pb-based MOF for iodine capture and dye removal.

A 2-dimensional Pb(II) metal-organic framework, [Pb(bdc)0.5(py-Phen)NO3]n (SM-3), was synthesized under solvothermal conditions using a mixed ligand approach. SM-3 was assembled using dinuclear SBUs [Pb2(COO)2]2-, an oxygen donor H2bdc = 1,4-benzene dicarboxylic acid, and nitrogen donor py-Phen = pyrazino[2,3-f][1,10]-phenanthroline linkers. SM-3 was characterized by elemental analysis, FT-IR, powder-X-ray diffraction, thermal gravimetric analysis, SEM, EDS, TEM, and single-crystal X-ray diffraction techniques. Crystallographic studies confirmed that SM-3 displays a 2D layered structure with unique anagostic (Pb⋯H) interactions. Interestingly, the presence of abundant π-electron-rich rings embellished with free -N donor sites in the framework makes SM-3 an excellent adsorbent that exhibits adsorption performance for iodine and dyes. The experimental results show that SM-3 reversibly adsorbs radioactive iodine in the solution and vapor phases and exhibits selective adsorption performance for hazardous cationic dyes, namely, methylene blue (MB) and rhodamine-B (Rh-B), from aqueous solution. Moreover, the possible mechanism of iodine and dye adsorption was also discussed in detail. Thus, this work is remarkable for coordination chemists to engineer layered MOFs for adsorption purposes and expands their potential characteristics by converting them into 2D MOF nanosheets to further enhance the adsorption of hazardous pollutants for environment protection.

Recent Advances of Silver-Based Coordination Polymers on Antibacterial Applications.

With the continuous evolution of bacteria and the constant use of traditional antibiotics, the emergence of drug-resistant bacteria and super viruses has attracted worldwide attention. Antimicrobial therapy has become the most popular and important research field at present. Coordination Polymer (CP) and/or metal-organic framework (MOF) platforms have the advantages of a high biocompatibility, biodegradability, and non-toxicity, have a great antibacterial potential and have been widely used in antibacterial treatment. This paper reviewed the mechanism and antibacterial effect of three typical MOFs (pure Ag-MOFs, hybrid Ag-MOFs, and Ag-containing-polymer @MOFs) in silver-based coordination polymers. At the same time, the existing shortcomings and future views are briefly discussed. The study on the antibacterial efficacy and mechanism of Ag-MOFs can provide a better basis for its clinical application and, meanwhile, open up a novel strategy for the preparation of more advanced Ag-contained materials with antibacterial characteristics.

Recent advances in Ti-based MOFs in biomedical applications.

Currently, metal-organic frameworks (MOFs), basically inorganic-organic hybrid materials, have gained tremendous attention due to their vast applications. MOFs have shown enormous applications in almost every research field. However, the area of designing MOF materials for their biological applications is still an emerging field that needs attention. Titanium-based metal-organic framework (Ti-MOF) materials are used in many research areas due to their structural advantages, such as small particle size and large effective surface area. On the other hand, they have also shown unique advantages such as good biocompatibility, excellent catalytic oxidation and photocatalytic properties and ease of functionalization. This study reviews the recent research progress on Ti-MOFs in therapeutic areas such as antibacterial, oncology, anti-inflammation, and bone injury, which will provide new directions for further research in this biomedical field. Therefore, this article will help scientists working in the particular field to enhance their understanding of Ti-based MOFs for functional biomedical applications.

Effect of structural variation on enzymatic activity in tetranuclear (Cu4) clusters with defective cubane core.

The stimulus to the modeling of enzyme functioning sites comes from their potential to give insight into the natural enzyme's mechanistic pathways, ascertain the role of that different metal ion in the active site and construct better catalysts motivated by nature. The presence of metal ion leads to the activation of molecular oxygen in the metalloenzymes. The metalloenzymes such as the catechol oxidase (CO) enzyme that oxidizes the catechol to corresponding quinones which eventually protect damage tissues from plant and pathogen. Thus, the design and characterization of catalysts used as selectively and efficiently oxidation reactions have grown to be unique challenges for modern inorganic chemists. In this work, two novel tetranuclear complexes (1 and 2) have been synthesized in excellent yield. The complexes were characterized using various spectroscopic techniques such as FTIR, UV-Visible and PXRD pattern. The structure of 1 and 2 was elucidated by SC-XRD (single crystal X-ray diffraction) analysis. The magnetic study reveals the presence of the antiferromagnetic nature of 1 and 2. Both 1 and 2 shows a very good catecholase-like activity by oxidizing the catechol to analogous quinone in methanolic solution. Thus, a structure-activity relationship can further help us design other substituted tetranuclear complexes with enhanced catecholase like activity.Communicated by Ramaswamy H. Sarma.

Engineered Fe3 triangle for the rapid and selective removal of aromatic cationic pollutants: complexity is not a necessity.

In this study, a low-cost oxo-bridged {Fe3} triangular cluster was constructed based on a benzoate ligand via slow evaporation. The cluster was thoroughly characterized by FTIR and UV-visible spectroscopy, TGA, and PXRD, and the exact structure was elucidated by single-crystal XRD. The formation of C-H⋯π and π-π interactions is responsible for the extra stability of {Fe3} clusters, which further enhances the dye adsorption property. The dye adsorption experiments performed on cationic [methylene blue (MB) and rhodamine-B (Rh-B)] as well as anionic [methyl orange (MO) and congo red (CR)] dyes revealed the ultimate selectivity of the present cluster towards the cationic ones. The {Fe3} cluster exclusively adsorbs the cationic dyes, i.e., MB and Rh-B even in the presence of anionic dyes, i.e., CR and MO. The extra stability, reusability and high efficiency of the {Fe3} molecular ensemble make it an attractive and fascinating material of importance. The kinetics analysis was evaluated employing different kinetics models. Furthermore, the plausible adsorption mechanism was also proposed, which suggests the interplay of cation-π and π-π interactions consolidating the efficient adsorption. Thus, the present work opens new doors for coordination chemists to further tune the structural features to modulate the adsorption/separation capacities of simple low-cost clusters for environmental protection for future efforts.

How to identify a smoker: a salient crystallographic approach to detect thiocyanate content.

There is an increasing demand for monitoring environmental pollutants and the control requires new sensing materials with better sensitivity, selectivity and reliability. In this study, a series of Co7 clusters incorporating various flexible polyhydroxyamine ligands are explored, with the first report of thiocyanate recognition triggered by crystal formation using a Co7 crystal (1). For this, we have fortunately synthesized three new mixed metal Co7 clusters with fascinating structural features. The clusters were characterized by spectroscopic and single crystal X-ray diffraction methods and later by DFT calculations. Due to its better emission spectrum, 1 was further utilized for evaluating its sensing ability towards various anions in water. Surprisingly, 1 shows better quenching ability towards the recognition of SCN- with a better binding constant. The luminescence quenching towards SCN- detection was further verified by the single crystal method, HSAB principle (symbiosis) and theoretical calculations such as DFT studies. The SCXRD data clearly suggest that the Co7 (1) can be converted into Co14 (1a) by direct reaction with NaSCN under ambient conditions. Besides the soft/hard acid-base concept (symbiosis), the energies of formation, and Co-NCS and Co-OH2 bond energies (as unravelled by DFT) are responsible for this transformation. Therefore, 1 can be used as a selective and sensitive sensor for the detection of thiocyanate anions based on the fluorescence amplification and quenching method. Further, the designed cluster has also been utilized to detect anions in human blood samples to differentiate a smoker and a non-smoker. It has been concluded that the samples of smokers have a high degree of thiocyanate (∼12 or 9.5 mg L-1) in comparison to those of non-smokers (2-3 mg L-1). Thus, this kind of cluster material has high potentiality in the field of bio-medical science in future endeavours for identification of the extent of thiocyanate content in smokers.

Role of biologically important imidazole moiety on the antimicrobial and anticancer activity of Fe(III) and Mn(II) complexes.

Currently, most pathogens influencing a number of epidemics outline a notable warning to human health. It has pushed researchers to design new antimicrobial drugs using transition metals that are studied in proceeding fewer years for their antimicrobial properties. Henceforth, in this work, two mononuclear complexes [Imz-H][Fe(pda)2]⋅1⋅3H2O (1) and [Mn(Imz)6]⋅2Cl-⋅2H2O (2) [Imz = imidazole and H2pda = 2,6 pyridine dicarboxylic acid] are isolated and characterized systematically by various spectral and single-crystal XRD studies. The antimicrobial activity of the present hexadentate complexes of Fe(III) and Mn(II) against Gram-positive as well as Gram-negative bacteria is also assessed. Augmented activity against standard isolates of Staphylococcus aureus with a minimum inhibitory concentration (MIC) is observed. Similar activity was also observed toward Escherichia coli, Klebsiella pneumoniae and Listeria monocytogenes. 1 and 2 have excellent bactericidal activity, and no resistant mutant for S. aureus was seen. The compound also unveiled antibiofilm activity and was capable to disrupt significantly the pre-formed biofilms and this property was confirmed by XTT assay experiment. The MTT assay data indicate that 1 and 2 can be used as anticancer agents toward the RAW 64.7 (human macrophage/monocyte) cell line. Further, the molecular docking study reveals that the role of imidazole is very important in the biological activity of these complexes. Moreover, our results suggest that 1 and 2 with its effective anti-microbial, anti-biofilm and cytotoxicity activity can be used to treat bacterial and fungal infections and could be appraised clinically for further applications.Communicated by Ramaswamy H. Sarma.

Metal organic frameworks decorated with free carboxylic acid groups: topology, metal capture and dye adsorption properties.

In this report, metal organic frameworks (MOFs) are designed and tuned for structural variations in order to induce metal capture which in turn directs dye adsorption properties. The three MOFs, Cu-MOF-2COOH, Ni-MOF-COOH and Cd-MOF, are synthesized by employing 1,3,5-benzenetricarboxylic acid (H3-BTC) as the main ligand and 4,4'-dipyridyl (bipy) as the spacer. The MOFs have been characterized using various spectral techniques and single crystal X-Ray studies. A topological analysis using TOPOS Pro reveals that the MOFs possess varying topologies i.e.hcb, hxl, sql and 2C1. Cu-MOF-2COOH and Ni-MOF-COOH contain two and three uncoordinated carboxylic acid groups, respectively, and in Cd-MOF, all three -COOH groups are utilized in bonding. The dye adsorption properties of the MOFs with free carboxylate group(s) were checked and we found that both MOFs are unable to adsorb any of the dyes significantly. The free carboxylate group(s) in the MOFs inspire us to elaborate their metal capturing properties. In different solvents we checked the metal capturing properties of Cu-MOF-2COOH and Ni-MOF-COOH with different metal salts. Surprisingly, both MOFs show better metal capturing properties towards the hard and highly polarizing Fe3+ ion in aqueous medium. Theoretical studies show that the free carboxylate(s) are involved in binding with metals. The post synthetically modified materials (Fe@Cu-MOF-2COOH and Fe@Ni-MOF-COOH) were further checked for their dye adsorption properties and both the doped MOFs show better adsorption properties towards the MB and MO. Furthermore, three kinetic models were employed to understand the reaction mechanism of adsorption and the pseudo second order kinetic model fits the best in both cases. The uncoordinated carboxylate groups in the channels act as post synthetic modification sites for metal capture and the post synthetically modified material thus formed attracts organic dyes following the HSAB concept. The strong interaction existing between the hard Fe3+ ion and hard donors of the dyes is responsible for the enhanced adsorption.

Three-in-one is really better: exploring the sensing and adsorption properties in a newly designed metal-organic system incorporating a copper(ii) ion.

A 2-D copper(ii)-based coordination polymer, [Cu(SCN)(hmp)]n CP (1), was crystallized via the slow evaporation method after the reaction of CuSO4·5H2O, 2-pyridinemethanol (hmpH), sodium thiocyanate and sodium hydroxide in water for functional applications. CP (1) was characterized via elemental analysis, FTIR, PXRD, magnetic, EPR, crystallographic and TGA studies. The crystal structure and EPR data confirmed a square pyramidal geometry around the Cu(ii) ions. The topological analysis revealed that CP 1 has a {6^3} point symbol with a [6.6.6] extended point symbol and 3-c net, uninodal net having hcb and Shubnikov hexagonal plane net/(6,3) type of uncommon topology. The magnetic studies suggested the strong antiferromagnetic nature of CP (1). The fluorescence sensing property of CP (1) was investigated with different nitro aromatic compounds and hazardous metal ions. CP (1) demonstrated high selectivity and sensitivity towards nitrobenzene, even in the presence of other competitive nitro aromatics. In addition, CP (1) showed excellent selectivity and sensitivity toward Fe3+ over other metal ions. The possible detection mechanisms were proposed employing UV-visible and fluorescence spectroscopy and DFT calculations. CP (1) also showed excellent recyclability towards both analytes, and its initial intensity was almost regained after several washings. Moreover, CP (1) acted as an excellent adsorbent material for natural dyes with different charges and sizes, i.e., methylene blue (MB), methyl orange (MO) and Rhodamine-B. Furthermore, CP (1) was utilized repeatedly for the effective adsorption of MB from wastewater without significant loss in its adsorption capacity. Hence, the present CP (1) was designed to relate coordination chemistry with various functional applications of interest.

Two dimensional α-MoO3-x nanoflakes as bare eye probe for hydrogen peroxide in biological fluids.

We report a rapid and facile method for detection of hydrogen peroxide (H2O2) in biological fluids using sub-stoichiometric two-dimensional (2D) molybdenum trioxide (α-MoO3-x) nanoflakes. The two-dimensional nanoflakes, initially blue in color, is oxidized after interaction with hydrogen peroxide thereby changing its oxidation state to form α-MoO3. The change in oxidation state of nanoflakes transforms from blue to a visually distinct hazy blue color with change in absorption spectrum. The phenomenal property is explored here in sensing up to 34 nM as limit of detection. The efficacy of the detection system was analyzed by "zone of inhibition" based agar diffusion assay with different concentrations of H2O2. The current approach is highly accurate, effective and reproducible for quantification of physiological concentration of H2O2 in biological fluid such as human urine.

Graphene oxide@gold nanorods for chemo-photothermal treatment and controlled release of doxorubicin in mice Tumor.

Graphene oxide (GO) is a close derivative of graphene has unlocked many pivotal steps in drug delivery due to their inherent biocompatibility, excellent drug loading capacity, and shows antibacterial, antifungal properties etc. We used a novel plant material called Gum arabic (GA) to increase the solubility of GO as well as to chemically reduce it in the solution. GA functionalized GO (fGO) exhibited increased absorption in near infra-red region (NIR) which was exploited in photothermal therapy for cancer. In order to understand the shape and size effect of GO which may affect their rheological properties, we have conjugated them with gold nanorods (GNRs) using in situ synthesis of GO@GNRs via seed mediated method. To the above conjugate, Doxorubicin (DOX) was attached at ambient temperature (28±2°C). The release kinetics of DOX with the effect of NIR exposure was also carefully studied via in vitro photothermal killing of A549 cell lines. The enhancement in NIR induced drug release and photothermal property was observed which indicates that the fGO@GNRs-DOX method is an ideal choice for chemotherapy and photothermal therapy simultaneously.

Folic Acid navigated Silver Selenide nanoparticles for photo-thermal ablation of cancer cells.

Photothermal ablation of the cancer cells is a non-invasive technique for cancer treatment, involving cellular assassination in presence of photothermal agent. We are reporting silver selenide (Ag2Se) nanoparticles for photothermal therapy using folic acid for selective targeting. The material, when exposed to 808nm laser, the temperature got boosted to 54°C in 6.5min, thus proving its potential for photothermal ablation. The material was highly biocompatible (95%) at highest concentration (10µg/mL) against A 549 cells. However, in presence of laser, the cellular killing was 55%. The mode of death was analyzed using MALDI-TOF MS.

Fluorimetric detection of pathogenic bacteria using magnetic carbon dots.

A novel and facile approach of pathogenic bacteria detection, which utilizes fluorescent sensing and bacteria capture with Magnetic carbon dots (Mag-CDs), was proposed in this work. Magnetic nanoparticles were synthesized and then decorated with C-dots, and further functionalized with amine groups (chitosan). In this way, bacteria were strongly anchored on the hybrid material Mag-CDs for highly sensitive fluorescent detection. The Mag-CDs were characterized by UV-vis, FT-IR spectra, TEM images, XRD, and EDX. The characterizations validate the fabrication of amine-Mag-CDs and the promising applications of this material. Fluorescence spectroscope and MALDI-MS were used for the detection and identification of bacterial strains, respectively. The limit of detection for Staphylococcus aureus and Escherichia coli was found to be 3 × 10(2) and 3.5 × 10(2) cfu mL(-1), respectively. With these encouraging results, it is expected that it would open revenues for promising applications of Mag-CDs nanomaterial.

MALDI MS analysis, disk diffusion and optical density measurements for the antimicrobial effect of zinc oxide nanorods integrated in graphene oxide nanostructures.

Graphene oxide-zinc oxide hybrid nanostructures were synthesized and they demonstrated significant and promising antimicrobial activity on pathogenic bacteria. The combination of graphene oxide with zinc oxide nanorods showed an impressive antibacterial effect under intense scrutiny as compared with individual graphene oxide or zinc oxide nanomaterials. The characterization and investigation of GO-ZnO nanorod hybrid nanostructures were conducted using UV, FTIR, XRD, SEM, EDX and TEM measurements. The antimicrobial activity of the above hybrid material was evaluated by various methods including MALDI-MS analysis, a disk diffusion assay and optical density measurements.

Controlled delivery of dopamine hydrochloride using surface modified carbon dots for neuro diseases.

Delivery of therapeutic agents using water-soluble, highly biocompatible Carbon dots (C-dots) is an efficient strategy to control drug release under physiological milieu. Dopamine hydrochloride (DA), the most important inotropic vasopressor agent used in neurological diseases. In our study DA is anchored to water-soluble carbon dots for controlled release under mimicked in vitro physiological conditions. The tenure of the DA release at pH 7.4 was greatly extended to 60 h for C-dots-DA, in comparison with the control DA alone. The statistical calculation was used to comprehend the release pattern of the DA, which exhibited the pattern of Hixson-Crowell model of release. In order to understand the impact of the C-dots-DA conjugate under physiological conditions, Neuro 2A cells were taken under consideration. The conjugate C-dots-DA was found to be biocompatible against Neuro 2A cells. The survival rate was found to be 74% at maximum concentration of 9 µg mL(-1). In vivo toxicity was studied using thin section of tissues after staining with Hematoxyline and Eosin Yellow (H&E). As per microscopic observations, conjugates did not inflict any anatomical distortions or hostile effects on tissues. Body weight of mice was also taken into consideration after injecting 20 µg mL(-1) of nano-conjugates via tail vein. The impact of nano-conjugate on body weight was found to be negligible after 45 days of observation.

Design, characterization and applications of new ionic liquid matrices for multifunctional analysis of biomolecules: a novel strategy for pathogenic bacteria biosensing.

The design, preparation and performance for novel UV-light absorbing (room-temperature) ionic liquid matrices (UV-RTILMs) for matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) were reported. A series of UV-RTILMs was prepared by ultrasonication of equimolar of acid (mefenamic acid) and bases (aniline (ANI), pyridine (Pyr), dimethyl aniline (DMANI) and 2-methyl picoline (2-P)). The UV-RTILMs have not only significant absorbance at the desired wavelength (337 nm of the N2 Laser), but also have available protons that can easily undergo proton transfer reactions to ionize the target molecules. The novel UV-RTILMs have the ability to ionize different and wide classes of compounds such as drugs, carbohydrate, and amino acids. The new UV-RTILMs series have been successfully and selectively applied for biosensing the lysates of pathogenic bacteria in the presence of the cell macromolecules. A new strategy for biosensing pathogens was presented via sensing the pathogens lysate in the cell suspension. The new materials can effectively detect the bacterial toxins without separation or any pretreatment. They offered excellent ionization of labile oligosaccharides with protonated peaks. They could significantly enhance the analyte signals, produce homogeneous spotting, reducing spot-to-spot variation, excellent vacuum stability, higher ion peak intensity, and wide application possibility. The physical parameters such as molar refractivity, molar volume, parachor, surface tension, density and polarizability were calculated and tabulated. The new UV-RTILMs could offer excellent reproducibility and great repeatability and they are promising matrices for wide applications on MALDI-MS.