TY - JOUR A1 - Halder, A. A1 - Maiti, A. A1 - Dinda, S. A1 - Bhattacharya, Biswajit A1 - Ghoshal, D. T1 - Unraveling the Role of Structural Dynamism in Metal Organic Frameworks (MOF) for Excited-State Intramolecular Proton Transfer (ESIPT) Driven Water Sensing N2 - Ligand based modification has been performed to synthesize a pair of mixed ligands d10 MOF based materials related to a previously published compound as a base material. The previous compound was a Zn(II)-MOF, {[Zn(4-bpdh)(H2dht)](MeOH)(H2O)}n (1) [N,N′-bis(1-pyridin-4-yl-ethylidene)hydrazine = 4-bpdh and 2,5-dihydroxyterephthalic acid = H4dht], which is a five-fold interpenetrated framework and highly dynamic in nature. In the first synthetic modification, the central metal is replaced by Cd(II), which has the same framework formula as the base material, but this is a rigid compound and also there is no interpenetration in the framework. In the second modification, along with the metal center, the 4,4′- coordinating N,N′-donor ligand is replaced by an isomeric 3,3′-coordinating N,N′- donor linker. In this compound, the dynamism is regenerated. The dynamic nature can be realized by the extensive PXRD studies and characteristic “step-shaped” gas/solvent adsorption behavior for CO2, water, and ethanol. Furthermore, all these 3D MOFs show excited-state intramolecular proton transfer phenomena and water sensing properties in different organic solvents. Here excitingly, the ease of water sensing property is directly related to the dynamic behavior of the framework which has been studied thoroughly in terms of structural correlation. KW - MOFs PY - 2021 DO - https://doi.org/10.1021/acs.cgd.1c00446 SN - 1528-7483 VL - 21 IS - 11 SP - 6110 EP - 6118 PB - ACS Publications AN - OPUS4-53903 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lisec, Jan A1 - Hoffmann, F. A1 - Jaeger, C. A1 - Bhattacharya, A. A1 - Schmitt, C. A. T1 - Nontargeted Identification of Tracer Incorporation in High- Resolution Mass Spectrometry N2 - “Fluxomics” refers to the systematic analysis of metabolic fluxes in a biological system and may uncover novel dynamic properties of metabolism that remain undetected in conventional metabolomic approaches. In labeling experiments, tracer molecules are used to track changes in the isotopologue distribution of metabolites, which allows one to estimate fluxes in the metabolic network. Because unidentified compounds cannot be mapped on pathways, they are often neglected in labeling experiments. However, using recent developments in de novo annotation may allow to harvest the information present in these compounds if they can be identified. Here, we present a novel tool (HiResTEC) to detect tracer incorporation in high-resolution mass spectrometry data sets. The software automatically extracts a comprehensive, nonredundant list of all compounds showing more than 1% tracer incorporation in a nontargeted fashion. We explain and show in an example data set how mass precision and other filter heuristics, calculated on the raw data, can efficiently be used to reduce redundancy and noninformative signals by 95%. Ultimately, this allows to quickly investigate any labeling experiment for a complete set of labeled compounds (here 149) with acceptable false positive rates. We further re-evaluate a published data set from liquid chromatography-electrospray ionization (LC-ESI) to demonstrate broad applicability of our tool and emphasize importance of quality control (QC) tests. HiResTEC is provided as a package in the open source software framework R and is freely available on CRAN. KW - Fluxomics KW - R package KW - Mass-Spectrometry PY - 2018 DO - https://doi.org/10.1021/acs.analchem.8b00356 VL - 90 IS - 12 SP - 7253 EP - 7260 PB - ACS Publications AN - OPUS4-45493 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bhattacharya, Biswajit A1 - Das, S. A1 - Lal, G. A1 - Soni, S. R. A1 - Ghosh, A. A1 - Reddy, C. M. A1 - Ghosh, S. T1 - Screening, crystal structures and solubility studies of a series of multidrug salt hydrates and cocrystals of fenamic acids with trimethoprim and sulfamethazine N2 - Multidrug solids have a potential use to efficiently treat and control a superfluity of medical conditions. To address the current drawbacks of drug development in R&D, it was targeted to achieve new pharmaceutical solid forms of fenamic acids having improved solubility and thermal stability. Subsequently, five new multicomponent solids consisting of three salt hydrates of trimethoprim (TMP) with mefenamic acid (TMP-MFA-H2O), tolfenamic acid (TMP-TFA-H2O) and flufenamic acid (TMP-FFA-H2O), and two cocrystals of sulfamethazine (SFZ) with flufenamic acid (SFZ-FFA) and niflumic acid (SFZ-NFA) were prepared by liquid assisted grinding. Looking at the structures of active pharmaceutical ingredient (API) molecules, it was quite expected that a wide range of supramolecular synthons would lead to cocrystallization. New forms were characterized thoroughly by various solid-state techniques, including single crystal X-ray diffraction (SCXRD), which provided details of hydrogen bonding, molecular packing and interactions between drug and coformer. Kinetic solubility at pH 7.4 buffer study has been carried out and a comparison is made with respect to the parent drugs. A significant enhancement of NSAIDs solubility was observed in all salt hydrate systems of TMP. Thus with increasing physicochemical properties such as improved solubility further leads to the enhancement of bioavailability, which has implications to overcoming the formulation related problems of active pharmaceutical ingredients (APIs). KW - Cocrystals KW - Crystal engineering KW - Solubility PY - 2020 DO - https://doi.org/10.1016/j.molstruc.2019.127028 SN - 0022-2860 VL - 1199 SP - 127028 PB - Elsevier B.V. AN - OPUS4-49873 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pakrashy, S. A1 - Mandal, P. K. A1 - Goswami, J. N. A1 - Dey, S. K. A1 - Choudhury, S. M. A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Alasmary, F. A. A1 - Dolai, M. T1 - Bioinformatics and Network Pharmacology of the First Crystal Structured Clerodin: Anticancer and Antioxidant Potential against Human Breast Carcinoma Cell N2 - Clerodin was isolated from the medicinal plant Clerodendrum infortunatum, and CSD search showed the first crystal structure of clerodin by a single-crystal X-ray diffraction study. We checked its binding potential with target proteins by docking and conducted network pharmacology analysis, ADMET analysis, in silico pathway analysis, normal mode analysis (NMA), and cytotoxic activity studies to evaluate clerodin as a potential anticancer agent. The cell viability studies of clerodin on the human breast carcinoma cell line (MCF-7) showed toxicity on MCF-7 cells but no toxicity toward normal human lymphocyte cells (HLCs). The anticancer mechanism of clerodin was validated by its enhanced capacity to produce intracellular reactive oxygen species (ROS) and to lower the reduced glutathione content in MCF-7 cells. KW - Anticancer KW - Clerodin PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-567600 DO - https://doi.org/10.1021/acsomega.2c07173 SN - 2470-1343 VL - 7 IS - 51 SP - 48572 EP - 48582 PB - ACS Publ. CY - Washington, DC AN - OPUS4-56760 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Goswami, Juli Nanda A1 - Haque, Najirul A1 - Seikh, Asiful H. A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Bar, Nimai A1 - Ifseisi, Ahmad A. A1 - Biswas, Surajit A1 - Dolai, Malay T1 - Carboxylative cyclization of propargyl alcohols with carbon dioxide for the synthesis of α-alkylidene cyclic carbonates in presence of Co(III) schiff base complex catalyst N2 - A cobalt(III) complex, [Co(L)3](DMF) (1) of Schiff base ligand HL, 2-((E)-(benzylimino)methyl)-4-bromophenol is prepared and single crystal X-ray structural analysis have also been performed. The structures of complex 1 showed hexa-coordinated mononuclear systems that adopt octahedral geometry. The complex has also exhibited the supramolecular networks through non-covalent interactions like H-bonding, C–Hπ stacking. Moreover, the complex 1 is very effective in the catalytic fixation of carbon dioxide in propergyl alcohols to produce α-alkylidene cyclic carbonates. The catalytic production of α-alkylidene cyclic carbonates have been carried out through carboxylative cyclization of propargyl alcohols using CO2 balloon of 1 atm pressure at 80 ◦C. Solvent free condition (green synthesis) made this catalytic protocol eco-friendly towards the environment. Utilizing various substrates of propargyl alcohols moderate to high percentage yield (62–95%) of respective α-alkylidene cyclic carbonates product have been isolated over this catalytic reaction. Besides, the theoretical calculations (DFT) was performed for the prediction of probable mechanism of the catalytic reaction KW - Catalytic fixation of carbon dioxide KW - Carboxylative cyclization of propargyl alcohols KW - Cobalt (III) Schiff base complex KW - X-ray crystal analysis PY - 2024 DO - https://doi.org/10.1016/j.molstruc.2023.136868 SN - 0022-2860 VL - 1296 IS - Part 1 SP - 1 EP - 8 PB - Elsevier B.V. AN - OPUS4-58947 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dolai, Malay A1 - Saha, Urmila A1 - Goswami, Juli Nanda A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Ifseisi, Ahmad A. A1 - Biswas, Surajit ED - Bhattacharya, Biswajit T1 - Nickel(II)-mediated in situ complex formation with unexpected ligand transformations: crystal structures, DFT calculations, and catalytic activity in CO2 fixation reactions N2 - Two transformed ligands, namely 1,3,5-triazapentadienato(imidoylamidinato) and N-(methoxy(pyrimidin-2-yl)(pyrimidine-2-carboxamido)methyl)pyrimidine-2-carboxamide, are reported here as the first products derived from 2-cyano pyridine/pyrimidine, respectively, under nickel metal mediation in the presence of hydroxylamine hydrochloride in situ. Two different nickel-coordinated complexes (1 and 2) were formed. Single crystal X-ray diffraction revealed that complex 1 is a mononuclear complex with tetra-coordinated square planar geometry, whereas complex 2 is a dinuclear complex with hexa-coordinated distorted octahedral geometry. The synthetic pathways of both transformed ligands are explained with the support of energy calculations of different states via density functional theory (DFT) calculations. The catalytic addition reactions of epoxides and carbon dioxide efficiently produce organic cyclic carbonates in the presence of complexes 1–2, attributed to the presence of Lewis acidic nickel and Lewis basic centers, such as free amine, imine, methoxy, or nitrogen in complexes 1 and 2. Under mild reaction conditions (1 atm CO2 pressure and 60 °C temperature), different types of epoxides (exocyclic, endocyclic, and aromatic epoxides) yield high levels of respective cyclic carbonates in the presence of both complexes 1–2 as catalysts, with tert-butylammonium bromide (TBAB) acting as a co-catalyst. The high turnover number (TON) and turnover frequency (TOF) of these catalytic reactions clearly indicate the efficacy of the two catalysts. KW - Catalytic activity in CO2 fixation reactions DFT calculations KW - Nickel(II)-complex KW - In situ complex formation KW - Crystal Structure PY - 2025 DO - https://doi.org/10.1039/d4nj01801j SN - 1369-9261 VL - 49 IS - 11 SP - 4451 EP - 4463 PB - Royal Society of Chemistry (RSC) AN - OPUS4-62782 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ravi, J. A1 - Feiler, Torvid A1 - Mondal, A. A1 - Michalchuk, Adam A1 - Reddy, C. M. A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Chandrasekar, R. T1 - Plastically bendable organic crystals for monolithic and hybrid micro-optical circuits N2 - Fluorescent plastically bendable crystals are a promising alternative to silicon-based materials for fabricating photonic integrated circuits, owing to their optical attributes and mechanical compliance. Mechanically bendable plastic organic crystals are rare. Their formation requires anisotropic intermolecular interactions and slip planes in the crystal lattice. This work presents three fluorescent plastically bendable crystalline materials namely, 2-((E)-(6-methylpyridin-2-ylimino)methyl)-4-chlorophenol (SB1), 2-((E)-(6-methylpyridin-2-ylimino)methyl)-4-bromophenol (SB2), and 2-((E)-(6-Bromopyridin-2-ylimino)methyl)-4-bromophenol (SB3) molecules. The crystal plasticity in response to mechanical stress facilitates the fabrication of various monolithic and hybrid (with a tip-to-tip coupling) photonic circuits using mechanical micromanipulation with an atomic force microscope cantilever tip. These plastically bendable crystals act as active (self-guiding of fluorescence) and passive waveguides both in straight and extremely bent (U-, J-, and O-shaped) geometries. These microcircuits use active and passive waveguiding principles and reabsorbance and energy-transfer mechanisms for their operation, allowing input-selective and direction-specific signal transduction. KW - Flexible crystals KW - Flexible waveguide PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565302 DO - https://doi.org/10.1002/adom.202201518 SN - 2195-1071 SP - 1 EP - 10 PB - Wiley-VCH CY - Weinheim AN - OPUS4-56530 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bhattacharya, Biswajit A1 - Michalchuk, Adam A1 - Silbernagl, Dorothee A1 - Rautenberg, Max A1 - Schmid, Thomas A1 - Feiler, Torvid A1 - Reimann, K. A1 - Ghalgaoui, A. A1 - Sturm, Heinz A1 - Paulus, B. A1 - Emmerling, Franziska T1 - A Mechanistic Perspective on Plastically Flexible Coordination Polymers N2 - Mechanical flexibility in single crystals of covalently bound materials is a fascinating and poorly understood phenomenon. We present here the first example of a plastically flexible one-dimensional (1D) coordination polymer. The compound [Zn(m-Cl)2(3,5-dichloropyridine)2]n is flexible over two crystallographic faces. Remarkably, the single crystal remains intact when bent to 1808. A combination of microscopy, diffraction, and spectroscopic studies have been used to probe the structural response of the crystal lattice to mechanical bending. Deformation of the covalent polymer chains does not appear to be responsible for the observed macroscopic bending. Instead, our results suggest that mechanical bending occurs by displacement of the coordination polymer chains. Based on experimental and theoretical evidence, we propose a new model for mechanical flexibility in 1D coordination polymers. Moreover, our calculations propose a cause of the different mechanical properties of this compound and a structurally similar elastic material KW - Coordination polymer KW - Flexible crystals KW - Mechanical properties KW - Plastic deformation PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-504755 DO - https://doi.org/10.1002/anie.201914798 VL - 59 IS - 14 SP - 5557 EP - 5561 PB - Wiley-VCH AN - OPUS4-50475 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rodríguez-Sánchez, Noelia A1 - Prinz, Carsten A1 - Bienert, Ralf A1 - Ballesteros, Menta A1 - Ruiz Salvador, A. Rabdel A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska T1 - Mechanochemical ZIF-9 formation: in situ analysis and photocatalytic enhancement evaluation N2 - Efficient treatment of persistent pollutants in wastewater is crucial for sustainable water management and environmental protection. This study addresses this challenge by investigating the mechanochemical synthesis and photocatalytic performance of ZIF-9, a cobalt-based zeolitic imidazolate framework. Using synchrotron-based powder X-ray diffraction, we provide real-time insights into the formation dynamics of ZIF-9 during mechanosynthesis. Our results show that mechanochemically synthesised ZIF-9 exhibits superior photocatalytic activity compared to its solvothermally prepared counterpart, achieving a 2-fold increase in methylene blue degradation rate. This research not only advances our understanding of the synthesis and properties of ZIF-9, but also demonstrates the potential of mechanochemical approaches in the development of high-performance, sustainably produced materials for water treatment and other environmental applications. KW - MOFs KW - ZIF KW - Time-resolved in situ investigation KW - Photocatalysis synchrotron X-ray powder diffraction PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641416 DO - https://doi.org/10.1039/D4MR00114A SN - 2976-8683 VL - 2 IS - 1 SP - 116 EP - 126 PB - Royal Society of Chemistry (RSC) CY - Cambridge AN - OPUS4-64141 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rodríguez-Sánchez, Noelia A1 - Domínguez-Santos, J. Enrique A1 - Bhattacharya, Biswajit A1 - Prinz, Carsten A1 - Canosa, Inés A1 - Flores, Amando A1 - Jiménez-Rodríguez, Antonia A1 - Ruiz-Salvador, A. Rabdel A1 - Emmerling, Franziska A1 - Ballesteros, Menta T1 - Mechanochemical synthesis of multivariate UPO-3 (Cu-ZIF-9-ica) MOF for inactivation of antibiotic-resistant bacteria and irrigation-quality water production via heterogeneous photo-Fenton catalysis N2 - Water scarcity and pollution are critical global challenges, particularly in agriculture, the largest consumer of water. The development of sustainable, effective, and environmentally friendly disinfection methods is essential to address the risks posed by antibiotic-resistant bacteria and to ensure safe reuse of water for irrigation. In this study, we report the synthesis of the metal-organic framework (MOF) Universidad Pablo de Olavide-3 (UPO-3) via a mechanochemical approach, a scalable and sustainable method compared to traditional solvothermal synthesis. The resulting UPO-3/H2O2 system exhibits robust photocatalytic properties under visible light, achieving effective and broad-spectrum antibacterial activity. The disinfection efficiency of the catalyst was evaluated against Escherichia coli as a model of microbial pathogen in two saline matrices, considering the key parameters of the heterogeneous photo-Fenton process, including catalyst dosage, initial H2O2 concentration, and light irradiation. Notably, it inactivated two important virulent and antibiotic-resistant bacterial pathogens (Staphylococcus aureus and Pseudomonas aeruginosa). Furthermore, UPO-3 shows exceptional performance under real-world conditions, such as river water disinfection, achieving >5-log reduction of E. coli, fulfilling a critical criterion for Class A water reuse under Regulation (EU) 2020/741. These results highlight UPO-3 as a versatile and sustainable solution for water reuse, addressing water scarcity and advancing efforts to achieve United Nations Sustainable Development Goal 6. KW - Water reuse KW - Antibiotic-resistant bacteria KW - Water disinfection KW - Mechanochemical synthesis KW - Metal organic framework PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639766 DO - https://doi.org/10.1016/j.chemosphere.2025.144610 SN - 0045-6535 VL - 386 SP - 1 EP - 11 PB - Elsevier Ltd. AN - OPUS4-63976 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kumari, N. A1 - Bhattacharya, Biswajit A1 - Roy, P. A1 - Michalchuk, Adam A1 - Ghosh, A. A1 - Emmerling, Franziska T1 - Enhancing the Pharmaceutical Properties of Pirfenidone by Mechanochemical Cocrystallization N2 - Pirfenidone is an important drug molecule used in the treatment of idiopathic lung fibrosis. Although approved by the USFDA in 2014, pirfenidone’s aqueous solubility is too high and must be mitigated by additives. In this work, the cocrystallization of pirfenidone is explored as an alternative approach to reducing its solubility. Herein, an anhydrous form of pirfenidone is reported, alongside its first two reported cocrystals. The new crystalline solids are thoroughly characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction analysis (PXRD), Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Equilibrium solubility and intrinsic dissolution rates (IDR) are studied for the cocrystals and compared to that of the parent drug. Both cocrystal forms exhibit drastically lower aqueous solubility (by up to 90%) and dissolution rates, rationalized based on both lattice energy calculations and consideration of intermolecular interactions in the solid state. Furthermore, we compare the physicochemical properties of solution-based material with that of material produced mechanochemically. Importantly, no differences are observed between the two production methods. This work demonstrates the strength of crystal Engineering strategies to beneficially modify important pharmaceutical properties and highlights the potential of mechanochemistry to facilitate this in an environmentally benign way. KW - Mechanochemistry PY - 2019 DO - https://doi.org/10.1021/acs.cgd.9b00932 VL - 19 IS - 11 SP - 6482 EP - 6492 PB - ACS Publications AN - OPUS4-49828 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rodríguez-Sánchez, Noelia A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska A1 - Prinz, Carsten A1 - Prieto-Laria, P. A1 - Ruiz-Salvador, A.R. A1 - Ballesteros, M. T1 - Engineering a multivariate cobalt metal–organic framework for high photocatalytic activity: the impact of mixed ligands and metal incorporation in a visible light-driven heterogeneous photo-Fenton reaction for water treatment N2 - Metal–organic frameworks (MOFs) have attracted increasing attention for the removal of organic pollutants in wastewater via photocatalysis. Here, we design a multivariate modification of ZIF-9 to tune its electronic properties for use in visible light photocatalysis. A controllable synthesis of ZIF-9 and its multivariate forms with the incorporation of copper and the 2-imidazolecarboxaldehyde (ica) ligand was carried out. The materials are tested for the removal of the model dye methylene blue (MB) by a heterogeneous photo-Fenton-like reaction at neutral pH and room temperature. Cu-ZIF-9-ica (UPO-3) shows high photocatalytic activity under both visible and ultraviolet A (UVA) light, achieving 94% MB degradation in 45 min, compared to 65% MB degradation in 120 min using bare ZIF-9. The study revealed a first-order rate constant of 0.0475 min−1 for Cu-ZIF-9-ica compared to 0.0088 min−1 for ZIF-9 under visible light. The improvement of the catalyst was clearly attributed to the co-incorporation of Cu and the ica ligand in the MOF, which reduces the band gap, in agreement with DFT calculations. Reproducibility and recyclability tests proved that Cu-ZIF-9-ica can be used for at least 3 cycles without a significant loss of efficiency, making it a promising material for the study and application of wastewater treatment. KW - Metal-Organic Framework (MOF) KW - Heterogeneous photo-Fenton KW - ZIF-9 KW - Methylene Blue PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630797 DO - https://doi.org/10.1039/d4na00954a SN - 2516-0230 VL - 7 IS - 8 SP - 2255 EP - 2265 PB - Royal Society of Chemistry AN - OPUS4-63079 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -