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1. Nitro Indole Derivatives as Novel Dual-Polarity Matrices for MALDIMass Spectrometry and Imaging with Broad Applications

   https://doi.org/10.1021/acs.analchem.3c04684  

   Liang, Q; Mondal, P; Li, Q; Maqbool, T; Zhao, C; Jiang, D; Szulczewski, G J; Wijeratne, G B (January 2024, Analytical Chemistry)

   A new matrix framework is presented in this studyfor the improved ionization efficiency of complex mixtures by matrix-assisted laser desorption ionization (MALDI) mass spectrometry/imaging. Five nitro indole (NI) derivatives [3-methyl-4-nitro-1H-indole (3,4-MNI), 3-methyl-6-nitro-1H-indole(3,6-MNI), 2,3-dimethyl-4-nitro-1H-indole (2,3,4-DMNI), 2,3-dimethyl-6-nitro-1H-indole (2,3,6-DMNI), and 4-nitro-1H-indole(4-NI)] were synthesized and shown to produce both positive and negative ions with a broad class of analytes as MALDI matrices. NI matrices were compared to several common matrices, such as 2,5-dihydroxybenzoic acid (DHB), alpha-cyano-4-hydroxylcinnamicacid (CHCA), sinapinic acid (SA), 1,5-diaminonaphthelene (1,5-DAN), and 9-aminoacridine (9-AA), for the analysis of lipid, peptide, protein, glycan, and perfluorooctanesulfonic acid (PFOS) compounds. 3,4-MNI demonstrated the best performance among the NI matrices. This matrix resulted in reduced ion suppression and better detection sensitivity for complex mixtures, for example, egg lipids/milk proteins/PFOS in tap water, while 2,3,6-DMNI was the best matrix for blueberry tissue imaging. Several important aspects of this work are reported: (1) dual-polarity ion production with NI matrices and complex mixtures; (2) quantitative analysis of PFOS with a LOQ of 0.5 ppb in tap water and 0.05 ppb in MQ water (without solid phase extraction enrichment), with accuracy and precision within 5%; (3) MALDI imaging with 2,3,6-DMNI as a matrix for plant metabolite/lipid identification with ionization enhancement in the negative ion mode m/z 600−900 region; and (4) development of a thin film deposition under/above tissue method for MALDI imaging with a vacuum sublimation matrix on a high-vacuum MALDI instrument. 

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2. A structural and computational comparison of close contacts and related intermolecular energies of interaction in the structures of 1,3-diiodo-5-nitrobenzene, 1,3-dibromo-5-nitrobenzene, and 1,3-dichloro-5-nitrobenzene

   https://doi.org/10.1107/S2053229622009275  

   Bosch, Eric; Bowling, Nathan P.; Speetzen, Erin D. (October 2022, Acta Crystallographica Section C Structural Chemistry)

   1,3-Diiodo-5-nitrobenzene, C₆H₃I₂NO₂, and 1,3-dibromo-5-nitrobenzene, C₆H₃Br₂NO₂, crystallize in the centrosymmetric space groupP2₁/m, and are isostructural with 1,3-dichloro-5-nitrobenzene, C₆H₃Cl₂NO₂, that has been redetermined at 100 K for consistency. While the three-dimensional packing in all three structures is similar, the size of the halogen atom affects the nonbonded close contacts observed between molecules. Thus, the structure of 1,3-diiodo-5-nitrobenzene features a close Type 1 I...I contact, the structure of 1,3-dibromo-5-nitrobenzene features a self-complementary nitro-O...Br close contact, while the structure of 1,3-dichloro-5-nitrobenzene also has a self-complementary nitro-O...Cl interaction, as well as a bifurcated C—H...O(nitro) close contact. Notably, the major energetically attractive intermolecular interaction between adjacent molecules in each of the three structures corresponds to a π-stacked interaction. The self-complementary halogen...O(nitro) and C—H...O(nitro) interactions correspond to significant cohesive attraction between molecules in each structure, while the Type 1 halogen–halogen contact is weakly cohesive. 

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3. Unraveling the origin of the “Turn-On” effect of Al-MIL-53-NO ₂ during H ₂ S detection

   https://doi.org/10.1039/C9CE01595G  

   Zhu, Zan; He, Xiang; Wang, Wei-Ning (January 2020, CrystEngComm)

   Nitro-functionalized metal–organic frameworks (MOFs), such as Al-MIL-53-NO 2 , have been widely used in quantitative hydrogen sulfide (H 2 S) detection based on the “turn-on” effect, where fluorescence enhancements were observed upon contact with H 2 S. This was believed to be caused by the fact that the electron-withdrawing –NO 2 groups in the initial non-luminescent MOFs were reduced to electron-donating –NH 2 groups in the sensing process. However, since most H 2 S detection is conducted in a suspension system consisting of MOFs and solvents, it is still unclear whether these –NH 2 groups are on MOFs or in the liquid. Using Al-MIL-53-NO 2 as a model MOF, this work aims to answer this question. Specifically, the supernatant and undissolved particles separated from the Al-MIL-53-NO 2 suspensions after being exposed to H 2 S were analyzed systematically. The results showed that it is the free BDC-NH 2 (2-aminobenzene-1,4-dicarboxylic acid) in the solution rather than the formation of Al-MIL-53-NH 2 that really caused the fluorescence enhancement. In particular, the formed BDC-NH 2 was reduced from the shedded BDC-NO 2 (2-nitrobenzene-1,4-dicarboxylic acid) during the decomposition of Al-MIL-53-NO 2 , which was attacked by OH − in the NaHS solution. We anticipate that this work will offer new ways of tracing fluorophores for MOF-based sensing applications in aqueous systems. 

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4. Employing Conductive Metal-Organic Frameworks for Voltammetric Detection of Neurochemicals

   https://doi.org/10.1021/jacs.9b13402  

   Ko, Michael; Mendecki, Lukasz; Eagleton, Aileen M.; Durbin, Claudia G.; Stolz, Robert M.; Meng, Zheng; Mirica, Katherine A (March 2020, Journal of the American Chemical Society)

   This paper describes the first implementation of an array of two-dimensional (2D) layered conductive metal–organic frameworks (MOFs) as drop-casted film electrodes that facilitate voltammetric detection of redox active neurochemicals in a multi-analyte solution. The device configuration comprises a glassy carbon electrode modified with a film of conductive MOF (M3HXTP2; M = Ni, Cu; and X = NH, 2,3,6,7,10,11-hexaiminotriphenylene (HITP) or O, 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP)). The utility of 2D MOFs in voltammetric sensing is measured by the detection of ascorbic acid (AA), dopamine (DA), uric acid (UA), and serotonin (5-HT) in 0.1 M PBS (pH=7.4). In particular, Ni3HHTP2 MOF demonstrated nanomolar detection limits of 63 ± 11 nM for DA and 40 ± 17 nM for 5-HT through a wide concentration range (40 nM – 200 µM). The applicability in biologically-relevant detection was further demonstrated in simulated urine using Ni3HHTP2 MOFs for the detection of 5-HT with nanomolar detection limit of 63 ± 11 nM for 5-HT through a wide concentration range (63 nM – 200 µM) in the presence of constant background of DA. The implementation of conductive MOFs in voltammetric detection holds promise for further development of highly modular, sensitive, selective, and stable electroanalytical devices. 

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5. Bridged and fused triazolic energetic frameworks with an azo building block towards thermally stable and applicable propellant ingredients

   https://doi.org/10.1039/d1ta07520a  

   Yu, Qiong; Li, Fengsheng; Yin, Ping; Pang, Siping; Staples, Richard J.; Shreeve, Jean'ne M. (November 2021, Journal of Materials Chemistry A)

   The assembly of nitrogen-rich building blocks determines the energy storage capacity and affects the stability of energetic materials. Owing to the environmentally harmful properties of the propellant, ammonium perchlorate (AP), much research has explored halogen-free replacements which often suffer from poor thermal stability. In our goal of balancing performance and stability, we report access to an energetic molecule (3) by smart assembly of an azo bridge into trinitromethyl triazoles. Compound 3 exhibits a decomposition temperature of 175 °C, which approaches the highest among reported trinitromethyl derivatives. The density (1.91 g cm −3 ) and oxygen balance (+29%) for 3 exceed other candidates, suggesting it as a high energy dense oxidizer (HEDO) replacement for AP in rocket propellants. One-step azo-involved cyclization of 3 give two fused nitro triazolones, (FNTO) 4 and its N -oxide 5, having thermal stabilities and energies superior to the analogous derivatives of 5-nitro-2,4-dihydro-3 H -1,2,4-triazole-3-one (NTO). The comparison of properties of the fused triazolones 4 and 8 and their N -oxide derivatives 5 and 9 shows that formation of an N -oxide is an effective strategy which results in an increase of the decomposition temperature, oxygen balance, specific impulse, and detonation properties and in a decrease of the sensitivity of the corresponding energetic material. This work highlights bridged and fused triazolic energetic frameworks with an azo building block providing an alternative structural motif for seeking an applicable high-energy ingredient. 

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