Mellitic Acid Research Articles

Mellitic Acid-Supported Synthesis of Anisotropic Nanoparticles Used as SERS Substrate.

A method for the synthesis of a new SERS substrate-anisotropic silver nanoparticles using mellitic acid as a new capping agent is presented. The synthesis is free of toxic substances and does not require special temperature or lighting conditions. Moreover, it is fast, easy, and inexpensive. Depending on the concentration of silver ions and nanoparticle seeds, four different colloids were obtained, representing the evolution of nanoparticle growth along different paths from the first common stage. One of the synthesized colloids consists mainly of triangular nanoplates, while the other consists of polyhedral NPs. The analysis of the synthesis process together with the observation of TEM images and UV-vis extinction spectra enabled the proposal of the mechanism of interaction of mellitic acid molecules as the capping agent. The ability of mellitic acid molecules to form a hydrogen bond network, together with a ratio of silver ions to the mellitic acid concentration, turned out to be crucial for determining the shape of the NPs. All obtained colloids strongly enhance the Raman spectra of analyte molecules, thus proving their applicability as efficient new SERS substrates. For the one that enhanced the spectra the most, the detection limit was set at 10-9 M. Using it as a SERS substrate enables the identification of a trace amount of a designer drug, i.e., 4-chloromethcathinone (4-CMC, clephedrone). For the first time, SERS spectra of this substance, illegal in many countries, are presented.

Investigating the stability of aromatic carboxylic acids in hydrated magnesium sulfate under UV irradiation to assist detection of organics on Mars

The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument onboard the Mars 2020 Perseverance rover detected so far some of the most intense fluorescence signals in association with sulfates analyzing abraded patches of rocks at Jezero crater, Mars. To assess the plausibility of an organic origin of these signals, it is key to understand if organics can survive exposure to ambient Martian UV after exposure by the Perseverance abrasion tool and prior to analysis by SHERLOC. In this work, we investigated the stability of organo-sulfate assemblages under Martian-like UV irradiation and we observed that the spectroscopic features of phthalic and mellitic acid embedded into hydrated magnesium sulfate do not change for UV exposures corresponding to at least 48 Martian sols and, thus, should still be detectable in fluorescence when the SHERLOC analysis takes place, thanks to the photoprotective properties of magnesium sulfate. In addition, different photoproduct bands diagnostic of the parent carboxylic acid molecules could be observed. The photoprotective behavior of hydrated magnesium sulfate corroborates the hypothesis that sulfates might have played a key role in the preservation of organics on Mars, and that the fluorescence signals detected by SHERLOC in association with sulfates could potentially arise from organic compounds.

Insight into structure features of coals with different metamorphic degrees via step-wise oxidation

A step-wise oxidation method, combining H2O2 oxidation and alkali-oxygen oxidation (AOO), was applied to study the structure features of coals with different metamorphic degrees. The results show that the conversion of Baiyinhua coal, Hongshaquan coal, Pingshuo coal and Hongliulin coal in 30 % H2O2 solution for 10 h at 60 °C are 89.8 wt%, 79.0 wt%, 29.5 wt%, and 14.8 wt%, respectively. The oxygen containing species retrieved from water-soluble product by ethyl acetate extraction are mainly concentrated in O4-O8 class species, including aliphatic carboxylic acids with a carboxylic range of 1–5 and carbon numbers from 3 to 11, and phenols or aromatic carboxylic acids of 1–3 ring. The residues from H2O2 oxidation of four coals can be completely depolymerized through AOO. The maximum benzene carboxylic acid (BCA) yield of RBYH is 7.66 wt%, while that of RHSQ, RPS, and RHLL are 18.24 wt%, 19.52 wt%, and 19.91 wt%, respectively. The AOO products of four residues show the similar BCA distributions, and mellitic acid, benzenepentacarboxylic acid, pyromellitic acid, trimellitic acid, hemimelitic acid, and phthalic acid are the main BCAs. Therefore, step-wise oxidation can be used as an effective method to understand the structural features of coal, including the small molecule structures obtained after breaking weak bonds and the aromatic substitution information in the residue.

Identification and Limit of Detection of Benzene, Chlorobenzene, Benzoic Acid, Phthalic Acid, and Mellitic Acid in Water Solutions Using Excitation, Emission, and Single-band Synchronous Fluorescence Spectroscopy

Introduction: This paper first introduces the use of computer-simulated single-band synchronous fluorescence (SF) obtained from experimental excitation and emission fluorescence spectra of a pure compound in solution. The simulation produces a single narrow band with a peak wavelength that identifies the compound. Methods: The method is used to show single peak identification of benzene, chlorobenzene, benzoic acid, phthalic acid, and mellitic acid in water solutions. Synchronous fluorescence spectroscopy (SFS) is a variant of fluorescence technique in which excitation and emission scans are simultaneously acquired and multiplied with a predetermined wavelength difference (Δλ) between the two. Commercial instruments have this option to get the SFS signals. Results: In response to the Δλ selected, the result will be an SFS signal producing a series of peaks that could be assigned to compounds. Instead of running the same experiment with different Δλ values to identify the compounds, our simulation program determines a specific Δλ value that generates a narrow SF band with a distinctive peak wavelength for identification purposes. Conclusion: Finally, binary mixtures of chlorobenzene with each compound in water are prepared. The SFS of the solution is acquired and compared with the SFS bands of the components for identification purposes. With the commercial lamp fluorimeter employed, the limits of detection are obtained at the ng/g concentration level with fluorescence emission. Possible limits of detection at lower concentrations are discussed using a laser source. The presence of these molecules in astrochemical studies is discussed.

An Upper Pleistocene and Holocene Black Carbon‐Related Fire Record From the SW Balkans

AbstractLake sediments are unique archives of human environment interactions. Lake Prespa is one of the oldest lakes in Europe, lying in the southwestern Balkans and thus on a possible dispersal route of anatomically modern humans from Africa. In this study, we investigated the effects of climate, vegetation and human activity on fire over the last 92,000 years in this region. Sediment samples were taken from Lake Prespa, and nearby Lake Ohrid for comparison of the regional relevance, and analyzed for benzene polycarboxylic acids as markers for burned organic carbon residues (black carbon, BC). Peaking contents of BC (up to 1 g BC kg−1 sediment) coincided with warm and humid phases, when forests expanded at marine isotope stages (MIS) 5 and 1. During the colder and more arid climates of MIS 4 and 2, BC contents were lowered by a factor of 10, with a distinct minimum during the Last Glacial Maximum (0.07 g BC kg−1). The ratio of pentacarboxylic acid to mellitic acid (B5CA/B6CA) declined from 1.2 at MIS 5 to values of 0.3 at MIS 2, confirming a change in fire regime. Overall, BC contents peaked at cycles of solar radiation, vegetation composition and fuel availability, and thus correspond to the BC signal of other environmental archives. However, in the Late Holocene and as a result of human sedentary settlement, BC production increased, independent of decreasing insolation forcing.

Systematic separation of carboxylic acids from H8[PMo7V5O40]-catalyzed lignite oxidation products via deep eutectic solvent

To separate the valuable carboxylic acids (CAs) from the complicated oxidized products (OPs) of H8[PMo7V5O40]-catalyzed lignite, systematic processes including distillation, ether extraction, acetone dissolution and separation by deep eutectic solvent (DES) were first constructed and sequentially performed. First, formic acid and acetic acid are separated in vacuum at 56 °C with the separation efficiency of 95% and 82%, respectively. Subsequently, sequential treatments of OPs by ether extraction and acetone/water dissolution are implemented to reduce the low-polarity compounds contents and fully dissolve CAs from concentrated residue. Separation results indicate that choline chloride (ChCl) shows a better separation performance compared to acetylcholine chloride and gives optimal separation efficiencies of 78.19% and 94.45% for benzenepentacarboxylic acid (BPA) and mellitic acid (MLA) within 2 h at ambient temperature, respectively. The hydrogen-bonded binding energies (BEs) formed in DES are calculated based on density functional theory, and results show that total BEs of MLA and ChCl is as high as −31.09 kcal/mol, and the next is −26.79 kcal/mol for BPA, leading to their quick and high separation efficiencies within 2 h. As a result, only MLA and BPA show the high correlation with pseudo-second-order kinetic model, and the rate constant of MLA is as high as 0.3367 g/(mg·h), which is far more than that of BPA. Additionally, the effect of hydrogen bonds on the separation of CAs follows the order of Cl∙∙∙H-O > O-H∙∙∙O-C > O-H∙∙∙O = C. Overall, this attractive strategy provides ideas for efficient separation of CAs, which will pave the way for utilization of lignite.

Dehydration-Triggered Afterglow Transition in a Mellitate-Based Coordination Polymer

Stimulus-responsive long persistent luminescence (LPL) materials have attracted wide attention due to their potential applications in information storage, anti-counterfeiting, optoelectronic devices, etc. However, LPL coordination polymers with room temperature afterglow transition characteristics have not been explored. Herein, mellitic acid and zinc ions were utilized to synthesize an acid–base stable coordination polymer (1) by an organic solvent-free hydrothermal method. 1 possesses a tightly stacked structure and exhibits dual-emission peaks with blue luminescence and blue-green afterglow. Upon exposure to heating, DMSO immersion, or vacuum, 1h, 1s, and 1v were obtained. The original blue luminescence changes to blue-green, while the afterglow turns yellow-green due to the loss of water molecules from the inner cavity. This is the first example of an LPL coordination polymer that can realize room temperature afterglow transition by dehydration operation. Moreover, the emission spectra of 1 can be recovered by exposing 1h, 1s, or 1v to water vapor, suggesting a reversible dehydration/hydration process. Experimental and density functional theory (DFT) results suggest that the fluorescence of 1 originates from the mixing of intra-ligand and ligand-to-metal charge transfer excited states. The triplet state from intersystem crossing is responsible for the long persistent luminescence of phosphorescence emission. The rational structural design along with the conceptual model of anti-counterfeiting and information encryption based on afterglow transition display the unique advantages of the LPL coordination polymer in realizing convenient multiple stimuli-responsive devices.

Molecular Composition and Biological Activity of a Novel Acetonitrile-Water Extract of Lens Culinaris Medik in Murine Native Cells and Cell Lines Exposed to Different Chemotherapeutics Using Mass Spectrometry.

We evaluated the effects of a new extract (70% acetonitrile, 2E0217022196DIPFARMTDA) of Lens culinaris Medik (Terre di Altamura SRL, Altamura BA) to prevent cytotoxic damage from cisplatin, staurosporine, irinotecan, doxorubicin, and the glucocorticoid dexamethasone. The acetonitrile-water extract (range 0.1-5 mg/mL) was obtained by extracting 10 g of lentil flour with 50 milliliters of the acetonitrile-water extraction mixture in a 70:30 ratio, first for 3 h and then overnight in a shaker at room temperature. The next day, the extract was filtered and passed through a Rotavapor to obtain only the aqueous component and eliminate that with acetonitrile, and then freeze-dried to finally have the powdered extract. In vitro experiments showed that the extract prevented the cytotoxic damage induced by cisplatin, irinotecan, and doxorubicin on HEK293 and SHSY5Y cell lines after 24-96 h. In murine osteoblasts after 24-72 h of incubation time, the extract was cytoprotective against all chemicals. The extract was effective against dexamethasone, leading to synergic cell proliferation in all cell types. In bone marrow cells, the extract is cytoprotective after 72 h against doxorubicin, staurosporine, and dexamethasone. Instead, on muscle fibers, the extract has a synergic effect with chemotherapeutics, increasing cytotoxicity induced by doxorubicin and staurosporine. LC-MS attested to the existence of several phenolic structures in the extract. The most abundant families of compounds were flavonoids (25.7%) and mellitic acid (18%). Thus, the development of this extract could be implemented in the area of research related to the chemoprevention of damage to renal, neuronal, bone marrow cells, and osteoblasts by chemotherapeutics; moreover, it could be used as a reinforcer of cytotoxic action of chemotherapeutics on muscle fibers.

Green two-step oxidation for efficient utilization of Huolinhe lignite under the vision of carbon neutrality

To realize carbon neutrality in energy transition process, a two-step oxidation of Huolinhe lignite (HL) with less CO2 emissions is proposed, including pretreatment with H2O2 (PT) or pretreatment with Fenton’s reagent (PTF) and further oxidation in aqueous sodium hypochlorite (ASHC). The results indicate that the insoluble macromolecular moieties in HL are mainly oxidized into alkanedioic acids (ADAs) and non-substituted benzenecarboxylic acids (NSBCAs) and the yield of soluble portion is elevated by PTF from 60.56 % to 74.99 %. The increase in the ADA carbon number indicates that PT and PTF could enhance the oxidation ability of ASHC to break bridged linkages with longer chains. As for NSBCAs, the carboxylic group number (CGN) ranges from 2 to 5 in E1 and 2 to 6 in E2 and E3, respectively. The absence of mellitic acid in E1 states the limited oxidation capacity of ASHC to degrade highly condensed aromatic rings, which could be improved by PT and PTF. Moreover, the highest yield of NSBCAs is achieved at CGN = 2 in E2 and CGN = 4 in E3, implying that PTF is more effective to destruct highly condensed aromatic species in HL. According to the characterizations of coal samples, PT could increase the volatile matter and oxygen contents of HL and create new micropores to corrode HL viaOH attack, which would be enhanced by the introduction of Fe2+ during PTF to break weak covalent bonds, resulting in the preliminary degradation of macromolecular networks in HL. Then, cleavage of strong bonds undergoes easily via the attack of O2− generated from ASHC, leading to the deep decomposition of macromolecular moieties in HL.

Reversible multi-electron redox chemistry of organic salt as anode for high-performance Li-ion/dual-ion batteries

Organic electrode materials are attracting increasing attention for rechargeable secondary batteries because of their low cost, high capacity, nontoxic and environmentally friendly. Herein, we report an excellent anode of a novel organic hexalithium salt of mellitic acid (Li6C12O12) for lithium-ion battery (LIB)/dual-ion battery (DIB). A combination of electrochemical and spectroscopic studies verifies a reversible coordination reaction mechanism based on carboxylic carbonyl and Li+ ions. Li6C12O12 delivers large reversible capacities of 730 mA h g−1 at 0.21 A/g and 372 mA h g−1 even at 2 A/g. Furthermore, the Li6C12O12 electrode enables LiFePO4//Li6C12O12 full LIB and graphite//Li6C12O12 full DIB to exhibit high capacity and good cycling stability. This work presents a new perspective on designing and tailoring organic electrode materials to build high-performance lithium-ion batteries/dual-ion batteries.

Design of a robust and strong-acid MOF platform for selective ammonium recovery and proton conductivity.

Metal-organic frameworks (MOFs) are potential candidates for the platform of the solid acid; however, no MOF has been reported that has both aqueous ammonium stability and a strong acid site. This manuscript reports a highly stable MOF with a cation exchange site synthesized by the reaction between zirconium and mellitic acid under a high concentration of ammonium cations (NH4+). Single-crystal XRD analysis of the MOF revealed the presence of four free carboxyl groups of the mellitic acid ligand, and the high first association constant (pKa1) of one of the carboxyl groups acts as a monovalent ion-exchanging site. NH4+ in the MOF can be reversibly exchanged with proton (H+), sodium (Na+), and potassium (K+) cations in an aqueous solution. Moreover, the uniform nanospace of the MOF provides the acid site for selective NH4+ recovery from the aqueous mixture of NH4+ and Na+, which could solve the global nitrogen cycle problem. The solid acid nature of the MOF also results in the proton conductivity reaching 1.34 × 10-3 S cm-1 at 55 °C by ion exchange from NH4+ to H+.

Clean two-step oxidative degradation of Yima long flame coal for benzenecarboxylic acid production

Low rank coals are promising raw materials to afford oxygenated organic chemicals due to the high oxygen contents. This study reported a clean two-step coal oxidative degradation approach for low-carbon and high value-added chemical production. Oxidative degradation of Yima long flame coal (YLFC) was performed in aqueous hydrogen peroxide solution (AHPS) to activate the aromatic ring structures in YLFC, followed by the further oxidation with aqueous sodium hypochlorite solution (ASHS) to degrade the macromolecular networks in YLFC into soluble portions. Meanwhile, oxidation of YLFC with ASHS was also performed to investigate the role of pretreatment with AHPS in the oxidative degradation of YLFC in ASHS. The results show that 95.5% of the macromolecular structure in YLFC was converted by the two-step oxidation, while the conversion rate of YLFC in ASHS is only 59.3%. Noteworthily, the pretreatment with AHPS is more effective to increase the yields of more valuable pentacarboxy benzene and mellitic acid compared with benzenecarboxylic acids with fewer carboxylic groups. The sharp increase in the yield of oxidation products by pretreatment with AHPS could be related to .OH produced from H2O2 decomposition, which can break the weak oxygenated linkages and generate oxygenated functional groups. Thus, the activated aromatic ring structures and improved hydrophilicity of YLFC contribute to the deep decomposition of condensed aromatic rings caused by aggression of the reactive intermediate O2–. generated from ionization equilibriums in ASHC. The synergistic effect of the two-step oxidation leads to the complete degradation of macromolecular networks in YLFC.

Two Neptunium(III) Mellitate Coordination Polymers: Completing the Series Np-Cf of Trans-Uranic An(III) Mellitates.

Two neptunium(III) mellitates, 237Np2(mell)(H2O)9·1.5H2O (Np-1α) and 237Np2(mell)(H2O)8·2H2O (Np-1β), have been synthesized from 237NpCl4(dme)2 by reduction with KC8 and subsequent reaction with an aqueous solution of mellitic acid (H6mell). Characterization by single-crystal X-ray crystallography and UV-vis-NIR spectroscopy confirms that the neptunium is in its +3 oxidation state and both polymorphs are isostructural to the previously reported plutonium mellitates. Of the two morphologies, Np-1α is indefinitely stable in air, while Np-1β slowly oxidizes over several months. This is due to the change in the energy of the metal-ligand charge-transfer absorption exhibited by these compounds attributed to differing numbers of carboxylate bonds to Np(III), where in Np-1β the energy is low enough to result in spontaneous oxidation.

Comparative study on the relative significance of low-/high-condensation aromatic moieties in biochar to organic contaminant sorption

Aromatic moieties of biochar are considered as key components for immobilizing hydrophobic organic contaminants in the environment. However, the relative importance of different aromatic moieties such as low-/high-condensation components in sorption has not been comprehensively investigated. In this study, biochar was produced from flue-cured tobacco straw (TB) and pine wood sawdust (WB) at various pyrolysis temperatures (200–600 °C). Aromatic moieties were characterized via elemental analysis, Fourier transform infrared spectroscopy, Raman spectroscopy, and benzene polycarboxylic acid molecular markers (BPCAs). The significance of different aromatic moieties in the sorption of phenanthrene (PHE) and bisphenol A (BPA) was assessed based on the individual BPCA patterns. The results indicated that aromaticity and aromatic moiety contents increased with increasing pyrolysis temperature. Biochar at 200 °C produced lower mellitic acid (B6CA) contents (18.7–27.9%) than the others. When the pyrolysis temperature was increased to 600 °C, the B6CA contents representing high-condensation aromatic moieties accounted for 55.4–60.9% of all the aromatic moieties. The unitary linear regressions between the individual BPCA distribution patterns and the n values and log Kd suggested that the high-condensation aromatic moieties played a more significant role than the low-condensation aromatic moieties (represented by B3CA–B5CA) in facilitating sorption nonlinearity (for PHE and BPA) and sorption capacity (for PHE). The elevated sorption of PHE can be attributed to the increased specific surface area and hydrophobicity of the newly formed aromatic moieties. Hydrogen bonds and π–π electron–donor–acceptor were the main mechanisms of BPA sorption. Because the WB biochar contained more aromatic moieties and more O-containing groups on the surface of the TB biochar, the WB exhibited a higher sorption for PHE; however, slightly elevated sorption was observed on the TB for BPA. This research may provide a new perspective in understanding the behavior of biochar aromatic moieties in sorption of organic contaminants.

The molecular markers provide complementary information for biochar characterization before and after HNO3/H2SO4 oxidation

Biochar inevitably goes through long-term aging under biotic and abiotic processes in the environment, which results in various changes in its physicochemical properties. However, the traditional characterization methods based on particle separation cannot effectively monitor biochar in complex matrixes. Molecular markers, especially benzene polycarboxylic acids (BPCAs), can be used to directly identify the source and properties of biochar. In this study, biochars were prepared using corn straw (CS) and pinewood (PW) and were oxidized with HNO3/H2SO4 to simulate the aging processes. Molecular markers of lignin-derived phenols showed that PW has more vanillyl unit and thus more stable than CS. The overall BPCAs content and the relative content of mellitic acid (B6CA) both increased with pyrolysis temperature, indicating increased aromatic condensation/aromaticity. The pristine CS biochar has a higher BPCAs content compared to PW biochar. HNO3/H2SO4 treatment greatly decreased the lignin components and more vanillyl and cinnamyl units were removed from CS biochar than PW biochar. In addition, BPCAs contents decreased by 41–60 mg/g for CS biochar, while increased by 86–133 mg/g for PW biochar after HNO3/H2SO4 oxidation. This is owing to the release of the condensed aromatic structures in CS biochars, but the concentration of the condensed aromatic structures in PW biochars after oxidation. These results showed that PW biochars are more stable than CS biochars. The application of the molecular markers can help understanding the dynamic change of biochar in the environment.

Effect of preoxidation treatment with H2O2 on ruthenium ion-catalyzed oxidation of Yima long flame coal

Environmental concerns have led researches to investigate carbon neutral and sustainable strategies to satisfy well-being of present and future generations, in which coal oxidation becomes a promising approach to achieve this goal. In this study, Yima long flame coal (YLFC) was subjected to ruthenium-ion-catalyzed oxidation (RICO) after peroxidation with H2O2 (PO). The results indicate that the organic matter in YLFC is mainly oxidized into benzenecarboxylic acids, accounting for 70.36% of all the oxidation products, and the yields of the valuable resulting carboxylic acids are significantly elevated by PO from 12.99 wt% to 35.06 wt%, leading to a higher utilization of carbon and lower CO2 emission. Moreover, PO can enhance remarkably the reactivity of the macromolecular precursors of coals, especially highly condensed aromatic species to produce benzenepentacarboxylic acid and mellitic acid more efficiently with a 20-fold increase and 200-fold increase, which is ascribed to the formation of carboxyl groups from other oxygen-containing groups or bonds in coals via PO. The reactive intermediates OH and OOH generated from H2O2 decomposition can attack the carbon atom of alkyl side chains, ether bonds, C=O bonds, and the bridged linkages to undergo a preliminary degradation of macromolecular networks in coals and produce more active sites for the subsequent RICO, leading to the yield and species number increase of carboxylic acids via PO.

Synthesis, characterization, and high-pressure studies of a 3D berkelium(III) carboxylate framework material.

A berkelium(III) mellitate, Bk2[C6(CO2)6](H2O)8·2H2O, was synthesized and rapidly crystallized by reacting mellitic acid, C6(CO2H)6, and BkBr3·nH2O in an aqueous medium. Single crystal X-ray diffraction shows that the compound crystallizes as a three-dimensional framework isostructural with Pu(III), Am(III), and Cm(III) mellitates. UV-vis-NIR spectroscopic studies as a function of pressure were performed using a diamond anvil cell and show that the 5f → 5f transitions of Bk3+ display enhanced hypsochromic shifting when compared to other An(III) mellitates.

Crystallographic, spectroscopic, thermal and computational studies of polymeric cobalt(II)–mellitate complex with 2,2′-bipyridine

Orange single crystals of new polymeric cobalt(II) complex {[Co(bipy)(H2O)4]2[Co(μ-mell)(H2O)2]·10H2O}n, 1, were synthesized by slow evaporation method at room temperature (bipy = 2,2′-bipyridine, mell = hexaanion of mellitic acid) and its crystal structure was determined by single-crystal X-ray diffraction. The complex 1 was characterized based on elemental analysis, FTIR spectroscopy and thermal (TG/DTA) analysis followed by computational analysis of noncovalent interactions and quantum chemical calculations of interaction energies. In 1, two crystallographically different Co(II) atoms adopt a deformed octahedral geometry, while bridging mell acts as a tetrakis monodentate ligand allowing the development of wavy-like anionic chains running along [100] direction. The 3D supramolecular network of 1 is composed of alternating supramolecular and water layers connected by hydrogen bonds. The supramolecular layer is formed of ionic interactions between complex cations and polymeric complex anions, established mainly through O–H···O hydrogen bonds, as well as stacking interactions between bipy ligands, while the water layers are comprised of hydrogen bonded lattice water molecules. Upon heating up to 1200 °C in nitrogen and air atmosphere, complex 1 showed multiple-step degradation that resulted in the formation of Co and Co3O4, respectively. Computed Hirshfeld surfaces and 2D fingerprint plots indicated that O–H···O hydrogen bonds are the most dominant in the crystal structure, while the shape index and curvedness mapped on the Hirshfeld surfaces of 1 revealed that stacking interactions have an important role in the stabilization of the crystal packing. Quantum chemical calculations showed that, aside from ionic hydrogen-bonded interaction between cation and anionic polymer, the important role in the stability of supramolecular structure of 1 is played by hydrogen bonds of cation and anionic polymer with lattice water, as well as by stacking interactions between bipy ligands.

Effect of Small Polyanions on In Vitro Assembly of Selected Members of Alpha-, Beta- and Gammaretroviruses.

The assembly of a hexameric lattice of retroviral immature particles requires the involvement of cell factors such as proteins and small molecules. A small, negatively charged polyanionic molecule, myo-inositol hexaphosphate (IP6), was identified to stimulate the assembly of immature particles of HIV-1 and other lentiviruses. Interestingly, cryo-electron tomography analysis of the immature particles of two lentiviruses, HIV-1 and equine infectious anemia virus (EIAV), revealed that the IP6 binding site is similar. Based on this amino acid conservation of the IP6 interacting site, it is presumed that the assembly of immature particles of all lentiviruses is stimulated by IP6. Although this specific region for IP6 binding may be unique for lentiviruses, it is plausible that other retroviral species also recruit some small polyanion to facilitate the assembly of their immature particles. To study whether the assembly of retroviruses other than lentiviruses can be stimulated by polyanionic molecules, we measured the effect of various polyanions on the assembly of immature virus-like particles of Rous sarcoma virus (RSV), a member of alpharetroviruses, Mason-Pfizer monkey virus (M-PMV) representative of betaretroviruses, and murine leukemia virus (MLV), a member of gammaretroviruses. RSV, M-PMV and MLV immature virus-like particles were assembled in vitro from truncated Gag molecules and the effect of selected polyanions, myo-inostol hexaphosphate, myo-inositol, glucose-1,6-bisphosphate, myo-inositol hexasulphate, and mellitic acid, on the particles assembly was quantified. Our results suggest that the assembly of immature particles of RSV and MLV was indeed stimulated by the presence of myo-inostol hexaphosphate and myo-inositol, respectively. In contrast, no effect on the assembly of M-PMV as a betaretrovirus member was observed.

Permeability of the HIV-1 capsid to metabolites modulates viral DNA synthesis.

Reverse transcription, an essential event in the HIV-1 life cycle, requires deoxynucleotide triphosphates (dNTPs) to fuel DNA synthesis, thus requiring penetration of dNTPs into the viral capsid. The central cavity of the capsid protein (CA) hexamer reveals itself as a plausible channel that allows the passage of dNTPs into assembled capsids. Nevertheless, the molecular mechanism of nucleotide import into the capsid remains unknown. Employing all-atom molecular dynamics (MD) simulations, we established that cooperative binding between nucleotides inside a CA hexamer cavity results in energetically favorable conditions for passive translocation of dNTPs into the HIV-1 capsid. Furthermore, binding of the host cell metabolite inositol hexakisphosphate (IP6) enhances dNTP import, while binding of synthesized molecules like benzenehexacarboxylic acid (BHC) inhibits it. The enhancing effect on reverse transcription by IP6 and the consequences of interactions between CA and nucleotides were corroborated using atomic force microscopy, transmission electron microscopy, and virological assays. Collectively, our results provide an atomistic description of the permeability of the HIV-1 capsid to small molecules and reveal a novel mechanism for the involvement of metabolites in HIV-1 capsid stabilization, nucleotide import, and reverse transcription.