Molecular Formula Research Articles

Development of Small HN Linked Radionuclide Iodine-125 for Nanocarrier Image Tracing in Mouse Model.

Radionuclides have important roles in clinical tumor radiotherapy as they are used to kill tumor cells or as imaging agents for drug tracing. The application of radionuclides has been developing as an increasing number of nanomaterials are used to deliver radionuclides to tumor areas to kill tumor cells. However, promoting the efficient combination of radionuclides and nanocarriers (NCs), enhancing radionuclide loading efficiency, and avoiding environmental pollution caused by radionuclide overuse are important challenges that hinder their further development. In the present study, a new small molecule compound (3-[[(2S)-2-hydroxy-3-(4-hydroxyphenyl)-1-carbonyl] amino]-alanine, abbreviation: HN, molecular formula: C12H16N2O5) was synthesized as a linker between radionuclide iodine-125 (125I) and NCs to enable a more efficient binding between NCs and radionuclides. In vitro evidence indicated that the linker was able to bind 125I with higher efficiency (labeling efficiency >80%) than that of tyrosine, as well as various NCs, such as cellulose nanofibers, metal oxide NCs, and graphene oxide. Single-photon emission computed tomography/computed tomography imaging demonstrated the biological distribution of 125I-labeled NCs in different organs/tissues after administration in mice. These results showed an improvement in radionuclide labeling efficiency for nanocarriers and provided an approach for nanocarrier image tracing.

Effect of Magnesium Site Doping on Electrochemical Properties of Mg-Mn Composite Materials and Application of Carpet-Like Sheets Composite Formed by Cr Doping in Aqueous Zinc-Ion Batteries

Manganese based compounds have very stable electrochemical properties, thus they are widely applied in aqueous zinc-ion battery. However, it is easy to dissolve manganese in the process of charge and discharge, which leads to the collapse of the cathode material structure. In this paper, the composite materials of manganese carbonate and magnesium carbonate were synthesized by hydrothermal method, and its properties were optimized by doping modification. According to the electrochemical tests, the electrochemical performance of the material synthesized with 5% Cr doping is relatively stable. Moreover, with the increase of Cr content, the charge transfer impedance of the material can be significantly reduced. In the cyclic tests, after 60 cycles of charge and discharge under different current densities, and another several cycles at the current density of 50 mA g−1, the capacity rises to 212.01 mAh g−1, higher than the first discharge capacity. SEM tests are also conducted to survey the micro-structure of the material, besides the cube unit, there are also carpet-like sheets made of nano-sized joined petal-like unit, which greatly increases the specific surface area of the material. According to the data of EDS and XPS, the fact that that the types and valence states of elements in the composites were consistent with those in manganese carbonate and magnesium carbonate are confirmed. Through the infrared and Raman tests, the functional groups in the synthesized material are proven to correspond to the molecular formula. From the XRD pattern, no obvious impurity peaks can be observed. With all the data obtained from physical characterization, it can be concluded that the material is mainly composed of manganese carbonate and magnesium carbonate.

ChloroDBPFinder: Machine Learning-Guided Recognition of Chlorinated Disinfection Byproducts from Nontargeted LC-HRMS Analysis.

High-resolution mass spectrometry (HRMS) is a prominent analytical tool that characterizes chlorinated disinfection byproducts (Cl-DBPs) in an unbiased manner. Due to the diversity of chemicals, complex background signals, and the inherent analytical fluctuations of HRMS, conventional isotopic pattern (37Cl/35Cl), mass defect, and direct molecular formula (MF) prediction are insufficient for accurate recognition of the diverse Cl-DBPs in real environmental samples. This work proposes a novel strategy to recognize Cl-containing chemicals based on machine learning. Our hierarchical machine learning framework has two random forest-based models: the first layer is a binary classifier to recognize Cl-containing chemicals, and the second layer is a multiclass classifier to annotate the number of Cl present. This model was trained using ∼1.4 million distinctive MFs from PubChem. Evaluated on over 14,000 unique MFs from NIST20, this machine learning model achieved 93.3% accuracy in recognizing Cl-containing MFs (Cl-MFs) and 92.9% accuracy in annotating the number of Cl for Cl-MFs. Furthermore, the trained model was integrated into ChloroDBPFinder, a standalone R package for the streamlined processing of LC-HRMS data and annotating both known and unknown Cl-containing compounds. Tested on existing Cl-DBP data sets related to aspartame chlorination in tap water, our ChloroDBPFinder efficiently extracted 159 Cl-containing DBP features and tentatively annotated the structures of 10 Cl-DBPs via molecular networking. In another application of a chlorinated humic substance, ChloroDBPFinder extracted 79 high-quality Cl-DBPs and tentatively annotated six compounds. In summary, our proposed machine learning strategy and the developed ChloroDBPFinder provide an advanced solution to identifying Cl-containing compounds in nontargeted analysis of water samples. It is freely available on GitHub (https://github.com/HuanLab/ChloroDBPFinder).

High-pressure study of a 3d-4f heterometallic CuEu-organic skeleton.

We prepared a 3d-4f heterobimetallic CuEu-organic framework NBU-8 with a density of 1921 kg m-3 belonging to the family of dense packing materials (dense metal-organic frameworks or MOFs). This MOF material was prepared from 4-(pyrimidin-5-yl)benzoic acid (HPBA) with a bifunctional ligand site as a tripodal ligand and Cu2+ and Eu3+ as the metal centres; the molecular formula is Cu3Eu2(PBA)6(NO3)6·H2O. This material is a very promising dimethylformamide (DMF) molecular chemical sensor. Systematic high-pressure studies of NBU-8 were carried out by powder X-ray diffraction, high-pressure X-ray diffraction and molecular dynamics simulation. The high-pressure experiment shows that the (006) diffraction peak of the crystal structure moves toward a low angle with increasing pressure, accompanied by the phenomenon that the d-spacing increases, and as the pressure increases, the (10-2) diffraction peak moves to a higher angle, the amplitude of the d-spacing is significantly reduced and finally merges with the (006) diffraction peak into one peak. The amplitude of the d-spacing is significantly reduced, indicating that NBU-8 compresses and deforms along the a-axis direction when subjected to uniform pressure. This is caused by tilting of the ligands to become more vertical along the c direction, leading to its expansion. This allows greater contraction along the a direction. We also carried out a Rietveld structure refinement and a Birch-Murnaghan solid-state equation fitting for the high-pressure experimental results. We calculated the bulk modulus of the material to be 45.68 GPa, which is consistent with the calculated results. The framework is among the most rigid MOFs reported to date, exceeding that of Cu-BTC. Molecular dynamics simulations estimated that the mechanical energy absorbed by the system when pressurized to 5.128 GPa was 249.261 kcal mol-1. The present work will provide fresh ideas for the study of mechanical energy in other materials.

New polypyridine Ru(II) dinuclear complex capable of catalyzing the water oxidation reaction

AbstractIn natural and artificial photosynthesis, the water oxidation reaction is the bottleneck for the conversion of solar energy into chemical energy. In this work, we report the syntheses and physicochemical characterization of two new dinuclear Ru(II) complexes, with molecular formula [{Ru(tpy)Cl}2(μ‐dpp)](PF6)2 (1) and [{Ru(tpy)(H2O)}2(μ‐dpp)](PF6)4 (2) (with tpy=2,2’ : 6’,2”‐terpyridine and dpp=2,3‐bis(2‐pyridyl)pyrazine). Chloro‐complex (1) was used as a precursor for the aquo‐complex (2) which can act as an active water oxidation reaction catalyst using Ce(IV) in CF3COOH 0.1 M as sacrificial oxidant. The mechanism and rate constants were explored by combining conventional mixing and stopped‐flow experiments with spectrophotometric monitoring in the UV‐visible region. DFT and TD‐DFT calculations were done to support the assignments of the experimental data. From the kinetic and theoretical data obtained, we propose‐ that (2) catalyses water oxidation via a nucleophillic water attack mechanism (WNA). Besides, catalytic activity for (2) was evaluated from reported values of turnover frequency (TOF) and turnover number (TON) values at pH=1.

Comparison of Cu+, Ag+, and Au+ Ions as Ionization Agents of Volatile Organic Compounds at Subatmospheric Pressure.

Ionization of volatile organic compounds (VOCs) by coinage metal ions (Cu+, Ag+, and Au+) generated by laser desorption and ionization (LDI) of a metal nanolayer in subatmospheric conditions is explored. The study was performed in a commercial subatmospheric dual MALDI/ESI ion source. Five compounds representing different VOC classes were chosen for a detailed study of the metal ionization mechanism: ethanol, acetone, acetic acid, xylene, and cyclohexane. In the gas phase, ion molecular complexes of all three metal ions were formed, typically with two ligand molecules. The successful detection of the metal complexes with VOCs strongly depended on the applied voltages across the ion source, minimizing the in-source fragmentation. The employed orbital trap with ultrahigh resolving power and sub-parts-per-million mass accuracy allowed unambiguous identification of the formed complexes based on their molecular formulas. The detection limits of the studied compounds in the gas were in the range 0.1-1.4 nmol/L. Compared to Cu+ and Ag+ ions, Au+ ions exhibited the highest reactivity, often complicating spectra by side products of reactions. On the other hand, they also allowed detecting saturated hydrocarbons, which did not produce any signals with Ag+ and Cu+.

Molecular insights into the microbial degradation of sediment-derived DOM in a macrophyte-dominated lake under aerobic and hypoxic conditions

The mineralization of dissolved organic matter (DOM) in sediments is an important factor leading to the eutrophication of macrophyte-dominated lakes. However, the changes in the molecular characteristics of sediment-derived DOM during microbial degradation in macrophyte-dominated lakes are not well understood. In this study, the microbial degradation process of sediment-derived DOM in Lake Caohai under aerobic and hypoxic conditions was investigated using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and metagenomics. The results revealed that the microbial degradation of sediment-derived DOM in macrophyte-dominated lakes was more intense under aerobic conditions. The microorganisms mainly metabolized the protein-like substances in the macrophyte-dominated lakes, and the carbohydrate-active enzyme genes and protein/lipid-like degradation genes played key roles in sediment-derived DOM degradation. Organic compounds with high H/C ratios such as lipids, carbohydrates, and protein/lipid-like compounds were preferentially removed by microorganisms during microbial degradation. Meanwhile, there was an increase in the abundance of organic molecular formula with a high aromaticity such as tannins and unsaturated hydrocarbons with low molecular weight and low double bond equivalent. In addition, aerobic/hypoxic environments can alter microbial metabolic pathways of sediment-derived DOM by affecting the relative abundance of microbial communities (e.g., Gemmatimonadetes and Acidobacteria) and functional genes (e.g., ABC.PE.P1 and ABC.PE.P) in macrophyte-dominated lakes. The abundances of lipids, unsaturated hydrocarbons, and protein compounds in aerobic environments decreased by 58 %, 50 %, and 44 %, respectively, compared to in hypoxic environments under microbial degradation. The results of this study deepen our understanding of DOM biodegradation in macrophyte-dominated lakes under different redox environments and provide new insights into nutrients releases from sediment and continuing eutrophication in macrophyte-dominated lakes.

Jugiones A-D: Antibacterial Xanthone-Anthraquinone Heterodimers from Australian Soil-Derived Penicillium shearii CMB-STF067.

The Australian roadside soil-derived fungus Penicillium shearii CMB-STF067 was prioritized for chemical investigation based on an SDA cultivation extract exhibiting both antibacterial properties and natural products with unprecedented molecular formulae (GNPS). Subsequent miniaturized 24-well plate cultivation profiling (MATRIX) identified red rice as optimal for the production of the target chemistry, with scaled-up cultivation, extraction and fractionation yielding four new xanthone-anthraquinone heterodimers, jugiones A-D (1-4), whose structures were assigned by detailed spectroscopic analysis and biosynthetic considerations. Of note, where 1-2 and 4 were active against the Gram-positive bacteria vancomycin-resistant Enterococcus faecalis (IC50 2.6-3.9 μM) and multiple-drug-resistant clinical isolates of Staphylococcus aureus (IC50 1.8-6.4 μM), and inactive against the Gram-negative bacteria Escherichia coli (IC50 > 30 μM), the closely related analog 3 exhibited no antibacterial properties (IC50 > 30 μM). Furthermore, where 1 was cytotoxic to human carcinoma (IC50 9.0-9.8 μM) and fungal (IC50 4.1 μM) cells, 2 and 4 displayed no such cytotoxicity (IC50 > 30 μM), revealing an informative structure activity relationship (SAR). We also extended the SAR study to other known compounds of this heterodimer class, which showed that the modification of ring G can reduce or eliminate the cytotoxicity while retaining the antibacterial activity.

Pharmacology of Veratrum californicum Alkaloids as Hedgehog Pathway Antagonists.

Veratrum californicum contains steroidal alkaloids that function as inhibitors of hedgehog (Hh) signaling, a pathway involved in the growth and differentiation of cells and normal tissue development. This same Hh pathway is abnormally active for cell proliferation in more than 20 types of cancer. In this current study, alkaloids have been extracted from the root and rhizome of V. californicum, followed by their separation into five fractions using high performance liquid chromatography. Mass spectrometry was used to identify the presence of twenty-five alkaloids, nine more than are commonly cited in literature reports, and the Bruker Compass Data Analysis software was used to predict the molecular formula for every detected alkaloid. The Gli activity of the raw extract and each fraction were compared to 0.1 µM cyclopamine, and fractions 1, 2, and 4 showed increased bioactivity through suppression of the Hh signaling pathway. Fractions 2 and 4 had enhanced bioactivity, but fraction 1 was most effective in inhibiting Hh signaling. The composition of fraction 1 consisted of veratrosine, cycloposine, and potential isomers of each.

A novel cobalt-based coordination polymer for rapid degradation of organic dyes in water by visible light assistance

It is crucial to construct an effective photocatalyst for the removal of dyes from aqueous environments. In the present work, a novel cobalt-based coordination polymer was synthesized and characterized with the molecular formula [Co(ipa)(ptt)]n (Co-CP), (ipa = isophthalic acid, ptt = 5-(4-Pyridyl)-1H-tetrazole). In Co-CP, each cobalt ion is in a six-coordination mode and is connected to two adjacent ligands to form a three-dimensional network structure. Furthermore, Co-CP excellent degradation properties and can effectively degrade methylene blue (MB) and rhodamine B (Rh B) under visible light with degradation efficiencies of 84.3 % and 94.6 %, respectively. Additionally, its PXRD patterns and FTIR spectra remained consistent with the original complex after three cycles, which proved that it was very stable, and there was no significant decrease in degradation ability after three cycling cycles, indicating its excellent reusability. The photocatalytic degradation mechanism was subsequently rationalized through free radical trapping experiments and analysis the energy band structure of Co-CP.

Selective Separation of Cobalt Ions from Some Fission Products Using Synthesized Inorganic Sorbent

In this work, the separation of Co(II) ions from some fission products using zirconium molybdo silicate (ZrMoSi) sorbent was studied. ZrMoSi sorbent was prepared by the co-precipitation method and characterized using different analytical tools such as FT-IR, SEM, XRF, XRD, TGA, and DTA. ZrMoSi sorbent was found to have the molecular formula ZrO2.MoO3(0.1).SiO2(10.2).4.3 H2O. The sorption behavior of Co(II) involves the effect of shaking time, pH, initial Co(II) concentrations, desorption, and recycling. The sorption data is dependent on pH and ZrMoSi has high separation factors for Co(II) from Cs(I) and Sr(II). Reaction kinetics follow the pseudo-2nd-order model with an equilibrium time of 60 min and sorption isotherms are more applicable to a Langmuir isotherm. Desorption of Co(II) from the loaded sorbent was studied using different eluents and the best eluant is HCl (93.39%). The recycling results of Co(II) from aqueous solutions are excellent and revealed that ZrMoSi sorbent can be used as a promising sorbent to remove Co(II) from liquid waste.

Transcriptomics and Metabolomics Reveal Tomato Consumption Alters Hepatic Xenobiotic Metabolism and Induces Steroidal Alkaloid Metabolite Accumulation in Mice.

Tomato consumption is associated with many health benefits including lowered risk for developing certain cancers. It is hypothesized that tomato phytochemicals are transported to the liver and other tissues where they alter gene expression in ways that lead to favorable health outcomes. However, the effects of tomato consumption on mammalian liver gene expression and chemical profile are not well defined. The study hypothesizes that tomato consumption would alter mouse liver transcriptomes and metabolomes compared to a control diet. C57BL/6J mice (n = 11-12/group) are fed a macronutrient matched diet containing either 10% red tomato, 10% tangerine tomato, or no tomato powder for 6 weeks after weaning. RNA-Seq followed by gene set enrichment analyses indicates that tomato type and consumption, in general, altered expression of phase I and II xenobiotic metabolism genes. Untargeted metabolomics experiments reveal distinct clustering between control and tomato fed animals. Nineteen molecular formulas (representing 75 chemical features) are identified or tentatively identified as steroidal alkaloids and isomers of their phase I and II metabolites; many of which are reported for the first time in mammals. These data together suggest tomato consumption may impart benefits partly through enhancing detoxification potential.

Solid-State [2+2] Photoreaction of Isostructural Cd(II) Metal Complexes and Solid-State Fluorescence.

A green method to synthesize cyclobutane derivatives has been developed over the past three decades in the form of solid-state [2+2] photochemical reactions. These solid-state reactions also play a major role in the structural transformation of hybrid materials. In this regard, crystal engineering has played a major role in designing photoreactive molecular systems. Here, we report three novel binuclear Cd(II) complexes with the molecular formula [Cd2(4spy)4L4], where 4spy = 4-styryl pyridine and L = p-toluate (1); 4-fluorobenzoate (2); and 3-fluorobenzoate (3). Although three different benzoates are used, all three complexes are isostructural, as corroborated through SCXRD experiments. Structural analysis also helped in identifying two potential photoreactions. These are both intra- and intermolecular in nature and are driven by the head-to-head (HH) and head-to-tail (HT) alignment of 4spy linkers within these metal complexes. 1H NMR spectroscopy studies showed evidence of a quantitative head-to-head photoreaction in all these three complexes, and SCXRD analysis of the recrystallization of the photoproducts also provided confirmation. TGA studies of these photoreactive complexes showed an increase in the thermal stability of the complexes due to the solid-state photoreaction. Photoluminescence studies of these complexes have been conducted, showing a blue shift in emission spectra across all three cases after the photoreaction.

Percarbonate activation catalyzed by nanoblocks of basic copper molybdate for antibiotics degradation: High performance, degradation pathways and mechanism

Sodium percarbonate (Na2CO3·1.5H2O2, SPC) has been extensively employed as a solid substitute of H2O2 for Fenton process in water treatment, because of its high stability during the production, transport, storage and usage. In addition, SPC can be applied in a wider range of work pH, it is also applied as a buffer in Fenton reaction for preventing a drop in pH. Herein, we have synthesized basic copper molybdate (BCM) nanoblocks with the molecular formula of Cu3(MoO4)2(OH)2 as an efficient and heterogeneous catalyst for antibiotics degradation via percarbonate activation. First, fully physical characterizations confirmed BCM nanocomposite exhibited a structure of nanoblocks. We also found that BCM/SPC system could work in a much wider pH range, compared with H2O2. Then, BCM/SPC system presented a good anti-interference ability for natural organic matter in OTC degradation. EPR results and Quenching tests confirmed that the co-presence of ·CO3−, ·O2−, 1O2 and ·OH in BCM/SPC system.

Atrachinenins D–S, novel meroterpenoids with geranyl hydroquinone moiety from Atractylodes chinensis by the LC/MS-based molecular decoy and targeted isolation

To mine fascinating molecules from the rhizomes of Atractylodes chinensis, the known molecular formula of atrachinenin A was used as a bait to search LC-HRMS data in different subfractions. Sixteen new meroterpenoids, atrachinenins D–S (1–16) including three unprecedented carbon skeletons (1–5) and eleven new oxygen-bridged hybrids (6–16) were obtained by the targeted isolation. Their structures and absolute configurations were elucidated by the spectroscopic data and electronic circular dichroism (ECD) calculations. The isolated compounds were evaluated for their inhibitory activity of NO production and compounds 1, 4, 8, and 13 showed moderate anti-inflammatory activity. The proposed biosynthetic pathways of 1–5 were also discussed.

Dissolved organic matter composition and characteristics during extreme flood events in the Yangtze River Estuary

Understanding the molecular composition and fate of dissolved organic matter (DOM) during transport in estuaries is essential for gaining a comprehensive understanding of its role within the global biogeochemical cycle. In 2020, a catastrophic flood occurred in the Yangtze River basin. It is currently unknown whether differences in hydrologic conditions due to extreme flooding will significantly impact the estuarine to oceanic DOM cycle. We determined the DOM composition in the Yangtze River estuary (YRE) to the East China Sea by using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) during the high discharge and the flood period (monthly average discharge was 1.2 times higher) on the same trajectory. Our study found that the composition of DOM is more diverse, and more DOM molecules were introduced to the YRE during the flood, especially in the freshwater end member. The result revealed that the DOM was significantly labile and unstable during the flood period. A total of 1840 unique molecular formulas were identified during the flood period, most of which were CHON, CHONS, and CHOS compounds, most likely resulting from anthropogenic inputs from upstream. Only 194 of these molecules were detected in the seawater end member after transporting to the sea, suggesting that the YRE served as a ‘filter’ of DOM. However, the flood enhances the transport of a group of terrigenous DOM, that is resistant to photodegradation and biodegradation. As a result, YRE experienced ~1.6 times higher terrigenous DOC flux than high discharge period. Considering the increased frequency of future floods, our study provides a preliminary basis for further research on how floods affect the composition and characteristics of estuarine DOM. With the help of the FT-ICR MS technique, we can now better understand the dynamic of DOM composition and characteristics in large river estuaries.

Mining Secondary Metabolites of Chassalia curviflora Leaves Using SIRIUS and High-Resolution Mass Spectrometry Data

Chassalia curviflora (Wall ex Kurz.) Thwaites is a flowering plant from Rubiaceae family. Previous phytochemical investigation on Chassalia species led to the isolation of benzoic acid, benzoquinone derivatives, flavonoids, monoterpenoid indole alkaloids and its essential oil composition. However, these are still scarce in terms of its scientific report on studied species. This study was carried out to investigate fast screening of secondary metabolites by using data-dependent acquisition (DDA) LC-MS/MS analysis of methanolic extract of the leaf of the C. curviflora in positive ionization mode. The data were analysed using computational mass spectrometry method from molecular structure database search implemented in Sirius. This led in discovering of 13 known secondary metabolites from a distinct tandem MS data. De novo molecular formula annotations and predictions from SIRIUS suggested five major class compounds classified as coumarin, benzofuran, fatty acids, esters and triterpenes. Stigmasterol 12 and β-sitosterol 13 were successfully isolated, thus used to verify the data obtained from the Sirius. With our results, we advocate the MS-based approach as a useful starting method for the dereplication of compounds from the complex crude extract of plants.

Классификация и характеристика нового антимикробного пептида

In recent years, significant progress has been achieved in AMP research, revealing the potential of these compounds as alternatives to traditional antibiotics. Due to the diverse mechanisms of action and a wide range of antibacterial activity, AMP provides new opportu­nities for preventing and treating multidrug-resistant infections by creating foods with anti­microbial properties, new antimicrobial biologically active additives and medicines. This study aimed to create, characterise and classify a new AMP. The DRAMP proteo­mic database was used to design the AMP, and the Peptide Ranker was utilised to predict biological activity (http://distilldeep.ucd.ie/PeptideRanker). The peptide was identified with the help of the EROP-Moscow database (http://erop.inbi.ras.ru/index.html), and its physio-chemical properties were studied using the APD, DRAMP and PepCalc databases (http://pepcalc.com). The research resulted in the design of a new AMP consisting of 11 ami­no acid residues with the following percentages: Val, Ala, Trp, Gly, Pro, Tyr, Glu, His, Lys by 9 % and Arg by 18 %. The total hydrophobic ratio in the peptide, determined by APD, is 27 %; the total net charge is +2.25. Its molecular formula is C64H96N21O15S0, with protein binding potential (Boman index) at 3.44 kcal/mol. The peptide can form an alpha helix. The resulting peptide can be classified as a synthesised cationic hydrophobic alpha-helical antimi­crobial polypeptide.

Monoterpene antifungal activities: evaluating geraniol, citronellal, and linalool on Candida biofilm, host inflammatory responses, and structure-activity relationships.

Introduction: Despite the rising concern with fungal resistance, a myriad of molecules has yet to be explored. Geraniol, linalool, and citronellal are monoterpenes with the same molecular formula (C10H18O), however, neither the effect of these compounds on inflammatory axis induced by Candida spp. nor the antibiofilm Structure-Activity Relationship (SAR) have been well-investigated. Herein we analyzed geraniol, linalool and citronellal antifungal activity, cytotoxicity, and distinctive antibiofilm SAR, also the influence of geraniol on Candida spp induced dysregulated inflammatory axis, and in vivo toxicity. Methods: Minimal inhibitory (MIC) and fungicidal (MFC) concentrations against Candida spp were defined, followed by antibiofilm activity (CFU-colony forming unit/mL/g of dry weight). Cytotoxic activity was assessed using human monocytes (THP-1) and oral squamous cell (TR146). Geraniol was selected for further analysis based on antifungal, antibiofilm and cytotoxic results. Geraniol was tested using a dual-chamber co-culture model with TR146 cells infected with C. albicans, and THP-1 cells, used to mimic oral epithelium upon fungal infection. Expression of Candida enzymes (phospholipase-PLB and aspartyl proteases-SAP) and host inflammatory cytokines (interleukins: IL-1β, IL-6, IL-17, IL-18, IL-10, and Tumor necrosis factor-TNF) were analyzed. Lastly, geraniol in vivo toxicity was assessed using Galleria mellonella. Results: MIC values obtained were 1.25-5mM/mL for geraniol, 25-100mM/mL for linalool, and 100-200mM/mL for citronellal. Geraniol 5 and 50mM/mL reduced yeast viability during biofilm analysis, only 500mM/mL of linalool was effective against a 72h biofilm and no biofilm activity was seen for citronellal. LD50 for TR146 and THP-1 were, respectively: geraniol 5.883 and 8.027mM/mL; linalool 1.432 and 1.709mM/mL; and citronellal 0.3006 and 0.1825mM/mL. Geraniol was able to downregulate expression of fungal enzymes and host pro-inflammatory cytokines IL-1β, IL-6, and IL-18. Finally, safety in vivo parameters were observed up to 20mM/Kg. Discussion: Despite chemical similarities, geraniol presented better antifungal, antibiofilm activity, and lower cytotoxicity when compared to the other monoterpenes. It also showed low in vivo toxicity and capacity to downregulate the expression of fungal enzymes and host pro-inflammatory cytokines. Thus, it can be highlighted as a viable option for oral candidiasis treatment.

Enhancing Blocking Temperatures in {Cr III 2 Dy III 2 } Butterfly SMMs: Deciphering the Role of Exchange Interactions and Developing Magneto-Structural Maps

A heterometallic butterfly-shaped complex with molecular formula; [CrIII2DyIII2(OMe)2(mdea)2(benz)4(NO3)2] (mdeaH2 = N-methyldiethanolamine, benz = benzoate) was reported by us and found to display single-molecule magnetism (SMM) behaviour with a Ueff =...