Nitrate Moiety Research Articles

Rational Molecular Engineering via Electron Reconfiguration toward Robust Dual-Electrode/Electrolyte Interphases for High-Performance Lithium Metal Batteries.

High-energy-density lithium-metal batteries (LMBs) coupling lithium-metal anodes and high-voltage cathodes are hindered by unstable electrode/electrolyte interphases (EEIs), which calls for the rational design of efficient additives. Herein, we analyze the effect of electron structure on the coordination ability and energy levels of the additive, from the aspects of intramolecular electron cloud density and electron delocalization, to reveal its mechanism on solvation structure, redox stability, as-formed EEI chemistry, and electrochemical performances. Furthermore, we propose an electron reconfiguration strategy for molecular engineering of additives, by taking sorbide nitrate (SN) additive as an example. The lone pair electron-rich group enables strong interaction with the Li ion to regulate solvation structure, and intramolecular electron delocalization yields further positive synergistic effects. The strong electron-withdrawing nitrate moiety decreases the electron cloud density of the ether-based backbone, improving the overall oxidation stability and cathode compatibility, anchoring it as a reliable cathode/electrolyte interface (CEI) framework for cathode integrity. In turn, the electron-donating bicyclic-ring-ether backbone breaks the inherent resonance structure of nitrate, facilitating its reducibility to form a N-contained and inorganic Li2O-rich solid electrolyte interface (SEI) for uniform Li deposition. Optimized physicochemical properties and interfacial biaffinity enable significantly improved electrochemical performance. High rate (10 C), low temperature (-25 °C), and long-term stability (2700 h) are achieved, and a 4.5 Ah level Li||NCM811 multilayer pouch cell under harsh conditions is realized with high energy density (462 W h/kg). The proof of concept of this work highlights that the rational ingenious molecular design based on electron structure regulation represents an energetic strategy to modulate the electrolyte and interphase stability, providing a realistic reference for electrolyte innovations and practical LMBs.

Impact of calcium nitrate supplementation on the oxygen-carrying capacity of lactating sows and their offspring.

Calcium nitrate supplementation has recently been suggested to provide potential benefits to sows and, in particular, their offspring when administered at a level of 1,200 ppm in feed shortly before farrowing through lactation. More specifically, nitrate supplementation has been suggested as one opportunity for improved placental and/or fetal blood flow and has been hypothesized in previous work to be important to the swine industry in light of the global trend toward larger litter sizes. The benefit is likely manifested through exposure to the nitrate moiety, but interestingly, nitrate has historically been considered a compound of concern for swine. High levels of nitrate once metabolized to nitrite can interfere with the oxygen-carrying capacity of hemoglobin, resulting in increased methemoglobin and, subsequently, methemoglobinemia (MetHb) if the animal is deprived of significant amounts of oxygen; however, the level of nitrate exposure necessary to induce MetHb in sows is not clearly defined. This work was undertaken to examine methemoglobin levels in sows and piglets exposed to the potentially beneficial levels of 1,200 and 6,000 ppm nitrate added to their diets over the course of the periparturient period. Other oxygen capacity blood variables were evaluated (e.g., hemoglobin, hematocrit, and various measures of hemoglobin and red blood cell volumes and concentrations), as well as performance endpoints (weight changes and feed intake) and general observations over the 27-d period. No evidence of treatment-related toxicity manifestation was observed at these supplemental levels. Nearly all oxygen-related variables were affected by time (independent of treatment), indicating adaptive general effects of farrowing. These findings support the hypothesis that MetHb is not a concern up to at least 6,000 ppm supplemental nitrate exposure, even in combination with additional nitrate in the sow’s daily diet. This work is important to help swine producers understand that consideration of nitrate benefit should outweigh concern for risk of nitrate-induced toxicity.

Assessing the impact of long-term soil phosphorus on N-transformation pathways using 15N tracing

A laboratory incubation study was conducted on a temperate grassland soil to quantify the main mineral nitrogen (N) transformation rates and pathways via a15N tracing approach. Soil samples were taken from a long-term phosphorus (P) trial to investigate the effects on gross N-transformations under high and low phosphorus amendment. The soils were incubated over a 2-week period and treated with ammonium-nitrate (NH4NO3) which was applied to the soil both with and without a glucose amendment and labelled with 15N either on the ammonium (NH4+) or nitrate (NO3−) moiety at 50% atom enrichment. The results showed immobilisation to greatly outweigh mineralisation and that NO3− was predominantly produced via heterotrophic nitrification. Individual pathways for NO3− production were quantified including oxidation of NH4+, recalcitrant and labile organic N. Oxidation of labile organic N to NO3−, a newly considered pathway, accounted for between 63 and 83% of total NO3− production across the various treatments and P levels. This process was significantly higher in the low-P rather than the high-P soils (p < 0.05), highlighting the effect of soil P on the microbial community.

Sigma Receptor Ligands Carrying a Nitric Oxide Donor Nitrate Moiety: Synthesis, In Silico, and Biological Evaluation.

We report the development of molecular hybrids in which a nitrate group serving as nitric oxide (NO) donor is covalently joined to σ receptor ligands to give candidates for double-targeted cancer therapy. The compounds have been evaluated in radioligand binding assay at both σ receptors and selected compounds tested for NO release. Compounds 9, 15, 18, 19, and 21 were subjected to MTT test. Compound 15 produced a significant reduction of MCF-7 and Caco-2 cellular viability with comparable IC50 as doxorubicin, being also not toxic for fibroblast HFF-1 cells. Compound 15 has shown a σ1 receptor antagonist/σ2 receptor agonist profile. Two derivatives of compound 15 lacking the nitrate group did not induce a reduction of MCF-7 cellular viability, suggesting a potential synergistic effect between the σ receptors and the NO-mediated events. Overall, the combination of NO donor and σ receptors ligands provided compounds with beneficial effects for the treatment of cancer.

Synthesis and Cytotoxicity Evaluation of Dehydroabietic Acid Derivatives Bearing Nitrate Moiety

Synthesis and Cytotoxicity Evaluation of Dehydroabietic Acid Derivatives Bearing Nitrate Moiety

Vapor-pressure pathways initiate but hydrolysis products dominate the aerosol estimated from organic nitrates.

Organic nitrates contribute significantly to the total organic aerosol burden. However, the formation and loss mechanisms of particulate organic nitrates (PONs) remain poorly understood. In this study, with the CMAQ modeling system, we implement a detailed biogenic volatile organic carbon gas phase oxidation mechanism and an explicit representation of multiphase organic nitrate formation and loss, including both aqueous-phase uptake and vapor-pressure driven partitioning into organic aerosol as well as condensed-phase reactions. We find vapor-pressure dependent partitioning is the leading mechanism for formation of PONs and hydrolysis is a major loss mechanism for PON resulting in substantial amounts of organic aerosol that originate as an organic nitrate. Partitioning and hydrolysis together can produce high concentrations (up to 5 μg/m3) of PON-derived aerosols over the southeast United States. The main source of PON-derived aerosols is monoterpene nitrates that have been chemically processed to lose their nitrate functionality through aqueous chemistry. In contrast, the major portion of aqueous aerosol and in-cloud PON, which retains its nitrate moiety, are soluble isoprene nitrates. We evaluate the model using the observations from the Southern Oxidant and Aerosol Study (SOAS) campaign in the Southeast US in summer 2013 and show implementing aerosol-phase pathways for organic nitrates dramatically improves the magnitude of total alkyl nitrates (ANs) in CMAQ. The contribution of PONs to the total ANs at the SOAS site is estimated to be ~20%, a value in the range of the measurements. The predicted AN composition is shifted from monoterpene to isoprene and anthropogenic organic nitrates.

Abstract 5825: Structure-based drug design to overcome temozolomide resistance in glioblastoma (GBM) through a dual inhibition of MGMT and base excision repair

Abstract The incidence of pediatric and adult brain tumors has continued to rise and temozolomide (TMZ) has remained the sole choice for chemotherapy in these cancers. TMZ alkylates the DNA to generate N7-methylguanine (~70%) and O6-methylguanine (~6-9%) lesions, with the latter being considered the cytotoxic residue. However, the N7-methylations can also contribute to cell killing by producing abasic sites, strand-breaks, and mutagenicity. Therefore, inhibiting the two major mechanisms of resistance to TMZ in brain cancers, namely, the MGMT DNA repair, which removes the O6-methyl groups, and the APE1 endonuclease, which cleaves the apurinic/apyrimidinic sites, is a logical choice for enhancing the alkylator therapy; incidentally, both these proteins are highly expressed in brain tumors. Pseudosubstrates for MGMT such as O6-BG + TMZ therapies suffer from a high level of bone marrow suppression and there is no clinically approved inhibitor for APE1. Recently, we discovered that nitroaspirin (NCX-4016) is a powerful and clinically relevant inhibitor of human MGMT for increasing the efficacy of alkylating agents (Proc of AACR 54, 2013;1094). Further extensive structure-activity relationship studies revealed that the 3-hydroxybenzyl nitrate moiety of NCX-4016 is essential for its MGMT inhibition activity. To develop a dual inhibitor of APE1 and MGMT, we designed a hybrid compound called MGAP-9 by combining 3-hydroxybenzyl nitrate with 7-nitroindole-2-carboxylic acid, a known potent, nontoxic, and cell-permeable APE1 inhibitor through an ester bond. MGAP-9 exhibited significant inhibition of MGMT activity and a corresponding decrease in protein levels in both concentrations- and time-dependent manner. Similarly, we observed potent inhibition of APE1 nuclease activity both in vitro and in tumor cells using a biotin-labeled oligonucleotide/polyacrylamide gel-electrophoresis assay. Inhibition of both targets occurred at pharmacologically achievable concentrations (5-25 µM). MGAP-9 exhibited more than 100-fold sensitization of various GBM cell lines towards the methylating agents such as TMZ and dacarbazine, but surprisingly not to BCNU or CCNU. A substantial increase in γ-H2AX further confirmed the DNA damage induced by MGAP-9 through a dual inhibition. In addition, the hybrid drug displayed potent antiangiogenic activity against human umbilical vein cells (HUVECs). Finally, MGAP-9 showed significant regression of tumor growth in mouse orthotopic glioblastoma xenograft models and did not elicit systemic toxicity at the therapeutic doses used. The findings suggest the clinical relevance of MGAP-9 and its usefulness in reducing the TMZ doses to curtail the marrow suppression in brain tumor therapy. Supported by CPRIT grants RP130266 and RP170207 to KSS. Citation Format: Hanumantha Rao Madala, Viswanath Arutla, Surendra Punganuru, Kalkunte Srivenugopal. Structure-based drug design to overcome temozolomide resistance in glioblastoma (GBM) through a dual inhibition of MGMT and base excision repair [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2018; 2018 Apr 14-18; Chicago, IL. Philadelphia (PA): AACR; Cancer Res 2018;78(13 Suppl):Abstract nr 5825.

Nitrate radical oxidation of &amp;lt;i&amp;gt;γ&amp;lt;/i&amp;gt;-terpinene: hydroxy nitrate, total organic nitrate, and secondary organic aerosol yields

Abstract. Polyolefinic monoterpenes represent a potentially important but understudied source of organic nitrates (ONs) and secondary organic aerosol (SOA) following oxidation due to their high reactivity and propensity for multi-stage chemistry. Recent modeling work suggests that the oxidation of polyolefinic γ-terpinene can be the dominant source of nighttime ON in a mixed forest environment. However, the ON yields, aerosol partitioning behavior, and SOA yields from γ-terpinene oxidation by the nitrate radical (NO3), an important nighttime oxidant, have not been determined experimentally. In this work, we present a comprehensive experimental investigation of the total (gas + particle) ON, hydroxy nitrate, and SOA yields following γ-terpinene oxidation by NO3. Under dry conditions, the hydroxy nitrate yield = 4(+1/−3) %, total ON yield = 14(+3/−2) %, and SOA yield ≤ 10 % under atmospherically relevant particle mass loadings, similar to those for α-pinene + NO3. Using a chemical box model, we show that the measured concentrations of NO2 and γ-terpinene hydroxy nitrates can be reliably simulated from α-pinene + NO3 chemistry. This suggests that NO3 addition to either of the two internal double bonds of γ-terpinene primarily decomposes forming a relatively volatile keto-aldehyde, reconciling the small SOA yield observed here and for other internal olefinic terpenes. Based on aerosol partitioning analysis and identification of speciated particle-phase ON applying high-resolution liquid chromatography–mass spectrometry, we estimate that a significant fraction of the particle-phase ON has the hydroxy nitrate moiety. This work greatly contributes to our understanding of ON and SOA formation from polyolefin monoterpene oxidation, which could be important in the northern continental US and the Midwest, where polyolefinic monoterpene emissions are greatest.

Design and synthesis of pyrazolo[3,4-d]pyrimidines: Nitric oxide releasing compounds targeting hepatocellular carcinoma

A new series of pyrazolo[3,4-d]pyrimidines tethered with nitric oxide (NO) producing functionality was designed and synthesized. Sulforhodamine B (SRB) protein assay revealed that NO releasing moiety in the synthesized compounds significantly decreased the cell growth more than the des-NO analogues. Compounds 7C and 7G possessing N-para-substituted phenyl group, released the highest NO concentration of 4.6% and 4.7% respectively. Anti-proliferative activity of synthesized compounds on HepG2 cell line identified compounds 7h, 7p, 14a and 14b as the most cytotoxic compounds in the series of IC50=3, 5, 3 and 5μM, respectively, compared to erlotinib as a reference drug (IC50=25μM). Flow cytometry studies revealed that 7h arrested the cells in G0/G1 phase of cell cycle while 7p arrested the cells in S phase. Moreover, docking study of the synthesized compounds on EGFR (PDB code: 1M17) and cytotoxicity study indicated that N-1 phenyl para substitution, pyrazole C-3 alkyl substitution and tethering the nitrate moiety through butyl group had a significant impact on the activity.

New organic nitrate-containing benzyloxy isonipecotanilide derivatives with vasodilatory and anti-platelet activity

A number of new nitric oxide (NO)-precursors were synthesized by grafting nitrate-containing moieties on the structures of the benzyloxy isonipecotanilide derivatives 1 and 2 already reported as moderately potent antiplatelet agents. Various nitrooxy (ONO2)-alkyl side chains were covalently linked to the piperidine nitrogen of the parent compounds through carbamate and amide linkage, and the synthesis of a benzyl nitrate analog (15) of compound 1 was also achieved. The in vitro vasodilatory activities, as well as platelet anti-aggregatory effects, of the newly synthesized organic nitrates were assessed. The (ONO2)methyl carbamate-based derivative 5a and the benzyl nitrate analog 15, which on the other hand retain activity as inhibitors of ADP-induced platelet aggregation, exhibited strong NO-mediated vasodilatory effects on pre-contracted rat aorta strips, with EC50 values in the low nanomolar range (13 and 29nM, respectively). Experiments carried out with the selectively inhibited soluble guanylate cyclase (sGC), which is the key enzyme of the NO-mediated pathway leading to vascular smooth muscle relaxation, confirmed the involvement of NO in the observed vasodilation. The nitrate derivatives proved to be stable in acidic aqueous solution and at pH 7.4. In human serum, unlike 5a, which showed not to undergo enzyme-catalyzed decomposition, the other tested (ONO2)-alkyl carbamate-based compounds (5b and 5e) and benzyl nitrate 15 underwent a faster degradation. However, their decomposition rates in serum were quite slow (t½>2.6h), which suggests that nitrate moiety is poorly metabolized in blood plasma and that much of the in vitro anti-platelet activity has to be attributed to the intact (ONO2)-containing molecules.

In vitro and in vivo Characterization of a New Organic Nitrate Hybrid Drug Covalently Bound to Pioglitazone

Background/Aims: Organic nitrates represent a group of nitrovasodilators that are clinically used for the treatment of ischemic heart disease. The new compound CLC-3000 is an aminoethyl nitrate (AEN) derivative of pioglitazone, a thiazolidinedione antidiabetic agent combining the peroxisome proliferator-activated receptor γ agonist activity of pioglitazone with the NO-donating activity of the nitrate moiety. Methods: In vitro and in vivo characterization was performed by isometric tension recording, platelet function, bleeding time and detection of oxidative stress. Results: In vitro, CLC-3000 displayed more potent vasodilation than pioglitazone alone or classical nitrates. In vitro, some effects on oxidative stress parameters were observed. Authentic AEN or the AEN-containing linker CLC-1275 displayed antiaggregatory effects. In vivo treatment with CLC-3000 for 7 days did neither induce endothelial dysfunction nor nitrate tolerance nor oxidative stress. Acute or chronic administration of AEN increased the tail vein bleeding time in mice. Conclusion: In summary, the results of these studies demonstrate that CLC-3000 contains a vasodilative and antithrombotic activity that is not evident with pioglitazone alone, and that 7 days of exposure in vivo showed no typical signs of nitrate tolerance, endothelial dysfunction or other safety concerns in Wistar rats.

Abstract 349: Characterization of a New Organic Nitrate Hybrid Drug Covalently Bound to Pioglitazone

Background and Purpose: Organic nitrates represent a group of nitrovasodilators that are clinically used for the treatment of ischemic heart disease. With the present studies we synthesized and characterized a new organic nitrate hybrid molecule. Compound CLC-3000 is an aminoethyl nitrate (AEN) derivative of pioglitazone, a thiazolidinedione antidiabetic agent. This new molecular entity combines the peroxisome proliferator-activated receptor gamma (PPAR-γ) agonist activity of pioglitazone with the NO-donating activity of the nitrate moiety. Experimental Approach: In vitro and in vivo characterization was performed by isometric tension recording, bleeding time and detection of oxidative stress. Key Results: The vasodilative potency of CLC-3000 in vitro was shown to be markedly superior to that of pioglitazone alone or a classical nitrate, although in vitro, at high concentrations, some effects on oxidative stress parameters were observed. Following seven days exposure to CLC-3000 in vivo, no change was seen in the vasodilative response of rat aortic rings towards acetylcholine, nitroglycerin or CLC-3000 itself. Similarly, no remarkable increase in oxidative stress parameters was observed under CLC-3000 therapy. Acute or chronic administration of AEN decreased the tail vein bleeding time in mice. Conclusions and Implications: In summary, the results of these studies demonstrate that CLC-3000 contains a vasodilative and anti-thrombotic activity that is not evident with pioglitazone alone, and that seven days exposure in vivo showed no typical signs of nitrate tolerance, endothelial dysfunction or other safety concerns in Wistar rats.

Design, synthesis and biological evaluation of D-ring opened galantamine analogs as multifunctional anti-Alzheimer agents

Facing the multifactorial nature of Alzheimer's disease, twelve dibenzofuran/carbazole derivatives, which can be considered as the D-ring opened analogs of galantamine, have been designed and synthesized as multifunctional anti-Alzheimer agents. In vitro tests revealed that compounds 3 and 5, which bear a nitrate moiety in the molecule, showed a potent inhibition activity towards AChE and compound 3 showed a good Aβ42 aggregation inhibitory activity. Moreover, 3 and 5 could also release a relative low concentration of NO in vitro and they did not show toxicity to neuronal cells, while exerted a neuroprotective effect against the Aβ-induced toxicity. More importantly, compound 3 showed a significant spatial memory improving effect in vivo, and a good safety in the ex vivo toxicity study.

Effect of Chemical Precursors On the Optical and Electrical Properties of p-Type Transparent Conducting Cr2O3:(Mg,N)

Cr2O3:(Mg,N) has been reported as a p-type transparent conducting oxide. In this contribution the effect of each precursor used for deposition by spray-pyrolysis will be explored and their role in determining the optical and electrical properties of Cr2O3 will be outlined. A correlation between the structural, electrical, and optical properties upon introducing nitrogen precursors has been established. In particular it has been shown that the presence of ammonium salts in the deposition environment results in less absorbing films. By combining optical measurements and NEXAFS studies, a mechanism is proposed to explain the change in the optical properties. Moreover, it is shown that the presence of the nitrate moiety in the reaction environment is necessary to improve the electrical conductivity of the deposited films. The reaction of the nitrate moiety with the ammonium moiety has been proposed as the mechanism to explain the boost in conductivity.

Metabolism and Pathways for Denitration of Organic Nitrates in the Human Liver

Liver first-pass metabolism differs considerably among organic nitrates, but little information exists on the mechanism of denitration of these compounds in hepatic tissue. The metabolism of nitrooxybutyl-esters of flurbiprofen and ferulic-acid, a class of organic nitrates with potential therapeutic implication in variety of different conditions, was investigated in comparison with glyceryl trinitrate (GTN) in human liver by a multiple approach, using a spontaneous metabolism-independent nitric oxide (NO) donor [3-(aminopropyl)-1-hydroxy-3-isopropyl-2-oxo-1-triazene (NOC-5)] as a reference tool. Nitrooxybutyl-esters were rapidly and quantitatively metabolized to their respective parent compounds and the organic nitrate moiety nitrooxybutyl-alcohol (NOBA). Differently from GTN, which was rapidly and completely metabolized to nitrite, NOBA was slowly metabolized to nitrate. In contrast to the spontaneous NO donor NOC-5, NOBA and GTN did not generate detectable NO and failed to suppress the activity of cytochrome P450, an enzyme known to be inhibited by NO. The direct identification of NOBA after liver metabolism targets this compound as the functional organic nitrate metabolite of nitrooxybutyl-esters. Moreover, the investigation of the pathways for denitration of NOBA and GTN suggests that organic nitrates are not primarily metabolized to NO in the liver but to different extents of nitrite or nitrate depending in their different chemical structure. Therefore, cytochrome P450-dependent metabolism of concomitant drugs is not likely to be affected by oral coadministration of organic nitrates. However, the first pass may differently affect the pharmacological profile of organic nitrates in connection with the different extent of denitration and the distinct bioactive species generated and exported from the liver (nitrate or nitrite).

Nitrogen-Containing Organic Compounds and Oligomers in Secondary Organic Aerosol Formed by Photooxidation of Isoprene

Electrospray ionization high-resolution mass spectrometry (ESI HR-MS) was used to probe molecular structures of oligomers in secondary organic aerosol (SOA) generated in laboratory experiments on isoprene photooxidation at low- and high-NO(x) conditions. Approximately 80-90% of the observed products are oligomers and up to 33% by number are nitrogen-containing organic compounds (NOC). We observe oligomers with maximum 8 monomer units in length. Tandem mass spectrometry (MS(n)) confirms NOC compounds are organic nitrates and elucidates plausible chemical building blocks contributing to oligomer formation. Most organic nitrates are comprised of methylglyceric acid units. Other important multifunctional C(2)-C(5) monomer units are identified including methylglyoxal, hydroxyacetone, hydroxyacetic acid, and glycolaldehyde. Although the molar fraction of NOC in the high-NO(x) SOA is high, the majority of the NOC oligomers contain only one nitrate moiety resulting in a low average N:C ratio of 0.019. Average O:C ratios of the detected SOA compounds are 0.54 under the low-NO(x) conditions and 0.83 under the high-NO(x) conditions. Our results underscore the importance of isoprene photooxidation as a source of NOC in organic particulate matter.

Reversible Shuttle Action upon Dehydration and Rehydration Processes in Cationic Coordinatively-Bonded (4,4) Square-Grid Nets Threaded by Supramolecular Bonded Anions, {[CuII(4,4′-bpy)2(H2O)][CuII(2-pySO3)3](NO3)}·H2O

{[Cu(II)(4,4'-bpy)(2)(H(2)O)][Cu(II)(2-pySO(3))(3)](NO(3))}·H(2)O, obtained serendipitously by the reaction of the constituents in water, consists of parallel coordinatively bonded cationic (4,4) corrugated square-grids polymer of {[Cu(II)(4,4'-bpy)(2)(H(2)O)](2+)}(n) threaded by π-π and H-bonded supramolecular chains of [Cu(II)(2-pySO(3))(3)](-) through the open squares. A single-crystal to single-crystal transformation takes place upon removal of the noncoordinated water by controlled heating. The resulting structure exhibits a rearrangement of the coordination of the copper atoms in the grids, where the Cu-H(2)O bond is elongated from 2.250(3) to 2.628(3) Å while the Cu-NO(3) is shortened from 3.122(3) to 2.796(1) Å. This process is reversible as demonstrated by the single crystal structure after rehydration with corresponding bond distances of 2.224(3) and 3.152(3) Å. Such a cooperative effect may be associated with the Jahn-Teller distortion of the copper(II) ion accompanying the shuttle action of the hydrogen-bonded water and nitrate moiety.

Real Time In Situ Detection of Organic Nitrates in Atmospheric Aerosols

A novel instrument is described that quantifies total particle-phase organic nitrates in real time with a detection limit of 0.11 microg m(-3) min(-1), 45 ppt min(-1) (-ONO(2)). Aerosol nitrates are separated from gas-phase nitrates with a short residence time activated carbon denuder. Detection of organic molecules containing -ONO(2) subunits is accomplished using thermal dissociation coupled to laser induced fluorescence detection of NO(2). This instrument is capable of high time resolution (seconds) measurements of particle-phase organic nitrates, without interference from inorganic nitrate. Here we use it to quantify organic nitrates in secondary organic aerosol generated from high-NO(x) photooxidation of limonene, alpha-pinene, Delta-3-carene, and tridecane. In these experiments the organic nitrate moiety is observed to be 6-15% of the total SOA mass.

NO-donors. Part 17 : Synthesis and antimicrobial activity of novel ketoconazole–NO-donor hybrid compounds

Novel hybrid compounds combining the antifungal drug ketoconazole with a diazen-1-ium-1,2-diolate or an organic nitrate moiety and the corresponding NO-donors without ketoconazole were synthesized and their activities against a broad variety of fungal strains were tested. Hybridization modifies the spectrum of antimicrobial activities and generally, the ketoconazole–NO-donor hybrids are more potent than ketoconazole. The NO-donors alone show insufficient effectiveness.

Chemically Adjusting Plasma Temperature, Energy, and Reactivity (CAPTEAR) Method Using NOx and Combustion for Selective Synthesis of Sc3N@C80 Metallic Nitride Fullerenes

Goals are (1) to selectively synthesize metallic nitride fullerenes (MNFs) in lieu of empty-cage fullerenes (e.g., C60, C70) without compromising MNF yield and (2) to test our hypothesis that MNFs possess a different set of optimal formation parameters than empty-cage fullerenes. In this work, we introduce a novel approach for the selective synthesis of metallic nitride fullerenes. This new method is "Chemically Adjusting Plasma Temperature, Energy, and Reactivity" (CAPTEAR). The CAPTEAR approach with copper nitrate hydrate uses NOx vapor from NOx generating solid reagents, air, and combustion to "tune" the temperature, energy, and reactivity of the plasma environment. The extent of temperature, energy, and reactive environment is stoichiometrically varied until optimal conditions for selective MNF synthesis are achieved. Analysis of soot extracts indicate that percentages of C60 and Sc3N@C80 are inversely related, whereas the percentages of C70 and higher empty-cage C2n fullerenes are largely unaffected. Hence, there may be a "competitive link" in the formation and mechanism of C60 and Sc3N@C80. Using this CAPTEAR method, purified MNFs (96% Sc3N@C80, 12 mg) have been obtained in soot extracts without a significant penalty in milligram yield when compared to control soot extracts (4% Sc3N@C80, 13 mg of Sc3N@C80). The CAPTEAR process with Cu(NO3)2.2.5H2O uses an exothermic nitrate moiety to suppress empty-cage fullerene formation, whereas Cu functions as a catalyst additive to offset the reactive plasma environment and boost the Sc3N@C80 MNF production.