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1.
J Environ Manage ; 281: 111882, 2021 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-33421937

RESUMO

Three of the primary functions of green roofs in urban areas are to delay rainwater runoff, moderate building temperatures, and ameliorate the urban heat island (UHI) effect. A major impediment to the survival of plants on an unirrigated extensive green roof (EGR) is the harsh rooftop environment, including high temperatures and limited water during dry periods. Factors that influence EGR thermal and hydrologic performance include the albedo (reflectivity) of the roof and the composition of the green roof substrate (growing media). In this study we used white, reflective shading structures and three different media formulations to evaluate EGR thermal and hydrologic performance in the Pacific Northwest, USA. Shading significantly reduced daytime mean and maximum EGR media temperatures and significantly increased nighttime mean and minimum temperatures, which may provide energy benefits to buildings. Mean media moisture was greater in shaded trays than in exposed (unshaded) trays but differences were not statistically significant. Warmer nighttime media temperatures and lack of dew formation in shaded trays may have partially compensated for greater daytime evaporation from exposed trays. Media composition did not significantly influence media temperature or moisture. Results of this study suggest that adding shade structures to green roofs will combine thermal, hydrologic, and ecological benefits, and help achieve temperature and light regimes that allow for greater plant diversity on EGRs.


Assuntos
Conservação dos Recursos Naturais , Temperatura Alta , Cidades , Noroeste dos Estados Unidos , Temperatura
2.
J Environ Manage ; 277: 111418, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-33080432

RESUMO

Green roofs are among the most popular type of green infrastructure implemented in highly urbanized watersheds due to their low cost and efficient utilization of unused or under-used space. In this study, we examined the effectiveness of green roofs to attenuate stormwater runoff across a large metropolitan area in the Pacific Northwest, United States. We utilized a spatially explicit ecohydrological watershed model called Visualizing Ecosystem Land Management Assessments (VELMA) to simulate the resulting stormwater hydrology of implementing green roofs over 25%, 50%, 75%, and 100% of existing buildings within four urban watersheds in Seattle, Washington, United States. We simulated the effects of two types of green roofs: extensive green roofs, which are characterized by shallow soil profiles and short vegetative cover, and intensive green roofs, which are characterized by deeper soil profiles and can support larger vegetation. While buildings only comprise approximately 10% of the total area within each of the four watersheds, our simulations showed that 100% implementation of green roofs on these buildings can achieve approximately 10-15% and 20-25% mean annual runoff reductions for extensive and intensive green roofs, respectively, over a 28-year simulation. These results provide an upper limit for volume reductions achievable by green roofs in these urban watersheds. We also showed that stormwater runoff reductions are proportionately smaller during higher flow regimes caused by increased precipitation, likely due to the limited storage capacity of saturated green roofs. In general, green roofs can be effective at reducing stormwater runoff, and their effectiveness is limited by both their areal extent and storage capacity. Our results showed that green roof implementation can be an effective stormwater management tool in highly urban areas, and we demonstrated that our modeling approach can be used to assess the watershed-scale hydrologic impacts of the widespread adoption of green roofs across large metropolitan areas.


Assuntos
Hidrologia , Movimentos da Água , Conservação dos Recursos Naturais , Ecossistema , Chuva , Washington
3.
Geobiology ; 18(5): 560-565, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-32347003

RESUMO

The chemical composition of fossil soft tissues is a potentially powerful and yet underutilized tool for elucidating the affinity of problematic fossil organisms. In some cases, it has proven difficult to assign a problematic fossil even to the invertebrates or vertebrates (more generally chordates) based on often incompletely preserved morphology alone, and chemical composition may help to resolve such questions. Here, we use in situ Raman microspectroscopy to investigate the chemistry of a diverse array of invertebrate and vertebrate fossils from the Pennsylvanian Mazon Creek Lagerstätte of Illinois, and we generate a ChemoSpace through principal component analysis (PCA) of the in situ Raman spectra. Invertebrate soft tissues characterized by chitin (polysaccharide) fossilization products and vertebrate soft tissues characterized by protein fossilization products plot in completely separate, non-overlapping regions of the ChemoSpace, demonstrating the utility of certain soft tissue molecular signatures as biomarkers for the original soft tissue composition of fossil organisms. The controversial problematicum Tullimonstrum, known as the Tully Monster, groups with the vertebrates, providing strong evidence of a vertebrate rather than invertebrate affinity.


Assuntos
Invertebrados , Vertebrados , Animais , Fósseis , Illinois , Filogenia
4.
J Phys Chem A ; 123(51): 10885-10892, 2019 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-31794665

RESUMO

The unimolecular dissociation of ionized tetralin was probed by tandem mass spectrometry, imaging photoelectron photoion coincidence (iPEPICO) spectroscopy, and theory. The major reactions observed were the loss of the hydrocarbons CH3•, C2H4, and C3H5• together with H•-atom loss. RRKM modeling of the iPEPICO data suggested a two-well potential energy surface. Ionized tetralin can lose all four neutrals via H-shift and ring-opening reactions or CH3• and C2H4 after interconversion to the 1-methylindane ion, a process similar to that found for ionized 1,2-dihydronaphthalene (isomerizing to form the 1-methylindene ion structure). This was confirmed at the B3LYP/6-31+G(d,p) level of theory, and potential mechanisms for all reactions are described. The ionization energy of tetralin was established from the threshold photoelectron spectrum to be 8.46 ± 0.01 eV.

5.
J Phys Chem A ; 123(50): 10694-10699, 2019 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-31765149

RESUMO

Tandem mass spectrometry was used to explore the trends in the unimolecular fragmentation of the ionized hydroxy-substituted polycyclic aromatic hydrocarbons 1-naphthol, 9-hydroxyphenanthrene, and 1-hydroxypyrene. The main dissociation reactions across all ring systems were CO- and HCO-losses, with ionized 1-naphthol also losing H atoms. Both ionized 1-naphthol and 9-hydroxyphenanthrene displayed the sequential loss of C2H2 and C4H2 from the [M-HCO]+ ions, reminiscent of unsubstituted PAH ions. CO-loss is slightly favored for 1-naphthol and 9-hydroxyphenanthrene, at low collision energy, but less so for 1-hydroxypyrene. Reaction mechanisms for HCO- and CO-losses from 1-hydroxypyrene were derived from CCSD/6-31G(d)//B3-LYP/6-31G(d) calculations. The CO-loss mechanism is dominated by two transition states: TS-A governing a 1,3-H shift in the molecular ion and TS-C which governs a ring-closing step to form a five-member ring in the product ion. HCO-loss occurs over a much flatter potential energy surface with the intermediate being the product ion bound to the carbon atom of HCO. Imaging photoelectron photoion coincidence spectroscopy of 1-hydroxypyrene yielded threshold photon-energy resolved breakdown curves and time-of-flight distributions that were modeled with RRKM theory to give 0 K reaction energies for HCO- and CO-losses of 3.92 ± 0.05 and 2.91 ± 0.05 eV, respectively. The entropies of activation for the two channels were very different, 14 and 95 JK-1 mol-1, respectively, a result consistent with the calculated mechanisms. The threshold photoelectron spectrum yielded an IE value of 7.14 ± 0.01 eV for 1-hydroxypyrene.

6.
J Phys Chem A ; 123(24): 5027-5034, 2019 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-31150240

RESUMO

Collision-energy resolved tandem mass spectrometry was used to probe the trends in unimolecular fragmentation in a series of ionized amino-substituted polycyclic aromatic hydrocarbons ranging from naphthalene to pyrene. As the ring system expands, the dominant dissociation process changes from HNC loss (aniline) to H loss for 1-aminopyrene. Imaging photoelectron photoion coincidence spectroscopy of 1-aminopyrene yielded threshold photon-energy resolved breakdown curves, the Rice-Ramsperger-Kassel-Marcus modeling of which gave a 0 K activation energy, E0, for H loss of 3.8 ± 0.4 eV. Calculations at the CCSD/6-31G(d)//B3LYP/6-31G(d) level of theory were used to explore the possible reaction mechanisms for H, HNC, and C,N,H2 losses, and details of the reaction pathways are presented. The H atom loss was found to be due both to direct N-H bond cleavage and isomerization to form an azepine derivative.

7.
J Phys Chem A ; 123(29): 6313-6318, 2019 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-31251045

RESUMO

The threshold photoelectron spectra (TPES) and ion dissociation breakdown curves for trifluoroacetic acid (TFA) and trifluoroacetic anhydride (TFAN) were measured by imaging photoelectron photoion coincidence spectroscopy employing both effusive room-temperature samples and samples introduced in a seeded molecular beam. The fine structure in the breakdown diagram of TFA mirroring the vibrational progression in the TPES suggests that direct ionization to the X̃+ state leads to parent ions with a lower "effective temperature" than nonresonant ionization in between the vibrational progression. Composite W1U, CBS-QB3, CBS-APNO, G3, and G4 calculations yielded an average ionization energy (IE) of 11.69 ± 0.06 eV, consistent with the experimental value of 11.64 ± 0.01 eV, based on Franck-Condon modeling of the TPES. The measured 0 K appearance energies (AE0K) for the reaction forming CO2H+ + CF3 from TFA were 11.92 for effusive data and 11.94 ± 0.01 eV for molecular beam data, consistent with the calculated composite method 0 K reaction energy of 11.95 ± 0.08 eV. Together with the 0 K heats of formation (ΔfH0K) of CO2H+ and CF3, this yields a ΔfH0K of neutral TFA of -1016.6 ± 1.5 kJ mol-1 (-1028.3 ± 1.5 kJ mol-1 at 298 K). TFAN did not exhibit a molecular ion at room-temperature conditions, but a small signal was observed when rovibrationally cold species were probed in a molecular beam. The two observed dissociation channels were CF3C(O)OC(O)+ + CF3 and the dominant, sequential reaction CF3CO+ + CF3 + CO2. Calculations revealed a low-energy isomer of ionized TFAN, incorporating the three moieties CF3CO+, CF3, and CO2 joined in a noncovalent complex, mediating its unimolecular dissociation.

8.
J Phys Chem A ; 123(16): 3569-3574, 2019 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-30939003

RESUMO

The reaction mechanisms for the loss of C2H2 from the ions of anthracene, phenanthrene, tetracene, and pyrene were calculated at the B3-LYP/6-311++G(2d,p) level of theory and compared to that previously published for ionized naphthalene. A common pathway emerged involving the isomerization of the molecular ions to azulene-containing analogues, followed by the contraction of the seven-member ring into a five- and four-member fused ring system, leading to the cleavage of C2H2. The key transition state was found to be for this last process, and its relative energy was consistent going from naphthalene to tetracene. That for pyrene, though, was significantly higher due to the inability of the azulene moiety to achieve a stable conformation because of the presence of the three fused rings. Thus, C2H2 loss is discriminated against in pericondensed PAHs. For catacondensed PAHs, C2H2 loss also drops in relative abundance as the PAH gets larger due to the increase in the number of available hydrogen atoms, increasing the rate constant for H atom loss over that for C2H2 loss as PAH size increases. The unimolecular reactions of four cyano-substituted polycyclic aromatic hydrocarbon (PAH) ions were also probed as a function of collision energy by collision-induced dissociation tandem mass spectrometry. As the size of the ring system increases, HCN loss decreases in importance relative to other processes (H and C2H2 loss). 9-Cyanophenanthrene ions were chosen for further exploration by theory and imaging photoelectron photoion coincidence (iPEPICO) spectroscopy. The calculated reaction pathway and energetics for C2H2 loss were consistent with those found above. The calculations suggest that larger PAHs of interest in the interstellar environment will behave independently of a CN substituent.

9.
PLoS One ; 14(1): e0210859, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-30682083

RESUMO

BACKGROUND: Synthetic lethality describes a relationship between two genes where single loss of either gene does not trigger significant impact on cell viability, but simultaneous loss of both gene functions results in lethality. Targeting synthetic lethal interactions with drug combinations promises increased efficacy in tumor therapy. MATERIALS AND METHODS: We established a set of synthetic lethal interactions using publicly available data from yeast screens which were mapped to their respective human orthologs using information from orthology databases. This set of experimental synthetic lethal interactions was complemented by a set of predicted synthetic lethal interactions based on a set of protein meta-data like e.g. molecular pathway assignment. Based on the combined set, we evaluated drug combinations used in late stage clinical development (clinical phase III and IV trials) or already in clinical use for ovarian cancer with respect to their effect on synthetic lethal interactions. We furthermore identified a set of drug combinations currently not being tested in late stage ovarian cancer clinical trials that however have impact on synthetic lethal interactions thus being worth of further investigations regarding their therapeutic potential in ovarian cancer. RESULTS: Twelve of the tested drug combinations addressed a synthetic lethal interaction with the anti-VEGF inhibitor bevacizumab in combination with paclitaxel being the most studied drug combination addressing the synthetic lethal pair between VEGFA and BCL2. The set of 84 predicted drug combinations for example holds the combination of the PARP inhibitor olaparib and paclitaxel, which showed efficacy in phase II clinical studies. CONCLUSION: A set of drug combinations currently not tested in late stage ovarian cancer clinical trials was identified having impact on synthetic lethal interactions thus being worth of further investigations regarding their therapeutic potential in ovarian cancer.


Assuntos
Protocolos de Quimioterapia Combinada Antineoplásica/uso terapêutico , Terapia de Alvo Molecular/métodos , Neoplasias Ovarianas/tratamento farmacológico , Neoplasias Ovarianas/genética , Mutações Sintéticas Letais/efeitos dos fármacos , Bevacizumab/administração & dosagem , Ensaios Clínicos como Assunto , Feminino , Humanos , Paclitaxel/administração & dosagem , Ftalazinas/administração & dosagem , Piperazinas/administração & dosagem , Inibidores de Poli(ADP-Ribose) Polimerases/administração & dosagem , Proteínas Proto-Oncogênicas c-bcl-2/antagonistas & inibidores , Proteínas Proto-Oncogênicas c-bcl-2/genética , Fator A de Crescimento do Endotélio Vascular/antagonistas & inibidores , Fator A de Crescimento do Endotélio Vascular/genética
10.
Ecol Eng ; 140: 1-105589, 2019 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-32020990

RESUMO

One of the primary functions of green roofs in urban areas is to moderate rainwater runoff, and one of the major impediments to the survival of plants on an extensive green roof (EGR) is a lack of available water during dry periods. Runoff moderation and water storage are both influenced by the composition of the growing media. Here we present a framework for evaluating the hydrologic performance of EGR growing media and also provide hydrologic attribute data for several commonly used EGR media constituents. In this three-phase study, we: 1) measured hydrologic attributes of individual EGR media constituents, 2) predicted attributes of media mixtures using individual constituent data, and 3) tested the seven top-ranking mixtures to evaluate hydrologic performance. Hydrologic attributes included wet weight and water held at maximum retentive capacity, long-term water retention, and hydraulic conductivity. Because perlite was light in weight yet held the greatest amount of water both at its maximum retentive capacity and in the long term, media mixtures dominated by perlite were predicted to have the best overall hydrologic performance. Mixtures dominated by pumice were also predicted to perform relatively well but were heavier. Despite the slightly greater weight and slightly lower performance, pumice may be a preferred alternative to perlite because perlite is a processed constituent with greater estimated embodied energy. Results indicate that performance of mixtures can be adequately predicted using performance of individual constituents for wet weight, water held, and long-term water retention. Hydraulic conductivity was less predictable because the pore volume in mixtures can be unrelated to the pore volume of the individual constituents. The framework presented here can be used to evaluate the performance of other EGR media, and the media attribute data can be used in formulating EGR media mixtures for specific applications. In addition, the attribute data can serve as a benchmark for evaluating other EGR media. Our results underscore the need for standardization of methods for more effective comparisons of EGR substrates, and also reinforce the need to evaluate EGR components using real-world scenarios.

11.
Ecol Eng ; 129: 123-133, 2019 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-32982067

RESUMO

Restoration and reconnection of floodplain systems provide multiple societal and ecosystem benefits, while providing municipalities the opportunity to attempt alternative approaches to maintain infrastructure protection and function. In some restored floodplains, treated wastewater effluent discharge is redirected over land instead of directly into rivers to allow natural flow and infiltration, to facilitate restoration designs such as levee setback, and to provide additional freshwater to floodplain ecosystems. However, indirect discharge of treated effluent over land may pose risks to surface and groundwater when pollutants like excess nutrients enter the floodplain and undergo transformation. We investigated the consequences for groundwater and surface water quality when effluent was redirected as open water channels over a floodplain surface. In this study, seasonal floodplain nutrient concentrations in groundwater and surface water were observed for more than 5 years as a floodplain and wastewater treatment plant underwent a major restoration project that included river-floodplain reconnection with levee setback and redirection of effluent discharge from a river channel to open flow across the restored floodplain. Nutrient loading to the surrounding floodplain groundwater and surface water was observed, but based on measures of hydrological connectivity, groundwater flow paths, and biogeochemistry, nutrients from the effluent moved within the floodplain with minimal effect to the surrounding floodplain water quality. We did not find evidence of substantial additional processing that could replace advanced nutrient treatment in this system, however we did observe evidence of diverse nutrient processes that may support enhanced retention if treatment channels were designed to enhance these processes. We suggest that indirect discharge of high quality treated effluent in a restored floodplain is a viable alternative to direct discharge into a river when groundwater flow directs that discharge to habitats where minimal nutrient sensitivity is expected.

12.
Sci Total Environ ; 652: 134-146, 2019 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-30359797

RESUMO

Regenerative stormwater conveyance (RSC), a relatively new stormwater management approach, is extensively implemented throughout the mid-Atlantic for nutrient control, but little is known of its pollutant reduction capabilities and controlling factors. This study examined effects of organic carbon (C) quantity and quality on stream water quality and nutrient retention at two RSCs near Annapolis, Maryland, USA by comparing longitudinal changes in water quality at paired restored and unrestored stream reaches, and conducting lab experiments simulating RSC processes. Results showed that RSCs consistently had lower dissolved oxygen saturation (DO%) and pH relative to nearby unrestored streams, probably due to release of labile dissolved organic carbon (DOC). At one RSC, with high nitrate (NO3-) inputs, retention of N (16-37%) and release of DOC (18-54%) were observed with the highest retention of N during summer, and the rates of N retention and DOC release were larger than that of the adjacent unrestored tributary (N: 5-8%, DOC: <18%). At another RSC site with lower NO3- concentrations, N retention and DOC release were not apparent. Mesocosm experiments showed that NO3- retention varies with organic C quantity and quality depending on incubating temperature; retention of total N did not increase with organic C due to release of other N species (e.g., organic N). Lab mesocosms showed an increase in the release of soluble reactive phosphorus (SRP) with increasing organic C quantity and quality. However, field measurements did not show any evidence of SRP release at RSCs. The changes in SRP concentrations in streams seemed to be a function of iron levels and leaf litter inputs, but control factors for SRP warrant further investigation. This study suggests that RSC as a restoration approach may be effective for reducing N depending upon C quantity and quality as well as water temperature and N levels.

13.
Hum Mol Genet ; 28(3): 448-458, 2019 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-30304512

RESUMO

Nicotinamide mononucleotide adenylyltransferase 2 (NMNAT2) is an endogenous axon maintenance factor that preserves axon health by blocking Wallerian-like axon degeneration. Mice lacking NMNAT2 die at birth with severe axon defects in both the peripheral nervous system and central nervous system so the complete absence of NMNAT2 in humans is likely to be similarly harmful but probably rare. However, there is evidence of widespread natural variation in human NMNAT2 mRNA expression so it is important to establish whether reduced levels of NMNAT2 have consequences that impact health. While mice that express reduced levels of NMNAT2, either those heterozygous for a silenced Nmnat2 allele or compound heterozygous for one silenced and one partially silenced Nmnat2 allele, remain overtly normal into old age, we now report that Nmnat2 compound heterozygote mice present with early and age-dependent peripheral nerve axon defects. Compound heterozygote mice already have reduced numbers of myelinated sensory axons at 1.5 months and lose more axons, likely motor axons, between 18 and 24 months and, crucially, these changes correlate with early temperature insensitivity and a later-onset decline in motor performance. Slower neurite outgrowth and increased sensitivity to axonal stress are also evident in primary cultures of Nmnat2 compound heterozygote superior cervical ganglion neurons. These data reveal that reducing NMNAT2 levels below a particular threshold compromises the development of peripheral axons and increases their vulnerability to stresses. We discuss the implications for human neurological phenotypes where axons are longer and have to be maintained over a much longer lifespan.


Assuntos
Axônios/metabolismo , Nicotinamida-Nucleotídeo Adenililtransferase/metabolismo , Fatores Etários , Animais , Feminino , Masculino , Camundongos , Degeneração Neural , Neurogênese , Neurônios/metabolismo , Nicotinamida-Nucleotídeo Adenililtransferase/genética , Cultura Primária de Células
14.
Environ Model Softw ; 109: 368-379, 2018 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-30505208

RESUMO

Decision-support tools (DSTs) are often produced from collaborations between technical experts and stakeholders to address environmental problems and inform decision making. Studies in the past two decades have provided key insights on the use of DSTs and the importance of bidirectional information flows among technical experts and stakeholders - a process that is variously referred to as co-production, participatory modeling, structured decision making, or simply stakeholder participation. Many of these studies have elicited foundational insights for the broad field of water resources management; however, questions remain on approaches for balancing co-production with uncertainty specifically for watershed modeling decision support tools. In this paper, we outline a simple conceptual model that focuses on the DST development process. Then, using watershed modeling case studies found in the literature, we discuss successful outcomes and challenges associated with embedding various forms of co-production into each stage of the conceptual model. We also emphasize the "3 Cs" (i.e., characterization, calculation, communication) of uncertainty and provide evidence-based suggestions for their incorporation in the watershed modeling DST development process. We conclude by presenting a list of best practices derived from current literature for achieving effective and robust watershed modeling decision-support tools.

15.
Oncotarget ; 9(91): 36379-36391, 2018 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-30555636

RESUMO

In recent years, the concept of synthetic lethality, describing a cellular state where loss of two genes leads to a non-viable phenotype while loss of one gene can be compensated, has emerged as a novel strategy for cancer therapy. Various compounds targeting synthetic lethal pathways are either under clinical investigation or are already routinely used in multiple cancer entities such as breast cancer. Most of them target the well-described synthetic lethal interplay between PARP1 and BRCA1/2. In our study, we investigated, using an in silico methodological approach, clinically utilized drug combinations for breast cancer treatment, by correlating their known molecular targets with known homologous interaction partners that cause synthetic lethality in yeast. Further, by creating a machine-learning algorithm, we were able to suggest novel synthetic lethal drug combinations of low-toxicity drugs in breast cancer and showed their negative effects on cancer cell viability in vitro. Our findings foster the understanding of evolutionarily conserved synthetic lethality in breast cancer cells and might lead to new drug combinations with favorable toxicity profile in this entity.

16.
Am J Trop Med Hyg ; 99(2): 477-481, 2018 08.
Artigo em Inglês | MEDLINE | ID: mdl-29893196

RESUMO

Substandard antibiotics are thought to be a major threat to public health in developing countries and a cause of antimicrobial resistance. However, assessing quality outside of a laboratory setting, using simple equipment, is challenging. The aim of this study was to validate the use of a portable Fourier transform infrared (FT-IR) spectrometer for the identification of substandard antibiotics. Results are presented for amoxicillin packages from Haiti, Ghana, Sierra Leone, Democratic Republic of Congo, India, Papua New Guinea, and Ethiopia collected over the course of 6 months in 2017, including two field trips with the FT-IR to Ghana and Sierra Leone. Canadian samples were used as a control. Regarding drug quality, of 290 individual capsules of amoxicillin analyzed, 13 were found to be substandard with total active pharmaceutical ingredients (API) lying outside the acceptable range of 90-110%. Of these 13, four were below 80% API. The FT-IR reliably identified these outliers and was found to yield results in good agreement with the established pharmacopeia liquid chromatography protocol. We conclude that the portable FT-IR may be suitable to intercept substandard antibiotics in developing countries where more sophisticated techniques are not readily available.


Assuntos
Antibacterianos/química , Antibacterianos/normas , Cromatografia Líquida , Sistemas Automatizados de Assistência Junto ao Leito , Controle de Qualidade , Espectroscopia de Infravermelho com Transformada de Fourier , Amoxicilina/química , Amoxicilina/normas , Canadá , Medicamentos Falsificados/química , Países em Desenvolvimento , Embalagem de Medicamentos , Gana , Haiti , Humanos , Índia , Garantia da Qualidade dos Cuidados de Saúde/métodos , Serra Leoa
17.
J Phys Chem A ; 122(20): 4730-4735, 2018 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-29727186

RESUMO

1-Methylpyrene radical cations undergo the loss of a hydrogen atom at internal energies above the first dissociation threshold. Imaging photoelectron photoion coincidence spectroscopy was employed in combination with RRKM modeling to determine a 0 K activation energy of 2.78 ± 0.25 eV and an entropy of activation of 6 ± 19 J K-1 mol-1 for this H-loss reaction. The ionization energy of 1-methylpyrene was measured by mass-selected threshold photoelectron spectroscopy to be 7.27 ± 0.01 eV. These values were found to be consistent with calculations at the CCSD/6-31G(d)//B3-LYP/6-31G(d) level of theory showing that the formation of the 1-methylenepyrene cation (resulting from H loss from the methyl group) is kinetically more favorable than the formation of a tropylium-containing product ion that is structurally analogous to the formation of the tropylium cation in H loss from ionized toluene. The shift away from a tropylium-containing structure was found to be due to the increased ring strain imposed on the C7 moiety when it is bound to three fused benzene rings. The RRKM results allow for the derivation of the Δf H0o (1-methylenepyrene cation) of 945 ± 31 kJ mol-1.

18.
Phys Chem Chem Phys ; 20(10): 7195-7205, 2018 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-29480289

RESUMO

Imaging photoelectron photoion coincidence spectroscopy was employed to explore the unimolecular dissociation of the ionized polycyclic aromatic hydrocarbons (PAHs) acenaphthylene, fluorene, cyclopenta[d,e,f]phenanthrene, pyrene, perylene, fluoranthene, dibenzo[a,e]pyrene, dibenzo[a,l]pyrene, coronene and corannulene. The primary reaction is always hydrogen atom loss, with the smaller species also exhibiting loss of C2H2 to varying extents. Combined with previous work on smaller PAH ions, trends in the reaction energies (E0) for loss of H from sp2-C and sp3-C centres, along with hydrocarbon molecule loss were found as a function of the number of carbon atoms in the ionized PAHs ranging in size from naphthalene to coronene. In the case of molecules which possessed at least one sp3-C centre, the activation energy for the loss of an H atom from this site was 2.34 eV, with the exception of cyclopenta[d,e,f]phenanthrene (CPP) ions, for which the E0 was 3.44 ± 0.86 eV due to steric constraints. The hydrogen loss from PAH cations and from their H-loss fragments exhibits two trends, depending on the number of unpaired electrons. For the loss of the first hydrogen atom, the energy is consistently ca. 4.40 eV, while the threshold to lose the second hydrogen atom is much lower at ca. 3.16 eV. The only exception was for the dibenzo[a,l]pyrene cation, which has a unique structure due to steric constraints, resulting in a low H loss reaction energy of 2.85 eV. If C2H2 is lost directly from the precursor cation, the energy required for this dissociation is 4.16 eV. No other fragmentation channels were observed over a large enough sample set for trends to be extrapolated, though data on CH3 and C4H2 loss obtained in previous studies is included for completeness. The dissociation reactions were also studied by collision induced dissociation after ionization by atmospheric pressure chemical ionization. When modeled with a simple temperature-based theory for the post-collision internal energy distribution, there was reasonable agreement between the two sets of data.

19.
Biogeochemistry ; 141(3): 281-305, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-31427837

RESUMO

In the Anthropocene1, watershed chemical transport is increasingly dominated by novel combinations elements, which are hydrologically linked together as 'chemical cocktails.' Chemical cocktails are novel because human activities greatly enhance elemental concentrations and their probability for biogeochemical interactions and shared transport along hydrologic flowpaths. A new chemical cocktail approach advances our ability to: trace contaminant mixtures in watersheds, develop chemical proxies with high-resolution sensor data, and manage multiple water quality problems. We explore the following questions: (1) Can we classify elemental transport in watersheds as chemical cocktails using a new approach? (2) What is the role of climate and land use in enhancing the formation and transport of chemical cocktails in watersheds? To address these questions, we first analyze trends in concentrations of carbon, nutrients, metals, and salts in fresh waters over 100 years. Next, we explore how climate and land use enhance the probability of formation of chemical cocktails of carbon, nutrients, metals, and salts. Ultimately, we classify transport of chemical cocktails based on solubility, mobility, reactivity, and dominant phases: (1) sieved chemical cocktails (e.g., particulate forms of nutrients, metals and organic matter); (2) filtered chemical cocktails (e.g., dissolved organic matter and associated metal complexes); (3) chromatographic chemical cocktails (e.g., ions eluted from soil exchange sites); and (4) reactive chemical cocktails (e.g., limiting nutrients and redox sensitive elements). Typically, contaminants are regulated and managed one element at a time, even though combinations of elements interact to influence many water-quality problems such as toxicity to life, eutrophication, infrastructure and water treatment. A chemical cocktail approach significantly expands evaluations of water-quality signatures and impacts beyond single elements to mixtures. High-frequency sensor data (pH, specific conductance, turbidity, etc.) can serve as proxies for chemical cocktails and improve real-time analyses of water-quality violations, identify regulatory needs, and track water quality recovery following and extreme climate events. Ultimately, a watershed chemical cocktail approach is necessary for effectively co-managing groups of contaminants and provides a more holistic approach for studying, monitoring, and managing water quality in the Anthropocene.

20.
Water (Basel) ; 9(815): 1-10, 2017 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-29225961

RESUMO

Land use and climate change can accelerate the depletion of freshwater resources that support humans and ecosystem services on a global scale. Here, we briefly review studies from around the world, and highlight those in this special issue. We identify stages that characterize increasing interaction between land use and climate change. During the first stage, hydrologic modifications and the built environment amplify overland flow via processes associated with runoff-dominated ecosystems (e.g., soil compaction, impervious surface cover, drainage, and channelization). During the second stage, changes in water storage impact the capacity of ecosystems to buffer extremes in water quantity and quality (e.g., either losses in snowpack, wetlands, and groundwater recharge or gains in water and nutrient storage behind dams in reservoirs). During the third stage, extremes in water quantity and quality contribute to losses in ecosystem services and water security (e.g., clean drinking water, flood mitigation, and habitat availability). During the final stage, management and restoration strategies attempt to regain lost ecosystem structure, function, and services but need to adapt to climate change. By anticipating the increasing interaction between land use and climate change, intervention points can be identified, and management strategies can be adjusted to improve outcomes for realistic expectations. Overall, global water security cannot be adequately restored without considering an increasing interaction between land use and climate change across progressive stages and our ever-increasing human domination of the water cycle from degradation to ecosystem restoration.

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