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1.
Opt Express ; 32(9): 16027-16039, 2024 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-38859240

RESUMO

We present the theory and experimental results of a microwave photonic (MWP) filter based instantaneous frequency measurement system. A quantum dash mode-locked laser is used as an optical frequency comb source. With up to 41 flat comb lines and a real-time feedback loop for comb shaping, a set of MWP filters with linear frequency responses for either linear unit or dB unit are experimentally demonstrated. The maximum measurement frequency can be up to 20 GHz limited by the available test-and-measurement instruments. By using one MWP filter, the root-mean-square error is 51∼66 MHz, which can be improved to 42.2 MHz for linear unit, and 30.7 MHz for dB unit by using two MWP filters together.

2.
Opt Express ; 32(1): 217-229, 2024 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-38175050

RESUMO

We investigate the capabilities and limitations of quantum-dash mode-locked lasers (QD-MLLDs) as optical frequency comb sources in coherent optical communication systems. We demonstrate that QD-MLLDs are on par with conventional single-wavelength narrow linewidth laser sources and can support high symbol rates and modulation formats. We manage to transmit 64 quadrature amplitude modulation (QAM) signals up to 80 GBd over 80 km of standard single-mode fiber (SSMF), which highlights the distinctive phase noise performance of the QD-MLLD. Using a 38.5 GHz (6 dB bandwidth) silicon photonic (SiP) modulator, we achieve a maximum symbol rate of 104 GBd with 16QAM signaling and a maximum net rate of 416 Gb/s per carrier in a single polarization setup and after 80 km-SSMF transmission. We also compare QD-MLLD performance with commercial narrow-linewidth integrable tunable laser assemblies (ITLAs) and explore their potential for use as local oscillators (LOs) and signal carriers. The QD-MLLD has 45 comb lines usable for transmission at a frequency spacing of 25 GHz, and an RF linewidth of 35 kHz.

3.
J Phys Chem A ; 127(44): 9178-9184, 2023 Nov 09.
Artigo em Inglês | MEDLINE | ID: mdl-37878768

RESUMO

An important concern related to the performance of Li-ion batteries is the formation of a solid electrolyte interphase on the surface of the anode. This film is formed from the decomposition of electrolytes and can have important effects on the stability and performance. Here, we evaluate the decomposition pathway of ethylene carbonate and related organic electrolyte molecules using a series of density functional approximations and correlated wave function (WF) methods, including the coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] and auxiliary-field quantum Monte Carlo (AFQMC). We find that the transition state barrier associated with ring opening varies widely across different functionals, ranging from 3.01 to 17.15 kcal/mol, which can be compared to the value of 12.84 kcal/mol predicted by CCSD(T). This large variation underscores the importance of benchmarking against accurate WF methods. A performance comparison of all of the density functionals used in this study reveals that the M06-2X-D3 (a meta-hybrid GGA), CAM-B3LYP-D3 (a range-separated hybrid), and B2GP-PLYP-D3 (a double hybrid) perform the best, with average errors of about 1.50-1.60 kcal/mol compared to CCSD(T). We also compared the performance of the WF methods that are more scalable than CCSD(T), finding that DLPNO-CCSD(T) and phaseless AFQMC with a DFT trial wave function exhibit average errors of 1.38 and 1.74 kcal/mol, respectively.

4.
J Chem Phys ; 158(14): 140901, 2023 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-37061483

RESUMO

Approximate solutions to the ab initio electronic structure problem have been a focus of theoretical and computational chemistry research for much of the past century, with the goal of predicting relevant energy differences to within "chemical accuracy" (1 kcal/mol). For small organic molecules, or in general, for weakly correlated main group chemistry, a hierarchy of single-reference wave function methods has been rigorously established, spanning perturbation theory and the coupled cluster (CC) formalism. For these systems, CC with singles, doubles, and perturbative triples is known to achieve chemical accuracy, albeit at O(N7) computational cost. In addition, a hierarchy of density functional approximations of increasing formal sophistication, known as Jacob's ladder, has been shown to systematically reduce average errors over large datasets representing weakly correlated chemistry. However, the accuracy of such computational models is less clear in the increasingly important frontiers of chemical space including transition metals and f-block compounds, in which strong correlation can play an important role in reactivity. A stochastic method, phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC), has been shown to be capable of producing chemically accurate predictions even for challenging molecular systems beyond the main group, with relatively low O(N3 - N4) cost and near-perfect parallel efficiency. Herein, we present our perspectives on the past, present, and future of the ph-AFQMC method. We focus on its potential in transition metal quantum chemistry to be a highly accurate, systematically improvable method that can reliably probe strongly correlated systems in biology and chemical catalysis and provide reference thermochemical values (for future development of density functionals or interatomic potentials) when experiments are either noisy or absent. Finally, we discuss the present limitations of the method and where we expect near-term development to be most fruitful.

5.
Appl Opt ; 62(32): 8696-8701, 2023 Nov 10.
Artigo em Inglês | MEDLINE | ID: mdl-38037987

RESUMO

We demonstrate photonic beamforming using a quantum-dash (QD) optical frequency comb (OFC) source. Thanks to the 25 GHz free spectral range (FSR) and up to 40 comb lines available from the QD OFC, we can implement phased antenna arrays (PAAs) with directional radiation and scanning. We consider two types of PAAs: a uniform linear array (ULA) and a uniform planar array (UPA). By selecting different comb lines with a programmable optical filter, we can tune the FSR of the OFC source and realize a discrete scanning function. We evaluate the beam squint of the ULAs, and the results show that we can achieve broadband operation. Finally, we show that we can achieve both directional radiation and scanning simultaneously using the UPA.

6.
Opt Lett ; 47(5): 1133-1136, 2022 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-35230309

RESUMO

We demonstrate a reconfigurable microwave photonic (MWP) filter using a quantum dash (QDash) mode-locked laser (MLL) that can generate an optical frequency comb (OFC) with ∼50 comb lines and a free spectral range of 25 GHz. Thanks to the large number of comb lines, the MWP filter responses can be easily programmed by tailoring the OFC spectrum. We implement MWP filter responses with Gaussian, sinc, flat-top, and multiple peaks, as well as demonstrate that tuning of the central frequency. We achieve a minimum 3 dB bandwidth of ∼100 MHz for a sinc-shaped MWP filter, while the maximum out-of-band rejection can be up to ∼30 dB with Gaussian apodization. Our results show that the QDash-MLL is a promising OFC source for developing integrated and reconfigurable MWP filters.

7.
J Am Chem Soc ; 142(47): 19917-19925, 2020 11 25.
Artigo em Inglês | MEDLINE | ID: mdl-33174728

RESUMO

Triplet-triplet annihilation upconversion (TTA-UC) is an unconventional photophysical process that yields high-energy photons from low-energy incident light and offers pathways for innovation across many technologies, including solar energy harvesting, photochemistry, and optogenetics. Within aromatic organic chromophores, TTA-UC is achieved through several consecutive energy conversion events that ultimately fuse two triplet excitons into a singlet exciton. In chromophores where the singlet exciton is roughly isoergic with two triplet excitons, the limiting step is the triplet-triplet annihilation pathway, where the kinetics and yield depend sensitively on the energies of the lowest singlet and triplet excited states. Herein we report up to 40-fold improvements in upconversion quantum yields using molecular engineering to selectively tailor the relative energies of the lowest singlet and triplet excited states, enhancing the yield of triplet-triplet annihilation and promoting radiative decay of the resulting singlet exciton. Using this general and effective strategy, we obtain upconversion yields with red emission that are among the highest reported, with remarkable chemical stability under ambient conditions.

8.
Molecules ; 25(19)2020 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-32987656

RESUMO

Parkinson's disease (PD) is a progressive neurodegenerative disorder that is characterized by a loss of dopaminergic neurons, leading to bradykinesia, rigidity, tremor at rest, and postural instability, as well as non-motor symptoms such as olfactory impairment, pain, autonomic dysfunction, impaired sleep, fatigue, and behavioral changes. The pathogenesis of PD is believed to involve oxidative stress, disruption to mitochondria, alterations to the protein α-synuclein, and neuroinflammatory processes. There is currently no cure for the disease. Polyphenols are secondary metabolites of plants, which have shown benefit in several experimental models of PD. Intake of polyphenols through diet is also associated with lower PD risk in humans. In this review, we provide an overview of the pathology of PD and the data supporting the potential neuroprotective capacity of increased polyphenols in the diet. Evidence suggests that the intake of dietary polyphenols may inhibit neurodegeneration and the progression of PD. Polyphenols appear to have a positive effect on the gut microbiome, which may decrease inflammation that contributes to the disease. Therefore, a diet rich in polyphenols may decrease the symptoms and increase quality of life in PD patients.


Assuntos
Neuroproteção , Fármacos Neuroprotetores/uso terapêutico , Doença de Parkinson , Polifenóis/uso terapêutico , Qualidade de Vida , Animais , Neurônios Dopaminérgicos/metabolismo , Neurônios Dopaminérgicos/patologia , Humanos , Doença de Parkinson/dietoterapia , Doença de Parkinson/metabolismo , Doença de Parkinson/patologia , Doença de Parkinson/fisiopatologia
9.
Can Pharm J (Ott) ; 153(2): 95-100, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32206154

RESUMO

BACKGROUND: The recent legalization of cannabis use in Canada requires pharmacists to be able to support their patients with accurate knowledge of its known risks and benefits. Certain populations, such as pregnant and breastfeeding women and their developing children, may be at higher risk than other populations. METHODS: The authors independently searched the literature for clinical reports or reviews of the literature regarding the safety of cannabis use in pregnancy and breastfeeding using search terms such as cannabis, marijuana, pregnancy and breastfeeding. RESULTS: This review combines the relevant pharmacological, pharmacokinetic and clinical evidence for the effects of cannabis in this special patient population. The literature demonstrates that some of the constituents of cannabis can reach children in utero and through breastmilk. Given that Δ9-tetrahydrocannabinol can be present in breastmilk as quickly as 1 hour after consumption and last up to 6 days, it may not be possible to use cannabis and avoid infant exposure. There is evidence that this exposure may result in cognitive, social and motor defects. Some of these effects may be long term, lasting years. The pharmacist must be able to educate and screen patients regarding marijuana use in pregnancy and breastfeeding, with the ultimate aim of harm reduction.

10.
Molecules ; 23(1)2017 Dec 22.
Artigo em Inglês | MEDLINE | ID: mdl-29271934

RESUMO

Several species of berries, such as blueberries (Vaccinium angustifolium) and lingonberries (Vaccinium vitis-idaea L.), have attracted much scientific attention in recent years, especially due to their reported antioxidant and anti-inflammatory properties. Berries, as with other types of plants, have developed metabolic mechanisms to survive various environmental stresses, some of which involve reactive oxygen species. In addition, the fruits and leaves of berries have high amounts of polyphenols, such as flavonoids, which act as potent antioxidants. These compounds could potentially be beneficial for brain aging and neurodegenerative disorders. There are now several studies documenting the beneficial effects of various berries in cell models of neurotoxicity as well as in vivo models of neurodegenerative disease. In the current review, we discuss the metabolic strategies that plants and animals have developed in order to combat reactive oxygen species. We then discuss issues of bioavailability of various compounds in mammals and provide a synopsis of studies demonstrating the neuroprotective ability of berries and polyphenols. We also summarize findings from our own research group. For example, we have detected various polyphenols in samples of blueberries and lingonberries and have found that the leaves have a much higher antioxidant capacity than the fruits. Extracts from these species have also demonstrated neuroprotective effects in cellular models of toxicity and inflammation, which are being further pursued in animal models.


Assuntos
Doença de Alzheimer/dietoterapia , Antioxidantes/farmacologia , Frutas/química , Doença de Huntington/dietoterapia , Fármacos Neuroprotetores/farmacologia , Doença de Parkinson/dietoterapia , Extratos Vegetais/administração & dosagem , Doença de Alzheimer/metabolismo , Doença de Alzheimer/fisiopatologia , Antioxidantes/isolamento & purificação , Disponibilidade Biológica , Mirtilos Azuis (Planta)/química , Mirtilos Azuis (Planta)/metabolismo , Flavonoides/isolamento & purificação , Flavonoides/farmacologia , Frutas/metabolismo , Humanos , Doença de Huntington/metabolismo , Doença de Huntington/fisiopatologia , Fármacos Neuroprotetores/isolamento & purificação , Doença de Parkinson/metabolismo , Doença de Parkinson/fisiopatologia , Fenóis/isolamento & purificação , Fenóis/farmacologia , Extratos Vegetais/química , Folhas de Planta/química , Folhas de Planta/metabolismo , Polifenóis/isolamento & purificação , Polifenóis/farmacologia , Espécies Reativas de Oxigênio/antagonistas & inibidores , Espécies Reativas de Oxigênio/metabolismo , Vaccinium vitis-Idaea/química , Vaccinium vitis-Idaea/metabolismo
11.
Ann Vasc Surg ; 30: 22-7, 2016 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-26365109

RESUMO

BACKGROUND: Median arcuate ligament syndrome (MALS) is a rare disorder characterized by postprandial abdominal pain, weight loss, and celiac stenosis. Diagnosis can be challenging, leading to a delay in treatment. We report on our continued experience using a laparoscopic approach for this uncommon diagnosis. METHODS: This is an Institutional Review Board-approved, prospectively collected retrospective analysis of patients treated with laparoscopic MAL release at our institution. Data collected included patient demographics, preoperative symptoms, operative approach, and postoperative outcomes. Patients were then contacted to complete a postoperative survey designed to assess the improvement of symptoms and overall patient satisfaction. RESULTS: A total of 39 patients (33 women and 6 men) underwent laparoscopic MAL release from March 2007 to July 2014. Mean age was 40.6 years (range, 17-77 years). Thirty of 39 patients had a postoperative celiac axis ultrasound. Twenty-three had a patent celiac axis on postoperative duplex. Of the remaining 7, 5 with residual celiac axis stenosis and 1 with occlusion, reported complete resolution of their symptoms. One remaining patient with occlusion remained symptomatic. Thirty-three of 39 (84.6%) reported symptom relief after surgery. Nine of 33 (27.3%) responders had cardiovascular risk factors versus 4 of 6 (67%) nonresponders. Five patients with atypical presentations underwent preoperative diagnostic celiac plexus block using local anesthetic, with 4 reporting symptom reliefs after block. These 4 patients also reported postoperative symptom relief. One patient of 39 received a postoperative celiac stent placement and remained symptomatic. There were 4 conversions to open surgery (10.3%) and no deaths. CONCLUSIONS: Laparoscopic MAL release continues to be a safe and effective means of managing MALS. Our data suggest that the symptoms associated with MALS are not related to vascular compromise, and atherosclerotic risk factors may predict poorer outcomes. Symptomatic relief is seen in the vast majority of patients undergoing this procedure. However, patient selection remains critically important in obtaining optimal results.


Assuntos
Doenças Cardiovasculares/complicações , Artéria Celíaca/anormalidades , Constrição Patológica/diagnóstico , Constrição Patológica/etiologia , Laparoscopia , Adolescente , Adulto , Fatores Etários , Idoso , Artéria Celíaca/cirurgia , Constrição Patológica/cirurgia , Feminino , Humanos , Masculino , Síndrome do Ligamento Arqueado Mediano , Pessoa de Meia-Idade , Estudos Retrospectivos , Fatores de Risco , Adulto Jovem
12.
J Environ Qual ; 44(4): 1127-36, 2015 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-26437094

RESUMO

Water quality threats associated with using phosphate-based amendments to remediate Pb-contaminated soils are a concern, particularly in riparian areas. This study investigated the effects of P application rates to a Pb-contaminated alluvial soil on Pb and P loss via surface water runoff, Pb accumulation in tall fescue ( Schreb; Kentucky 31), and Pb speciation. An alluvial soil was treated with triple superphosphate at P to Pb molar ratios of 0:1 (control), 4:1, 8:1, and 16:1. After a 6-mo reaction period, rainfall simulation (RFS) studies were conducted, followed by tall fescue establishment and a second set of RFS studies (1 yr after treatment). Results from the first RFS study (unvegetated) demonstrated that the total Pb and P concentrations in the effluents of 8:1 and 16:1 (P:Pb molar ratio) treatment levels were significantly greater ( < 0.05) than the control. One year after P treatment and 6 mo after vegetation establishment, total P and Pb concentrations of the effluents from a second RFS decreased by one to three orders of magnitude. Total and dissolved P concentration in runoff from the 16:1 P:Pb treatment remained significantly greater than all other treatments. However, total Pb concentration in the runoff was comparable among the treatments. Phosphorus treatment also reduced Pb uptake into tall fescue by >55%. X-ray absorption near-edge structure spectroscopy data showed that pyromorphite [Pb(PO)OH,Cl,F] abundance ranged from 0% (control) to 32% (16:1 P:Pb; 1 yr after treatment) of the total soil Pb. Although P treatment stimulated pyromorphite formation, pyromorphite abundance was comparable between the P-treated soils. These findings suggest that a 4:1 (P:Pb molar ratio) P treatment may be a sufficient means of reducing Pb bioavailability while minimizing concerns related to P loss in an alluvial setting.

13.
J Environ Manage ; 136: 27-36, 2014 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-24553295

RESUMO

In situ bioremediation is potentially a cost effective treatment strategy for subsurface soils contaminated with petroleum hydrocarbons, however, limited information is available regarding the impact of soil spatial heterogeneity on bioremediation efficacy. In this study, we assessed issues associated with hydrocarbon biodegradation and soil spatial heterogeneity (samples designated as FTF 1, 5 and 8) from a site in which in situ bioremediation was proposed for hydrocarbon removal. Test pit activities showed similarities in FTF soil profiles with elevated hydrocarbon concentrations detected in all soils at 2 m below ground surface. However, PCR-DGGE-based cluster analysis showed that the bacterial community in FTF 5 (at 2 m) was substantially different (53% dissimilar) and 2-3 fold more diverse than communities in FTF 1 and 8 (with 80% similarity). When hydrocarbon degrading potential was assessed, differences were observed in the extent of (14)C-benzene mineralisation under aerobic conditions with FTF 5 exhibiting the highest hydrocarbon removal potential compared to FTF 1 and 8. Further analysis indicated that the FTF 5 microbial community was substantially different from other FTF samples and dominated by putative hydrocarbon degraders belonging to Pseudomonads, Xanthomonads and Enterobacteria. However, hydrocarbon removal in FTF 5 under anaerobic conditions with nitrate and sulphate electron acceptors was limited suggesting that aerobic conditions were crucial for hydrocarbon removal. This study highlights the importance of assessing available microbial capacity prior to bioremediation and shows that the site's spatial heterogeneity can adversely affect the success of in situ bioremediation unless area-specific optimizations are performed.


Assuntos
Poluição Ambiental/análise , Hidrocarbonetos/química , Microbiologia do Solo , Poluentes do Solo/química , Benzeno/química , Biodegradação Ambiental , Biodiversidade , Biomassa , Fenômenos Químicos , DNA Bacteriano/isolamento & purificação , Enterobacteriaceae/isolamento & purificação , Enterobacteriaceae/metabolismo , Gammaproteobacteria/isolamento & purificação , Gammaproteobacteria/metabolismo , Nitratos/química , Petróleo/análise , Reação em Cadeia da Polimerase , Pseudomonas/isolamento & purificação , Pseudomonas/metabolismo , Solo/química , Sulfatos/química , Xanthomonas/isolamento & purificação , Xanthomonas/metabolismo
14.
JMIR Hum Factors ; 11: e54145, 2024 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-38787603

RESUMO

BACKGROUND: The fastest-growing neurological disorder is Parkinson disease (PD), a progressive neurodegenerative disease that affects 10 million people worldwide. PD is typically treated with levodopa, an oral pill taken to increase dopamine levels, and other dopaminergic agonists. As the disease advances, the efficacy of the drug diminishes, necessitating adjustments in treatment dosage according to the patient's symptoms and disease progression. Therefore, remote monitoring systems that can provide more detailed and accurate information on a patient's condition regularly are a valuable tool for clinicians and patients to manage their medication. The Parkinson's Remote Interactive Monitoring System (PRIMS), developed by PragmaClin Research Inc, was designed on the premise that it will be an easy-to-use digital system that can accurately capture motor and nonmotor symptoms of PD remotely. OBJECTIVE: We performed a usability evaluation in a simulated clinical environment to assess the ease of use of the PRIMS and determine whether the product offers suitable functionality for users in a clinical setting. METHODS: Participants were recruited from a user sign-up web-based database owned by PragmaClin Research Inc. A total of 11 participants were included in the study based on the following criteria: (1) being diagnosed with PD and (2) not being diagnosed with dementia or any other comorbidities that would make it difficult to complete the PRIMS assessment safely and independently. Patient users completed a questionnaire that is based on the Movement Disorder Society-sponsored revision of the Unified Parkinson's Disease Rating Scale. Interviews and field notes were analyzed for underlying themes and topics. RESULTS: In total, 11 people with PD participated in the study (female individuals: n=5, 45%; male individuals: n=6, 55%; age: mean 66.7, SD 7.77 years). Thematic analysis of the observer's notes revealed 6 central usability issues associated with the PRIMS. These were the following: (1) the automated voice prompts are confusing, (2) the small camera is problematic, (3) the motor test exhibits excessive sensitivity to the participant's orientation and position in relation to the cameras, (4) the system poses mobility challenges, (5) navigating the system is difficult, and (6) the motor test exhibits inconsistencies and technical issues. Thematic analysis of qualitative interview responses revealed four central themes associated with participants' perspectives and opinions on the PRIMS, which were (1) admiration of purpose, (2) excessive system sensitivity, (3) video instructions preferred, and (4) written instructions disliked. The average system usability score was calculated to be 69.2 (SD 4.92), which failed to meet the acceptable system usability score of 70. CONCLUSIONS: Although multiple areas of improvement were identified, most of the participants showed an affinity for the overarching objective of the PRIMS. This feedback is being used to upgrade the current PRIMS so that it aligns more with patients' needs.


Assuntos
Doença de Parkinson , Humanos , Doença de Parkinson/tratamento farmacológico , Doença de Parkinson/diagnóstico , Masculino , Feminino , Pessoa de Meia-Idade , Idoso , Interface Usuário-Computador , Monitorização Fisiológica/métodos , Monitorização Fisiológica/instrumentação
15.
Arch Environ Contam Toxicol ; 65(3): 598-610, 2013 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-23771631

RESUMO

Mining and smelting in the Southeast Missouri Lead Mining District has caused widespread contamination of soils with lead (Pb) and other metals. Soils from three study sites sampled in the district contained from approximately 1,000-3,200 mg Pb/kg. Analyses of earthworms [33-4,600 mg Pb/kg dry weight (dw)] collected in the district showed likely high Pb exposure of songbirds preying on soil organisms. Mean tissue Pb concentrations in songbirds collected from the contaminated sites were greater (p < 0.05) than those in songbirds from reference sites by factors of 8 in blood, 13 in liver, and 23 in kidney. Ranges of Pb concentrations in livers (mg Pb/kg dw) were as follows: northern cardinal (Cardinalis cardinalis) = 0.11-3.0 (reference) and 1.3-30 (contaminated) and American robin (Turdus migratorius) = 0.43-8.5 (reference) and 7.6-72 (contaminated). Of 34 adult and juvenile songbirds collected from contaminated sites, 11 (32%) had hepatic Pb concentrations that were consistent with adverse physiological effects, 3 (9%) with systemic toxic effects, and 4 (12%) with life-threatening toxic effects. Acid-fast renal intranuclear inclusion bodies, which are indicative of Pb poisoning, were detected in kidneys of two robins that had the greatest renal Pb concentrations (952 and 1,030 mg/kg dw). Mean activity of the enzyme delta-aminolevulinic acid dehydratase (ALAD) in red blood cells, a well-established bioindicator of Pb poisoning in birds, was decreased by 58-82% in songbirds from the mining sites. We conclude that habitats within the mining district with soil Pb concentrations of ≥1,000 mg Pb/kg are contaminated to the extent that they are exposing ground-feeding songbirds to toxic concentrations of Pb.


Assuntos
Exposição Ambiental , Chumbo/toxicidade , Oligoquetos/metabolismo , Poluentes do Solo/toxicidade , Aves Canoras/metabolismo , Animais , Monitoramento Ambiental , Chumbo/análise , Chumbo/sangue , Espectrometria de Massas , Metais Pesados/análise , Metais Pesados/sangue , Metais Pesados/toxicidade , Mineração , Missouri , Poluentes do Solo/análise , Poluentes do Solo/sangue
16.
Artigo em Inglês | MEDLINE | ID: mdl-23442111

RESUMO

In this study, lead (Pb) bioaccessibility was assessed in peri-urban contaminated soils using a variety of established in vitro assays. Bioaccessibility data was then used to predict Pb relative bioavailability (RBA) using published in vivo-in vitro regression models in order to compare calculated estimates and measured values. Lead bioaccessibility varied depending on the in vitro methodology employed with the relative bioavailability leaching procedure (RBALP) and in vitro gastrointestinal (IVG) assays providing more conservative Pb bioaccessibility values compared to those determined using PBET, UBM and Rel-SBRC-I assays. When Pb RBA was calculated, predicted values using PBET-G and UBM-G data were similar to measured Pb RBA values. However, Pb RBA was over-estimated by 1.6-5.5- and 2.6-6.6-fold when data and regression models from RBALP and IVG-G assays were employed.


Assuntos
Monitoramento Ambiental/métodos , Chumbo/análise , Chumbo/farmacocinética , Modelos Biológicos , Poluentes do Solo/análise , Poluentes do Solo/farmacocinética , Animais , Disponibilidade Biológica , Monitoramento Ambiental/estatística & dados numéricos , Previsões , Mucosa Gástrica/metabolismo , Humanos , Incineração , Mucosa Intestinal/metabolismo , Modelos Lineares , Eliminação de Resíduos , Suínos , Reforma Urbana
17.
J Chem Theory Comput ; 19(21): 7567-7576, 2023 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-37889331

RESUMO

We formulate and characterize a new constraint for auxiliary-field quantum Monte Carlo (AFQMC) applicable for general fermionic systems, which allows for the accumulation of phase in the random walk but disallows walkers with a magnitude of phase greater than π with respect to the trial wave function. For short imaginary times, before walkers accumulate sizable phase values, this approach is equivalent to exact free projection, allowing one to observe the accumulation of bias associated with the constraint and thus estimate its magnitude a priori. We demonstrate the stability of this constraint over arbitrary imaginary times and system sizes, highlighting the removal of noise due to the fermionic sign problem. Benchmark total energies for a variety of weakly and strongly correlated molecular systems reveal a distinct bias with respect to standard phaseless AFQMC, with a comparative increase in accuracy given sufficient quality of the trial wave function for the set of studied cases. We then take this constraint, termed linecut AFQMC (lc-AFQMC), and systematically release it (lcR-AFQMC), providing a route to obtain a smooth bridge between constrained AFQMC and the exact free projection results.

18.
J Chem Theory Comput ; 19(18): 6208-6225, 2023 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-37655473

RESUMO

Generating accurate ab initio ionization energies for transition metal complexes is an important step toward the accurate computational description of their electrocatalytic reactions. Benchmark-quality data is required for testing existing theoretical methods and developing new ones but is complicated to obtain for many transition metal compounds due to the potential presence of both strong dynamical and static electron correlation. In this regime, it is questionable whether the so-called gold standard, coupled cluster with singles, doubles, and perturbative triples (CCSD(T)), provides the desired level of accuracy─roughly 1-3 kcal/mol. In this work, we compiled a test set of 28 3d metal-containing molecules relevant to homogeneous electrocatalysis (termed 3dTMV) and computed their vertical ionization energies (ionization potentials) with CCSD(T) and phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) in the def2-SVP basis set. A substantial effort has been made to converge away the phaseless bias in the ph-AFQMC reference values. We assess a wide variety of multireference diagnostics and find that spin-symmetry breaking of the CCSD wave function and the PBE0 density functional correlate well with our analysis of multiconfigurational wave functions. We propose quantitative criteria based on symmetry breaking to delineate correlation regimes inside of which appropriately performed CCSD(T) can produce mean absolute deviations from the ph-AFQMC reference values of roughly 2 kcal/mol or less and outside of which CCSD(T) is expected to fail. We also present a preliminary assessment of density functional theory (DFT) functionals on the 3dTMV set.

19.
Nat Chem ; 15(1): 101-109, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36216892

RESUMO

State-of-the-art photoactivation strategies in chemical biology provide spatiotemporal control and visualization of biological processes. However, using high-energy light (λ < 500 nm) for substrate or photocatalyst sensitization can lead to background activation of photoactive small-molecule probes and reduce its efficacy in complex biological environments. Here we describe the development of targeted aryl azide activation via deep red-light (λ = 660 nm) photoredox catalysis and its use in photocatalysed proximity labelling. We demonstrate that aryl azides are converted to triplet nitrenes via a redox-centric mechanism and show that its spatially localized formation requires both red light and a photocatalyst-targeting modality. This technology was applied in different colon cancer cell systems for targeted protein environment labelling of epithelial cell adhesion molecule (EpCAM). We identified a small subset of proteins with previously known and unknown association to EpCAM, including CDH3, a clinically relevant protein that shares high tumour-selective expression with EpCAM.


Assuntos
Neoplasias do Colo , Luz , Humanos , Molécula de Adesão da Célula Epitelial , Catálise
20.
Micromachines (Basel) ; 14(12)2023 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-38138398

RESUMO

We present here a performance comparison of quantum-dash (Qdash) semiconductor amplifiers (SOAs) with three, five, eight, and twelve InAs dash layers grown on InP substrates. Other than the number of Qdash layers, the structures were identical. The eight-layer Qdash SOA gave the highest amplified spontaneous emission power (4.3 dBm) and chip gain (26.4 dB) at 1550 nm, with a 300 mA CW bias current and at 25 °C temperature, while SOAs with fewer Qdash layers (for example, three-layer Qdash SOA), had a wider ASE bandwidth (90 nm) and larger 3 dB gain saturated output power (18.2 dBm) in a shorter wavelength range. The noise figure (NF) of the SOAs increased nearly linearly with the number of Qdash layers. The longest gain peak wavelength of 1570 nm was observed for the 12-layer Qdash SOA. The most balanced performance was obtained with a five-layer Qdash SOA, with a 25.4 dB small-signal chip gain, 15.2 dBm 3 dB output saturated power, and 5.7 dB NF at 1532 nm, 300 mA and 25 °C. These results are better than those of quantum well SOAs reported in a recent review paper. The high performance of InAs/InP Qdash SOAs with different Qdash layers shown in this paper could be important for many applications with distinct requirements under uncooled scenarios.

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