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1.
Nature ; 586(7830): 538-542, 2020 10.
Artigo em Inglês | MEDLINE | ID: mdl-33087912

RESUMO

Monolithic integration of control technologies for atomic systems is a promising route to the development of quantum computers and portable quantum sensors1-4. Trapped atomic ions form the basis of high-fidelity quantum information processors5,6 and high-accuracy optical clocks7. However, current implementations rely on free-space optics for ion control, which limits their portability and scalability. Here we demonstrate a surface-electrode ion-trap chip8,9 using integrated waveguides and grating couplers, which delivers all the wavelengths of light required for ionization, cooling, coherent operations and quantum state preparation and detection of Sr+ qubits. Laser light from violet to infrared is coupled onto the chip via an optical-fibre array, creating an inherently stable optical path, which we use to demonstrate qubit coherence that is resilient to platform vibrations. This demonstration of CMOS-compatible integrated photonic surface-trap fabrication, robust packaging and enhanced qubit coherence is a key advance in the development of portable trapped-ion quantum sensors and clocks, providing a way towards the complete, individual control of larger numbers of ions in quantum information processing systems.

2.
Alzheimers Dement ; 20(7): 4935-4950, 2024 07.
Artigo em Inglês | MEDLINE | ID: mdl-38572865

RESUMO

INTRODUCTION: Emerging evidence links changes in the gut microbiome to late-onset Alzheimer's disease (LOAD), necessitating examination of AD mouse models with consideration of the microbiome. METHODS: We used shotgun metagenomics and untargeted metabolomics to study the human amyloid beta knock-in (hAß-KI) murine model for LOAD compared to both wild-type (WT) mice and a model for early-onset AD (3xTg-AD). RESULTS: Eighteen-month female (but not male) hAß-KI microbiomes were distinct from WT microbiomes, with AD genotype accounting for 18% of the variance by permutational multivariate analysis of variance (PERMANOVA). Metabolomic diversity differences were observed in females, however no individual metabolites were differentially abundant. hAß-KI mice microbiomes were distinguishable from 3xTg-AD animals (81% accuracy by random forest modeling), with separation primarily driven by Romboutsia ilealis and Turicibacter species. Microbiomes were highly cage specific, with cage assignment accounting for more than 40% of the PERMANOVA variance between the groups. DISCUSSION: These findings highlight a sex-dependent variation in the microbiomes of hAß-KI mice and underscore the importance of considering the microbiome when designing studies that use murine models for AD. HIGHLIGHTS: Microbial diversity and the abundance of several species differed in human amyloid beta knock-in (hAß-KI) females but not males. Correlations to Alzheimer's disease (AD) genotype were stronger for the microbiome than the metabolome. Microbiomes from hAß-KI mice were distinct from 3xTg-AD mice. Cage effects accounted for most of the variance in the microbiome and metabolome.


Assuntos
Doença de Alzheimer , Peptídeos beta-Amiloides , Modelos Animais de Doenças , Genótipo , Camundongos Transgênicos , Animais , Feminino , Humanos , Masculino , Camundongos , Doença de Alzheimer/microbiologia , Doença de Alzheimer/genética , Peptídeos beta-Amiloides/metabolismo , Microbioma Gastrointestinal , Técnicas de Introdução de Genes , Metabolômica , Microbiota , Caracteres Sexuais
3.
J Public Health Manag Pract ; 30(1): E21-E30, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-37966958

RESUMO

BACKGROUND: Since the onset of the COVID-19 pandemic, multiple public health interventions have been implemented to respond to the rapidly evolving pandemic and community needs. This article describes the scope, timing, and impact of coordinated strategies for COVID-19 vaccine uptake in Chicago for the first year of vaccine distribution. METHODS: Using a series of interviews with public health officials and leaders of community-based organizations (CBOs) who participated in the implementation of the citywide COVID-19 vaccine outreach initiatives, we constructed a timeline of vaccine outreach initiatives. The timeline was matched to the vaccine uptake rates to explore the impact of the vaccine outreach initiatives by community area. Finally, we discussed the nature of policy initiatives and the level of vaccine uptake in relation to community characteristics. RESULTS: The Chicago Department of Public Health (CDPH) implemented myriad vaccine outreach strategies, including mass vaccination sites, improved access, and community-level vaccine campaigns. Protect Chicago+ was the primary vaccine outreach effort initiated by the CDPH, which identified 15 highly vulnerable community areas. More than 2.7 million (67%) Chicagoans completed the vaccine regimen by December 2021. Black (51.3%) Chicagoans were considerably less likely to be vaccinated than Asian (77.6%), White (69.8%), and Hispanic (63.6%) Chicago residents. In addition, there were significant spatial differences in the rate of COVID-19 vaccine completion: predominantly White and Hispanic communities, compared with Black communities, had higher rates of vaccine completion. CONCLUSIONS: The community outreach efforts to improve COVID-19 vaccine uptake in Chicago have shown the importance of community-engaged approaches in pandemic responses. Despite citywide efforts to build community infrastructure, Black communities had relatively lower levels of vaccine uptake than other communities. Broader social restructuring to mitigate disinvestment and residential segregation and to ameliorate medical mistrust will be needed to prepare for future pandemics and disasters.


Assuntos
COVID-19 , Vacinas , Humanos , Vacinas contra COVID-19/uso terapêutico , Chicago , Pandemias/prevenção & controle , Confiança , COVID-19/epidemiologia , COVID-19/prevenção & controle , Políticas
4.
J Behav Med ; 46(5): 882-889, 2023 10.
Artigo em Inglês | MEDLINE | ID: mdl-37000323

RESUMO

To elucidate the role of neighborhood walkability and crime on weight loss, we examined data from older adults residing in Chicago who participated in a randomized controlled trial lifestyle intervention. Controlling for individual demographic characteristics and the intervention assignment, the neighborhood homicide rate was significantly associated with weight change. Participants who resided in neighborhoods above the 50th percentile of homicide rate actually gained weight between pre- and post-intervention. On the other hand, there was no significant relationship between the level of walkability and weight loss. Our findings suggest that the social environment related to neighborhood crime may play a more important role in weight loss than the built environment, such as walkability. Urban characteristics related to walkability, such as sidewalks, may increase physical activity, however, interventions aiming to increase physical activity to promote weight loss will benefit by addressing the neighborhood social environment that determines how people navigate space.


Assuntos
Planejamento Ambiental , Caminhada , Humanos , Idoso , Exercício Físico , Características de Residência , Redução de Peso
5.
Fam Community Health ; 46(2): 112-122, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36799944

RESUMO

Neighborhood context plays an important role in producing and reproducing current patterns of health disparity. In particular, neighborhood disorganization affects how people engage in health care. We examined the effect of living in highly disorganized neighborhoods on care engagement, using data from the Coordinated Healthcare for Complex Kids (CHECK) program, which is a care delivery model for children with chronic conditions on Medicaid in Chicago. We retrieved demographic data from the US Census Bureau and crime data from the Chicago Police Department to estimate neighborhood-level social disorganization for the CHECK enrollees. A total of 6458 children enrolled in the CHECK between 2014 and 2017 were included in the analysis. Families living in the most disorganized neighborhoods, compared with areas with lower levels of disorganization, were less likely to engage in CHECK. Black families were less likely than Hispanic families to be engaged in the CHECK program. We discuss potential mechanisms through which disorganization affects care engagement. Understanding neighborhood context, including social disorganization, is key to developing more effective comprehensive care models.


Assuntos
Anomia (Social) , Crime , Humanos , Criança , População Negra , Chicago , Doença Crônica , Características de Residência
7.
Support Care Cancer ; 30(3): 2487-2496, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-34783907

RESUMO

BACKGROUND: Patient navigation is an increasingly widespread intervention to address the persistent, severe, and disproportionate breast cancer (BC) burden that African Americans (AA) face. Navigation may have more widespread effects than previously estimated due to patient-driven diffusion of BC information. METHODS: This pilot study examined the network effects of a randomized controlled trial via recruitment of navigated and non-navigated AA BC patients as well as their network members. We estimated study arm differences in patient BC promotion (i.e., number of individuals to whom BC patients promote BC screening) and network BC screening (i.e., % BC screening among network members). RESULTS: Among our sample of 100 AA BC patients, navigated patients promoted BC screening to more individuals than non-navigated patients. BC patients were more likely to promote BC screening to children and individuals with whom they communicated more frequently. Some models further suggested more network BC screening among "navigated" network members relative to "non-navigated" network members. CONCLUSIONS: Navigated AA patients promoted BC screening more widely throughout their networks than non-navigated AA BC patients. There were also suggestive findings regarding increased BC screening among their network members. Our pilot study highlights the potential for social network analysis to improve the precision of intervention effect estimates and to inform future innovations (e.g., integrating navigation and network-based interventions) with multilevel effects on cancer health disparities.


Assuntos
Neoplasias da Mama , Navegação de Pacientes , Negro ou Afro-Americano , Criança , Feminino , Amigos , Humanos , Projetos Piloto
8.
Prev Med ; 153: 106849, 2021 12.
Artigo em Inglês | MEDLINE | ID: mdl-34662598

RESUMO

Cervical cancer is preventable through HPV vaccination and screening however, uptake falls below national targets. A scoping review was conducted to describe stigmas related to HPV infection and vaccination and cervical cancer and screening in the US. Results were organized into the domains proposed by Stangl and colleagues' Health Stigma and Discrimination Framework. Common drivers of stigma were fear of social judgement and rejection, self-blame, and shame. Positive facilitators included social norms that provided motivation to receive HPV vaccination and screening. Gender and social norms were notable negative facilitators of stigma. HPV infection and cervical cancer resulted in stigma marking through the belief that both result from incautious behavior-either multiple sexual partners or failing to get screening. Stereotyping and prejudice were stigma practices attributed to HPV infection and cervical cancer through these same behaviors. Stigma experiences related to HPV infection, cervical cancer, and abnormal screening results included altered self-image based on perceived/anticipated stigma, as well as discrimination. This review advances understanding of the multiple dimensions of stigma associated with these outcomes in the US population. Three areas warrant additional consideration. Future studies should 1) assess how stigma dimensions affect uptake of cervical cancer preventions efforts; 2) focus on US women most affected by cervical cancer incidence and mortality to identify potential differences in these dimensions and tailor interventions accordingly; 3) include women from geographic areas of the US with high rates of cervical cancer to adapt interventions that address potential regional variations in resources and need.


Assuntos
Infecções por Papillomavirus , Vacinas contra Papillomavirus , Neoplasias do Colo do Útero , Detecção Precoce de Câncer/métodos , Feminino , Humanos , Programas de Rastreamento/métodos , Infecções por Papillomavirus/complicações , Estigma Social , Neoplasias do Colo do Útero/diagnóstico , Vacinação
9.
BMC Ophthalmol ; 21(1): 346, 2021 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-34560849

RESUMO

BACKGROUND: In response to the COVID-19 pandemic, a web-based tele-triage system was created to prioritize in-person clinic visits and ensure safety at the University of Illinois at Chicago Department of Ophthalmology and Visual Sciences during a statewide shelter-in-place order. The aim of this study is to evaluate the impact of the tele-triage system on urgent visit volume and explore the characteristics of acute visit requests at a tertiary referral eye center. METHODS: This retrospective study analyzed acute visit requests between April 6, 2020 and June 6, 2020. Descriptive statistics, chi-square tests, ANOVA, and bivariate logistic regression were used to compare variables with a p-value of 0.05. RESULTS: Three hundred fifty-eight surveys were completed. Mean age was 49.7 ± 18.8 years (range 2-91). The majority of requests were determined as urgent (63.0%) or emergent (0.8%). Forty-nine patients had recent eye trauma (13.7%), and the most common reported symptoms were new onset eye pain (25.7%) and photophobia (22.9%). Most patients were self-referred (63.7%), though provider referral was more common in patients with symptoms of new onset lid swelling (p < 0.01), diplopia (p < 0.01), flashing lights (p = 0.02), or droopy eyelid (p < 0.01). Patients presenting with symptom onset within 48 h tended to be younger (45.8 years) versus those with symptom duration of 48 h to 1 week (49.6 years), or more than 1 week (52.6 years; p < 0.01). CONCLUSION: This novel tele-triage system screened out one-third of acute visit requests as non-urgent, which limited in-person visits during the initial shelter-in-place period of the pandemic. Tele-triage systems should be implemented in eye care practices for future emergency preparedness.


Assuntos
COVID-19 , Telemedicina , Adolescente , Adulto , Idoso , Idoso de 80 Anos ou mais , Criança , Pré-Escolar , Humanos , Pessoa de Meia-Idade , Pandemias , Estudos Retrospectivos , SARS-CoV-2 , Triagem , Adulto Jovem
10.
J Biol Chem ; 293(24): 9544-9552, 2018 06 15.
Artigo em Inglês | MEDLINE | ID: mdl-29588364

RESUMO

There is a general lack of understanding about how communities of bacteria respond to exogenous toxins such as antibiotics. Most of our understanding of community-level stress responses comes from the study of stationary biofilm communities. Although several community behaviors and production of specific biomolecules affecting biofilm development and associated behavior have been described for Pseudomonas aeruginosa and other bacteria, we have little appreciation for the production and dispersal of secreted metabolites within the 2D and 3D spaces they occupy as they colonize, spread, and grow on surfaces. Here we specifically studied the phenotypic responses and spatial variability of alkyl quinolones, including the Pseudomonas quinolone signal (PQS) and members of the alkyl hydroxyquinoline (AQNO) subclass, in P. aeruginosa plate-assay swarming communities. We found that PQS production was not a universal signaling response to antibiotics, as tobramycin elicited an alkyl quinolone response, whereas carbenicillin did not. We also found that PQS and AQNO profiles in response to tobramycin were markedly distinct and influenced these swarms on different spatial scales. At some tobramycin exposures, P. aeruginosa swarms produced alkyl quinolones in the range of 150 µm PQS and 400 µm AQNO that accumulated as aggregates. Our collective findings show that the distribution of alkyl quinolones can vary by several orders of magnitude within the same swarming community. More notably, our results suggest that multiple intercellular signals acting on different spatial scales can be triggered by one common cue.


Assuntos
Antibacterianos/farmacologia , Biofilmes/efeitos dos fármacos , Hidroxiquinolinas/metabolismo , Pseudomonas aeruginosa/efeitos dos fármacos , Quinolonas/metabolismo , Tobramicina/farmacologia , Humanos , Espectrometria de Massas , Viabilidade Microbiana/efeitos dos fármacos , Infecções por Pseudomonas/microbiologia , Pseudomonas aeruginosa/citologia , Pseudomonas aeruginosa/fisiologia , Análise Espectral Raman
11.
Chem Rev ; 117(19): 12532-12563, 2017 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-28921972

RESUMO

Nuclear resonance vibrational spectroscopy (NRVS; also known as nuclear inelastic scattering, NIS) is a synchrotron-based method that reveals the full spectrum of vibrational dynamics for Mössbauer nuclei. Another major advantage, in addition to its completeness (no arbitrary optical selection rules), is the unique selectivity of NRVS. The basics of this recently developed technique are first introduced with descriptions of the experimental requirements and data analysis including the details of mode assignments. We discuss the use of NRVS to probe 57Fe at the center of heme and heme protein derivatives yielding the vibrational density of states for the iron. The application to derivatives with diatomic ligands (O2, NO, CO, CN-) shows the strong capabilities of identifying mode character. The availability of the complete vibrational spectrum of iron allows the identification of modes not available by other techniques. This permits the correlation of frequency with other physical properties. A significant example is the correlation we find between the Fe-Im stretch in six-coordinate Fe(XO) hemes and the trans Fe-N(Im) bond distance, not possible previously. NRVS also provides uniquely quantitative insight into the dynamics of the iron. For example, it provides a model-independent means of characterizing the strength of iron coordination. Prediction of the temperature-dependent mean-squared displacement from NRVS measurements yields a vibrational "baseline" for Fe dynamics that can be compared with results from techniques that probe longer time scales to yield quantitative insights into additional dynamical processes.


Assuntos
Heme/química , Ferro/química , Espectroscopia de Ressonância Magnética , Vibração , Ligantes
13.
Cancer ; 124(22): 4350-4357, 2018 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-30246241

RESUMO

BACKGROUND: Black women are more likely to be diagnosed at a later stage of breast cancer in part due to barriers to timely screening mammography, resulting in poorer mortality and survival outcomes. Patient navigation that helps to overcome barriers to the early detection of breast cancer is an effective intervention for reducing breast cancer disparity. However, the ability to recognize and seek help to overcome barriers may be affected by gendered and racialized social expectations of women. METHODS: Data from a randomized controlled trial, the Patient Navigation in Medically Underserved Areas study, were used. The likelihood of obtaining a follow-up screening mammogram was compared between women who identified ≥1 barriers and those who did not. RESULTS: Of the 3754 women who received the Patient Navigation in Medically Underserved Areas navigation intervention, approximately 14% identified ≥ 1 barriers, which led to additional navigator contacts. Consequently, those women who reported barriers were more likely to obtain a subsequent screening mammogram. Black women, women living in poverty, and women with a higher level of distrust were less likely to report barriers. CONCLUSIONS: Minority women living in poverty have always been the source of social support for others. However, gendered and racialized social expectations may affect the ways in which women seek help for their own health needs. A way to improve the effectiveness of navigation would be to recognize how minority women's gender images and expectations could shape how they seek help and support. A report of no barriers does not always translate into no problems. Proactive approaches to identify potential barriers may be beneficial.


Assuntos
Neoplasias da Mama/diagnóstico por imagem , Neoplasias da Mama/etnologia , Diagnóstico Tardio , Navegação de Pacientes/métodos , Negro ou Afro-Americano/estatística & dados numéricos , Chicago/etnologia , Diagnóstico Tardio/estatística & dados numéricos , Detecção Precoce de Câncer , Feminino , Acessibilidade aos Serviços de Saúde , Humanos , Mamografia/estatística & dados numéricos , Programas de Rastreamento , Área Carente de Assistência Médica , Pessoa de Meia-Idade , Avaliação de Programas e Projetos de Saúde , Ensaios Clínicos Controlados Aleatórios como Assunto , Fatores Socioeconômicos
14.
Anal Chem ; 90(11): 6725-6734, 2018 06 05.
Artigo em Inglês | MEDLINE | ID: mdl-29723465

RESUMO

The inherent architectural and chemical complexities of microbial biofilms mask our understanding of how these communities form, survive, propagate, and influence their surrounding environment. Here we describe a simple and versatile workflow for the cultivation and characterization of model flow-cell-based microbial ecosystems. A customized low-shear drip flow reactor was designed and employed to cultivate single and coculture flow-cell biofilms at the air-liquid interface of several metal surfaces. Pseudomonas putida F1 and Shewanella oneidensis MR-1 were selected as model organisms for this study. The utility and versatility of this platform was demonstrated via the application of several chemical and morphological imaging techniques-including matrix-assisted laser desorption/ionization mass spectrometry imaging, secondary ion mass spectrometry imaging, and scanning electron microscopy-and through the examination of model systems grown on iron substrates of varying compositions. Implementation of these techniques in combination with tandem mass spectrometry and a two-step imaging principal component analysis strategy resulted in the identification and characterization of 23 lipids and 3 oligosaccharides in P. putida F1 biofilms, the discovery of interaction-specific analytes, and the observation of several variations in cell and substrate morphology present during microbially influenced corrosion. The presented workflow is well-suited for examination of both single and multispecies drip flow biofilms and offers a platform for fundamental inquiries into biofilm formation, microbe-microbe interactions, and microbially influenced corrosion.


Assuntos
Biofilmes , Lipídeos/análise , Oligossacarídeos/análise , Imagem Óptica , Pseudomonas putida/metabolismo , Shewanella/metabolismo , Espectrometria de Massas , Microscopia Eletrônica de Varredura , Oligossacarídeos/metabolismo , Pseudomonas putida/química , Shewanella/química
15.
Anal Chem ; 90(9): 5654-5663, 2018 05 01.
Artigo em Inglês | MEDLINE | ID: mdl-29623707

RESUMO

After several decades of widespread use for mapping elemental ions and small molecular fragments in surface science, secondary ion mass spectrometry (SIMS) has emerged as a powerful analytical tool for molecular imaging in biology. Biomolecular SIMS imaging has primarily been used as a qualitative technique; although the distribution of a single analyte can be accurately determined, it is difficult to map the absolute quantity of a compound or even to compare the relative abundance of one molecular species to that of another. We describe a method for quantitative SIMS imaging of small molecules in agar-based microbial communities. The microbes are cultivated on a thin film of agar, dried under nitrogen, and imaged directly with SIMS. By use of optical microscopy, we show that the area of the agar is reduced by 26 ± 2% (standard deviation) during dehydration, but the overall biofilm morphology and analyte distribution are largely retained. We detail a quantitative imaging methodology, in which the ion intensity of each analyte is (1) normalized to an external quadratic regression curve, (2) corrected for isomeric interference, and (3) filtered for sample-specific noise and lower and upper limits of quantitation. The end result is a two-dimensional surface density image for each analyte. The sample preparation and quantitation methods are validated by quantitatively imaging four alkyl-quinolone and alkyl-quinoline N-oxide signaling molecules (including Pseudomonas quinolone signal) in Pseudomonas aeruginosa colony biofilms. We show that the relative surface densities of the target biomolecules are substantially different from values inferred through direct intensity comparison and that the developed methodologies can be used to quantitatively compare as many ions as there are available standards.


Assuntos
Ágar/química , Imagem Molecular , Pseudomonas aeruginosa/química , Quinolinas/análise , Espectrometria de Massa de Íon Secundário , Biofilmes , Microbiota , Microscopia Confocal , Microscopia de Fluorescência , Tamanho da Partícula
16.
Acc Chem Res ; 50(1): 96-104, 2017 01 17.
Artigo em Inglês | MEDLINE | ID: mdl-28001363

RESUMO

In the two decades since mass spectrometry imaging (MSI) was first applied to visualize the distribution of peptides across biological tissues and cells, the technique has become increasingly effective and reliable. MSI excels at providing complementary information to existing methods for molecular analysis-such as genomics, transcriptomics, and metabolomics-and stands apart from other chemical imaging modalities through its capability to generate information that is simultaneously multiplexed and chemically specific. Today a diverse family of MSI approaches are applied throughout the scientific community to study the distribution of proteins, peptides, and small-molecule metabolites across many biological models. The inherent strengths of MSI make the technique valuable for studying microbial systems. Many microbes reside in surface-attached multicellular and multispecies communities, such as biofilms and motile colonies, where they work together to harness surrounding nutrients, fend off hostile organisms, and shield one another from adverse environmental conditions. These processes, as well as many others essential for microbial survival, are mediated through the production and utilization of a diverse assortment of chemicals. Although bacterial cells are generally only a few microns in diameter, the ecologies they influence can encompass entire ecosystems, and the chemical changes that they bring about can occur over time scales ranging from milliseconds to decades. Because of their incredible complexity, our understanding of and influence over microbial systems requires detailed scientific evaluations that yield both chemical and spatial information. MSI is well-positioned to fulfill these requirements. With small adaptations to existing methods, the technique can be applied to study a wide variety of chemical interactions, including those that occur inside single-species microbial communities, between cohabitating microbes, and between microbes and their hosts. In recognition of this potential for scientific advancement, researchers have adapted MSI methodologies for the specific needs of the microbiology research community. As a result, workflows exist for imaging microbial systems with many of the common MSI ionization methods. Despite this progress, there is substantial room for improvements in instrumentation, sample preparation, and data interpretation. This Account provides a brief overview of the state of technology in microbial MSI, illuminates selected applications that demonstrate the potential of the technique, and highlights a series of development challenges that are needed to move the field forward. In the coming years, as microbial MSI becomes easier to use and more universally applicable, the technique will evolve into a fundamental tool widely applied throughout many divisions of science, medicine, and industry.


Assuntos
Bactérias/química , Peptídeos/química , Proteínas/química , Bibliotecas de Moléculas Pequenas/química , Bactérias/metabolismo , Espectrometria de Massas , Peptídeos/metabolismo , Proteínas/metabolismo , Bibliotecas de Moléculas Pequenas/metabolismo
17.
Inorg Chem ; 57(15): 8788-8795, 2018 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-30010336

RESUMO

Compared to well studied diatomic ligands (NO, CN-, CO), the axial bonds of carbene hemes is much less known although its significance in biological chemistry. The unusually large quadrupole splitting (Δ EQ = +2.2 mm·s-1) and asymmetric parameter (η = 0.9) of the five-coordinate heme carbene [Fe(TTP)(CCl2)], which is the largest among all known low spin ferrohemes, has driven investigations by means of Mössbauer effect Nuclear Resonance Vibrational Spectroscopy (NRVS). Three distinct measurements on one single crystal (two in-plane and one out-of-plane) have demonstrated comprehensive vibrational structures including stretch (429) and bending modes (472 cm-1) of the axial Fe-CCl2, and revealed iron vibrational anisotropy in three orthogonal directions for the first time. Frontier orbital analysis especially comparisons with diatomic analogues (NO, CN-, CO) suggest that CCl2, similar to NO, has led to strong but anisotropic π bonding in a ligand-based "4C"-coordinate which induced the vibrational anisotropies and very large Mössbauer parameters. This is contrasted to CN- and CO complexes which possess a porphyrin-based "4N"-coordinate electronic and vibrational structures due to inherent on-axis linear ligation.


Assuntos
Monóxido de Carbono/química , Cianetos/química , Metaloporfirinas/química , Óxido Nítrico/química , Ligantes , Modelos Químicos , Estrutura Molecular
18.
Anal Chem ; 89(5): 3078-3086, 2017 03 07.
Artigo em Inglês | MEDLINE | ID: mdl-28194949

RESUMO

A high-throughput single cell profiling method has been developed for matrix-enhanced-secondary ion mass spectrometry (ME-SIMS) to investigate the lipid profiles of neuronal cells. Populations of cells are dispersed onto the substrate, their locations determined using optical microscopy, and the cell locations used to guide the acquisition of SIMS spectra from the cells. Up to 2,000 cells can be assayed in one experiment at a rate of 6 s per cell. Multiple saturated and unsaturated phosphatidylcholines (PCs) and their fragments are detected and verified with tandem mass spectrometry from individual cells when ionic liquids are employed as a matrix. Optically guided single cell profiling with ME-SIMS is suitable for a range of cell sizes, from Aplysia californica neurons larger than 75 µm to 7-µm rat cerebellar neurons. ME-SIMS analysis followed by t-distributed stochastic neighbor embedding of peaks in the lipid molecular mass range (m/z 700-850) distinguishes several cell types from the rat central nervous system, largely based on the relative proportions of four dominant lipids, PC(32:0), PC(34:1), PC(36:1), and PC(38:5). Furthermore, subpopulations within each cell type are tentatively classified consistent with their endogenous lipid ratios. The results illustrate the efficacy of a new approach to classify single cell populations and subpopulations using SIMS profiling of lipid and metabolite contents. These methods are broadly applicable for high throughput single cell chemical analyses.


Assuntos
Aplysia/metabolismo , Líquidos Iônicos/química , Neurônios/metabolismo , Fosfatidilcolinas/análise , Espectrometria de Massa de Íon Secundário/métodos , Animais , Diferenciação Celular , Análise Multivariada , Neurônios/química , Neurônios/citologia , Análise de Componente Principal , Ratos , Análise de Célula Única
19.
Chemistry ; 22(18): 6323-6332, 2016 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-26999733

RESUMO

The vibrational spectrum of a six-coordinate nitrosyl iron porphyrinate, monoclinic [Fe(TpFPP)(1-MeIm)(NO)] (TpFPP=tetra-para-fluorophenylporphyrin; 1-MeIm=1-methylimidazole), has been studied by oriented single-crystal nuclear resonance vibrational spectroscopy (NRVS). The crystal was oriented to give spectra perpendicular to the porphyrin plane and two in-plane spectra perpendicular or parallel to the projection of the FeNO plane. These enable assignment of the FeNO bending and stretching modes. The measurements reveal that the two in-plane spectra have substantial differences that result from the strongly bonded axial NO ligand. The direction of the in-plane iron motion is found to be largely parallel and perpendicular to the projection of the bent FeNO on the porphyrin plane. The out-of-plane Fe-N-O stretching and bending modes are strongly mixed with each other, as well as with porphyrin ligand modes. The stretch is mixed with v50 as was also observed for dioxygen complexes. The frequency of the assigned stretching mode of eight Fe-X-O (X=N, C, and O) complexes is correlated with the Fe-XO bond lengths. The nature of highest frequency band at ≈560 cm(-1) has also been examined in two additional new derivatives. Previously assigned as the Fe-NO stretch (by resonance Raman), it is better described as the bend, as the motion of the central nitrogen atom of the FeNO group is very large. There is significant mixing of this mode. The results emphasize the importance of mode mixing; the extent of mixing must be related to the peripheral phenyl substituents.


Assuntos
Heme/química , Imidazóis/química , Ferro/química , Metaloporfirinas/química , Ligantes , Espectroscopia de Ressonância Magnética , Modelos Moleculares
20.
Analyst ; 140(19): 6544-52, 2015 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-26331158

RESUMO

Two label-free molecular imaging techniques, confocal Raman microscopy (CRM) and secondary ion mass spectrometry (SIMS), are combined for in situ characterization of the spatiotemporal distributions of quinolone metabolites and signaling molecules in communities of the pathogenic bacterium Pseudomonas aeruginosa. Dramatic molecular differences are observed between planktonic and biofilm modes of growth for these bacteria. We observe patterned aggregation and a high abundance of N-oxide quinolines in early biofilms and swarm zones of P. aeruginosa, while the concentrations of these secreted components in planktonic cells and agar plate colonies are below CRM and SIMS detection limits. CRM, in conjunction with principal component analysis (PCA) is used to distinguish between the two co-localized isomeric analyte pairs 4-hydroxy-2-heptylquinoline-N-oxide (HQNO)/2-heptyl-3-hydroxyquinolone (PQS) and 4-hydroxy-2-nonylquinoline-N-oxide (NQNO)/2-nonyl-hydroxyquinolone (C9-PQS) based on differences in their vibrational fingerprints, illustrating how the technique can be used to guide tandem-MS and tandem-MS imaging analysis. Because N-oxide quinolines are ubiquitous and expressed early in biofilms, these analytes may be fundamentally important for early biofilm formation and the growth and organization of P. aeruginosa microbial communities. This study underscores the advantages of using multimodal molecular imaging to study complex biological systems.


Assuntos
Microscopia Confocal/métodos , Pseudomonas aeruginosa/metabolismo , Quinolonas/metabolismo , Espectrometria de Massa de Íon Secundário/métodos , Biofilmes , Isomerismo , Pseudomonas aeruginosa/fisiologia , Quinolonas/química
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