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1.
Cancers (Basel) ; 14(9)2022 Apr 24.
Artículo en Inglés | MEDLINE | ID: mdl-35565258

RESUMEN

Colorectal symptoms are common but only infrequently represent serious pathology, including colorectal cancer (CRC). A large number of invasive tests are presently performed for reassurance. We investigated the feasibility of urinary volatile organic compound (VOC) testing as a potential triage tool in patients fast-tracked for assessment for possible CRC. A prospective, multi-center, observational feasibility study was performed across three sites. Patients referred to NHS fast-track pathways for potential CRC provided a urine sample that underwent Gas Chromatography-Mass Spectrometry (GC-MS), Field Asymmetric Ion Mobility Spectrometry (FAIMS), and Selected Ion Flow Tube Mass Spectrometry (SIFT-MS) analysis. Patients underwent colonoscopy and/or CT colonography and were grouped as either CRC, adenomatous polyp(s), or controls to explore the diagnostic accuracy of VOC output data supported by an artificial neural network (ANN) model. 558 patients participated with 23 (4%) CRC diagnosed. 59% of colonoscopies and 86% of CT colonographies showed no abnormalities. Urinary VOC testing was feasible, acceptable to patients, and applicable within the clinical fast track pathway. GC-MS showed the highest clinical utility for CRC and polyp detection vs. controls (sensitivity = 0.878, specificity = 0.882, AUROC = 0.896) but it is labour intensive. Urinary VOC testing and analysis are feasible within NHS fast-track CRC pathways. Clinically meaningful differences between patients with cancer, polyps, or no pathology were identified suggesting VOC analysis may have future utility as a triage tool.

2.
Small ; 18(5): e2104621, 2022 02.
Artículo en Inglés | MEDLINE | ID: mdl-34825471

RESUMEN

Polymeric devices capable of releasing submicron particles (subMP) on demand are highly desirable for controlled release systems, sensors, and smart surfaces. Here, a temperature-memory polymer sheet with a programmable smooth surface served as matrix to embed and release polystyrene subMP controlled by particle size and temperature. subMPs embedding at 80 °C can be released sequentially according to their size (diameter D of 200 nm, 500 nm, 1 µm) when heated. The differences in their embedding extent are determined by the various subMPs sizes and result in their distinct release temperatures. Microparticles of the same size (D ≈ 1 µm) incorporated in films at different programming temperatures Tp (50, 65, and 80 °C) lead to a sequential release based on the temperature-memory effect. The change of apparent height over the film surface is quantified using atomic force microscopy and the realization of sequential release is proven by confocal laser scanning microscopy. The demonstration and quantification of on demand subMP release are of technological impact for assembly, particle sorting, and release technologies in microtechnology, catalysis, and controlled release.


Asunto(s)
Polímeros , Poliestirenos , Microscopía de Fuerza Atómica , Tamaño de la Partícula , Temperatura
3.
Molecules ; 26(23)2021 Nov 26.
Artículo en Inglés | MEDLINE | ID: mdl-34885767

RESUMEN

Mass spectrometry (MS) is an analytical technique that can be used for various applications in a number of scientific areas including environmental, security, forensic science, space exploration, agri-food, and numerous others. MS is also continuing to offer new insights into the proteomic and metabolomic fields. MS techniques are frequently used for the analysis of volatile compounds (VCs). The detection of VCs from human samples has the potential to aid in the diagnosis of diseases, in monitoring drug metabolites, and in providing insight into metabolic processes. The broad usage of MS has resulted in numerous variations of the technique being developed over the years, which can be divided into hyphenated and real-time MS techniques. Hyphenated chromatographic techniques coupled with MS offer unparalleled qualitative analysis and high accuracy and sensitivity, even when analysing complex matrices (breath, urine, stool, etc.). However, these benefits are traded for a significantly longer analysis time and a greater need for sample preparation and method development. On the other hand, real-time MS techniques offer highly sensitive quantitative data. Additionally, real-time techniques can provide results in a matter of minutes or even seconds, without altering the sample in any way. However, real-time MS can only offer tentative qualitative data and suffers from molecular weight overlap in complex matrices. This review compares hyphenated and real-time MS methods and provides examples of applications for each technique for the detection of VCs from humans.


Asunto(s)
Espectrometría de Masas , Proteómica , Compuestos Orgánicos Volátiles/aislamiento & purificación , Cuerpo Humano , Humanos , Compuestos Orgánicos Volátiles/metabolismo
4.
J Breath Res ; 15(3)2021 04 21.
Artículo en Inglés | MEDLINE | ID: mdl-33761469

RESUMEN

This paper comprises an updated version of the 2014 review which reported 1846 volatile organic compounds (VOCs) identified from healthy humans. In total over 900 additional VOCs have been reported since the 2014 review and the VOCs from semen have been added. The numbers of VOCs found in breath and the other bodily fluids are: blood 379, breath 1488, faeces 443, milk 290, saliva 549, semen 196, skin 623 and urine 444. Compounds were assigned CAS registry numbers and named according to a common convention where possible. The compounds have been included in a single table with the source reference(s) for each VOC, an update on our 2014 paper. VOCs have also been grouped into tables according to their chemical class or functionality to permit easy comparison. Careful use of the database is needed, as a number of the identified VOCs only have level 2-putative assignment, and only a small fraction of the reported VOCs have been validated by standards. Some clear differences are observed, for instance, a lack of esters in urine with a high number in faeces and breath. However, the lack of compounds from matrices such a semen and milk compared to breath for example could be due to the techniques used or reflect the intensity of effort e.g. there are few publications on VOCs from milk and semen compared to a large number for breath. The large number of volatiles reported from skin is partly due to the methodologies used, e.g. by collecting skin sebum (with dissolved VOCs and semi VOCs) onto glass beads or cotton pads and then heating to a high temperature to desorb VOCs. All compounds have been included as reported (unless there was a clear discrepancy between name and chemical structure), but there may be some mistaken assignations arising from the original publications, particularly for isomers. It is the authors' intention that this work will not only be a useful database of VOCs listed in the literature but will stimulate further study of VOCs from healthy individuals; for example more work is required to confirm the identification of these VOCs adhering to the principles outlined in the metabolomics standards initiative. Establishing a list of volatiles emanating from healthy individuals and increased understanding of VOC metabolic pathways is an important step for differentiating between diseases using VOCs.


Asunto(s)
Líquidos Corporales , Compuestos Orgánicos Volátiles , Pruebas Respiratorias , Heces , Humanos , Saliva
5.
ACS Appl Mater Interfaces ; 13(9): 10748-10759, 2021 Mar 10.
Artículo en Inglés | MEDLINE | ID: mdl-33594879

RESUMEN

High levels of reactive oxygen species (ROS) during stem cell expansion often lead to replicative senescence. Here, a polydopamine (PDA)-coated substrate was used to scavenge extracellular ROS for mesenchymal stem cell (MSC) expansion. The PDA-coated substrate could reduce the oxidative stress and mitochondrial damage in replicative senescent MSCs. The expression of senescence-associated ß-galactosidase of MSCs from three human donors (both bone marrow- and adipose tissue-derived) was suppressed on PDA. The MSCs on the PDA-coated substrate showed a lower level of interleukin 6 (IL-6), one of the senescence-associated inflammatory components. Cellular senescence-specific genes, such as p53 and p21, were downregulated on the PDA-coated substrate, while the stemness-related gene, OCT4, was upregulated. The PDA-coated substrate strongly promoted the proliferation rate of MSCs, while the stem cell character and differentiation potential were retained. Large-scale expansion of stem cells would greatly benefit from the PDA-coated substrate.


Asunto(s)
Técnicas de Cultivo de Célula/métodos , Materiales Biocompatibles Revestidos/farmacología , Indoles/farmacología , Células Madre Mesenquimatosas/efectos de los fármacos , Células Madre Mesenquimatosas/metabolismo , Polímeros/farmacología , Técnicas de Cultivo de Célula/instrumentación , Diferenciación Celular/efectos de los fármacos , Proliferación Celular/efectos de los fármacos , Senescencia Celular/efectos de los fármacos , Expresión Génica/efectos de los fármacos , Humanos , Interleucina-6/metabolismo , Mitocondrias/efectos de los fármacos , Estrés Oxidativo/efectos de los fármacos , beta-Galactosidasa/metabolismo
6.
Chem Sci ; 11(24): 6222-6228, 2020 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-32953017

RESUMEN

The bottom-up assembly of nanoelectronic devices from molecular building blocks is a target of widespread interest. Herein we demonstrate an in situ seeded growth approach to produce a nanowire-based electrical device. This exploits the chemisorption of block terpolymer-based seed fibres with a thiophene-functionalised corona onto metal electrodes as the initial step. We then use these surface-bound seeds to initiate the growth of well-defined one-dimensional fibre-like micelles via the seeded growth method known as "Living crystallisation-driven self-assembly'' and demonstrate that they are capable of spanning an interelectrode gap. Finally, a chemical oxidation step was used to transform the nanofibres into nanowires to generate a two-terminal device. This seeded growth approach of growing well-defined circuit elements provides a useful new design tool for bottom-up device fabrication.

7.
J Breath Res ; 14(4): 041001, 2020 07 21.
Artículo en Inglés | MEDLINE | ID: mdl-32531777

RESUMEN

The COVID-19 pandemic has highlighted the importance of rapid, cost effective, accurate, and non-invasive testing for viral infections. Volatile compounds (VCs) have been suggested for several decades as fulfilling these criteria. However currently very little work has been done in trying to diagnose viral infections using VCs. Much of the work carried out to date involves the differentiation of bacterial and viral sources of infection and often the detection of bacterial and viral co-infection. However, this has usually been done in vitro and very little work has involved the use of human participants. Viruses hijack the host cell metabolism and do not produce their own metabolites so identifying virus specific VCs is at best a challenging task. However, there are proteins and lipids that are potential candidates as markers of viral infection. The current understanding is that host cell glycolysis is upregulated under viral infection to increase the available energy for viral replication. There is some evidence that viral infection leads to the increase of production of fatty acids, alkanes, and alkanes related products. For instance, 2,3-butandione, aldehydes, 2,8-dimethyl-undecane and n-propyl acetate have all been correlated with viral infection. Currently, the literature points to markers of oxidative stress (e.g. nitric oxide, aldehydes etc) being the most useful in the determination of viral infection. The issue, however, is that there are also many other conditions that can lead to oxidative stress markers being produced. In this review a range of (mainly mass spectrometric) methods are discussed for viral detection in breath, including breath condensate. Currently MALDI-ToF-MS is likely to be the preferred method for the identification of viral strains and variants of those strains, however it is limited by its need for the viral strains to have been sequenced and logged in a database.


Asunto(s)
Pruebas Respiratorias/métodos , Virosis/diagnóstico , Aldehídos/metabolismo , Animales , Betacoronavirus , Biomarcadores/metabolismo , COVID-19 , Prueba de COVID-19 , Técnicas de Laboratorio Clínico , Infecciones por Coronavirus/diagnóstico , Infecciones por Coronavirus/metabolismo , Cromatografía de Gases y Espectrometría de Masas , Hepatitis B/diagnóstico , Hepatitis B/metabolismo , Humanos , Gripe Humana/diagnóstico , Gripe Humana/metabolismo , Espectrometría de Masas , Óxido Nítrico/metabolismo , Infecciones por Orthomyxoviridae/diagnóstico , Infecciones por Orthomyxoviridae/metabolismo , Estrés Oxidativo , Pandemias , Infecciones por Picornaviridae/diagnóstico , Infecciones por Picornaviridae/metabolismo , Neumonía Viral/diagnóstico , Neumonía Viral/metabolismo , Infecciones por Rotavirus/diagnóstico , Infecciones por Rotavirus/metabolismo , SARS-CoV-2 , Espectrometría de Masa por Ionización de Electrospray , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción , Porcinos , Virosis/metabolismo , Virus
8.
J Breath Res ; 14(3): 034001, 2020 05 27.
Artículo en Inglés | MEDLINE | ID: mdl-32163929

RESUMEN

The assessment of volatile compounds (VOCs) for disease diagnosis is a growing area of research. There is a need to provide hard evidence i.e. biochemical routes, to justify putative VOC biomarkers, as in many cases this remains uncertain, which weakens their authenticity. Recently reports of volatile hydrocarbons and or aldehydes in bodily fluids and breath have been attributed to oxidative stress, although as discussed here, fewer compounds have been reported than expected from a mechanistic examination. Oxidative stress can result from many disease states which produce inflammation, and a better understanding of the interconnection between oxidative stress and the release of VOCs from target diseased and healthy organs could greatly help diagnoses. It is generally considered that oxidation of unsaturated fatty acids are a major source of these VOCs. An investigation listing the many possible volatile oxidation products has not been undertaken. This is described here using a mechanistic analysis (based on the literature) of the compounds derived from molecular cleavage and the results compared with a recent review of all the VOCs emanating from the human body, which satisfactorily explains the presence of at least 100 VOCs. Six important unsaturated fatty acids, oleic, palmitoleic, linoleic, linolenic, arachidonic, and cervonic acids have been shown to be capable of producing up to 18 n+6 unique breakdown products (where n = the number of alkene double bonds in the fatty acid hydrocarbon chain), in total 299 compounds. In many cases these have not been reported. We suggest several reasons for this: these VOCs have not been expected, so researchers are not looking for them and importantly some are not present in the mass spectral libraries, or they are too low a concentration to have been detected, or are not present. Furthermore a theoretical explanation for the origins of branched aldehydes and other compounds arising from bacterial oxidative metabolism of unsaturated fatty acids are described.


Asunto(s)
Ácidos Grasos Insaturados/metabolismo , Cuerpo Humano , Peroxidación de Lípido , Compuestos Orgánicos Volátiles/análisis , Pruebas Respiratorias/métodos , Ácidos Grasos Insaturados/química , Humanos , Oxidación-Reducción
9.
Proc Natl Acad Sci U S A ; 117(4): 1895-1901, 2020 01 28.
Artículo en Inglés | MEDLINE | ID: mdl-31932451

RESUMEN

Stem cells are capable of sensing and processing environmental inputs, converting this information to output a specific cell lineage through signaling cascades. Despite the combinatorial nature of mechanical, thermal, and biochemical signals, these stimuli have typically been decoupled and applied independently, requiring continuous regulation by controlling units. We employ a programmable polymer actuator sheet to autonomously synchronize thermal and mechanical signals applied to mesenchymal stem cells (MSCs). Using a grid on its underside, the shape change of polymer sheet, as well as cell morphology, calcium (Ca2+) influx, and focal adhesion assembly, could be visualized and quantified. This paper gives compelling evidence that the temperature sensing and mechanosensing of MSCs are interconnected via intracellular Ca2+ Up-regulated Ca2+ levels lead to a remarkable alteration of histone H3K9 acetylation and activation of osteogenic related genes. The interplay of physical, thermal, and biochemical signaling was utilized to accelerate the cell differentiation toward osteogenic lineage. The approach of programmable bioinstructivity provides a fundamental principle for functional biomaterials exhibiting multifaceted stimuli on differentiation programs. Technological impact is expected in the tissue engineering of periosteum for treating bone defects.


Asunto(s)
Tejido Adiposo/citología , Calcio/metabolismo , Osteogénesis , Polímeros/química , Células Madre/citología , Estrés Mecánico , Temperatura , Tejido Adiposo/metabolismo , Diferenciación Celular , Linaje de la Célula , Células Cultivadas , Humanos , Mecanotransducción Celular , Células Madre/metabolismo , Ingeniería de Tejidos
10.
Biomacromolecules ; 21(2): 338-348, 2020 02 10.
Artículo en Inglés | MEDLINE | ID: mdl-31746189

RESUMEN

Within the field of shape-changing materials, synthetic chemical modification has been widely used to introduce key structural units and subsequently expand the mechanical functionality of actuator devices. The introduction of architectural elements that facilitate in situ control over mechanical properties and complete geometric reconfiguration of a device is highly desirable to increase the morphological diversity of polymeric actuator materials. The subject of the present study is a multiblock copolymer with semicrystalline poly(l-lactide) and poly(ε-caprolactone) (PLLA-PCL) segments. By harnessing the stereocomplexation of copolymer chains with a poly(d-lactide) oligomer (PDLA), we provide anchoring points for physical network formation and demonstrate how a blending process can be used to efficiently vary the mechanical properties of a shape-memory actuator. We investigate the effect of molecular structure on the actuation performance of the material in cyclic thermomechanical tests, with a maximum reversible shape change εrev' = 13.4 ± 1.5% measured at 3.1 wt % of polylactide stereocomplex content in the multiblock copolymer matrix. The thermophysical properties, crystalline structure, and phase morphology were analyzed by DSC, WAXS and AFM respectively, elucidating the structure-to-function relationship in physically cross-linked blended materials. The work demonstrates a one-step technique for manufacturing a polymeric actuator and tuning its performance in situ. This approach should greatly improve the efficiency of physically cross-linked actuator fabrication, allowing composition and physical behavior to be precisely and easily controlled.


Asunto(s)
Poliésteres/química , Polímeros/química , Rastreo Diferencial de Calorimetría , Cromatografía en Gel , Reactivos de Enlaces Cruzados/química , Espectroscopía de Resonancia Magnética , Microscopía de Fuerza Atómica , Peso Molecular , Polímeros/síntesis química , Dispersión de Radiación , Rayos X
11.
Clin Hemorheol Microcirc ; 74(1): 53-66, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-31743992

RESUMEN

Microfibers with a core-shell structure can be produced by co-axial electrospinning, allowing for the functionalization of the outer layer with bioactive molecules. In this study, a thermoplastic, degradable polyesteretherurethane (PEEU), consisting of poly(p-dioxanone) (PPDO) and poly(ɛ-caprolactone) (PCL) segments with different PPDO to PCL weight ratios, were processed into fiber meshes by co-axial electrospinning with gelatin. The prepared PEEU fibers have a diameter of 1.3±0.5 µm and an elastic modulus of around 5.1±1.0 MPa as measured by tensile testing in a dry state at 37°C, while the PEEU/Gelatin core-shell fibers with a gelatin content of 12±6 wt% and a diameter of 1.5±0.5 µm possess an elastic modulus of 15.0±1.1 MPa in a dry state at 37 °C but as low as 0.7±0.7 MPa when hydrated at 37 °C. Co-axial electrospinning allowed for the homogeneous distribution of the gelatin shell along the whole microfiber. Gelatin with conjugated Fluorescein (FITC) remained stable on the PEEU fibers after 7 days incubation in Phosphate-buffered saline (PBS) at 37 °C. The gelatin coating on PEEU fibers lead to enhanced human adipose tissue derived mesenchymal stem cell (hADSC) attachment and a proliferation rate 81.7±34.1 % higher in cell number in PEEU50/Gelatin fibers after 7 days of cell culture when compared to PEEU fibers without coating. In this work, we demonstrate that water-soluble gelatin can be incorporated as the outer shell of a polymer fiber via molecular entanglement, with a sustained presence and role in enhancing stem cell attachment and proliferation.


Asunto(s)
Proliferación Celular/fisiología , Gelatina/química , Células Madre Mesenquimatosas/metabolismo , Poliésteres/química , Polímeros/metabolismo , Ingeniería de Tejidos/métodos , Humanos , Andamios del Tejido/química
12.
Biomacromolecules ; 20(10): 3627-3640, 2019 10 14.
Artículo en Inglés | MEDLINE | ID: mdl-31529957

RESUMEN

Within the natural world, organisms use information stored in their material structure to generate a physical response to a wide variety of environmental changes. The ability to program synthetic materials to intrinsically respond to environmental changes in a similar manner has the potential to revolutionize material science. By designing polymeric devices capable of responsively changing shape or behavior based on information encoded into their structure, we can create functional physical behavior, including a shape-memory and an actuation capability. Here we highlight the stimuli-responsiveness and shape-changing ability of biological materials and biopolymer-based materials, plus their potential biomedical application, providing a bioperspective on shape-memory materials. We address strategies to incorporate a shape-memory (actuation) function in polymeric materials, conceptualized in terms of its relationship with inputs (environmental stimuli) and outputs (shape change). Challenges and opportunities associated with the integration of several functions in a single material body to achieve multifunctionality are discussed. Finally, we describe how elements that sense, convert, and transmit stimuli have been used to create multisensitive materials.


Asunto(s)
Materiales Biomiméticos/química , Polímeros de Estímulo Receptivo/química , Sistemas de Liberación de Medicamentos/métodos , Sistemas de Liberación de Medicamentos/tendencias , Ingeniería de Tejidos/métodos , Ingeniería de Tejidos/tendencias
13.
Clin Hemorheol Microcirc ; 73(1): 229-236, 2019.
Artículo en Inglés | MEDLINE | ID: mdl-31561331

RESUMEN

The mechanical properties of electrospun fiber meshes typically are measured by tensile testing at the macro-scale without precisely addressing the spatial scale of living cells and their submicron architecture. Atomic force microscopy (AFM) enables the examination of the nano- and micro-mechanical properties of the fibers with potential to correlate the structural mechanical properties across length scales with composition and functional behavior. In this study, a polyesteretherurethane (PEEU) polymer containing poly(p-dioxanone) (PPDO) and poly(ɛ-caprolactone) (PCL) segments was electrospun into fiber meshes or suspended single fibers. We employed AFM three point bending testing and AFM force mapping to measure the elastic modulus and stiffness of individual micro/nanofibers and the fiber mesh. The local stiffness of the fiber mesh including the randomized, intersecting structure was also examined for each individual fiber. Force mapping results with a set point of 50 nN demonstrated the dependence of the elasticity of a single fiber on the fiber mesh architecture. The non-homogeneous stiffness along the same fiber was attributed to the intersecting structure of the supporting mesh morphology. The same fiber measured at a point with and without axial fiber support showed a remarkable difference in stiffness, ranging from 0.2 to 10 nN/nm respectively. For the region, where supporting fibers densely intersected, the stiffness was found to be considerably higher. In the region where the degrees of freedom of the fibers was not restricted, allowing greater displacement, the stiffness were observed to be lower. This study elucidates the relationship between architecture and the mechanical properties of a micro/nanofiber mesh. By providing a greater understanding of the role of spatial arrangement and organization on the surface mechanical properties of such materials, we hope to provide insight into the design of microenvironments capable of regulating cell functionality.


Asunto(s)
Materiales Biocompatibles/química , Microscopía de Fuerza Atómica/métodos , Poliésteres/química , Humanos
14.
Clin Hemorheol Microcirc ; 73(1): 219-228, 2019.
Artículo en Inglés | MEDLINE | ID: mdl-31561335

RESUMEN

Electrospinning has attracted significant attention as a method to produce cell culture substrates whose fibrous structure mimics the native extracellular matrix (ECM). In this study, the influence of E-modulus of fibrous substrates on the lineage commitment of human adipose-derived stem cells (hADSCs) was studied using fiber meshes prepared via the electrospinning of a polyetheresterurethane (PEEU) consisting of poly(ρ-dioxanone) (PPDO) and poly(ɛ-caprolactone) (PCL) segments. The PPDO: PCL weight ratio was varied from 40:60 to 70:30 to adjust the physiochemical properties of the PEEU fibers. The cells attached on stiffer PEEU70 (PPDO:PCL,= 70:30) fiber meshes displayed an elongated morphology compared to those cultured on softer fibers. The nuclear aspect ratio (width vs. length of a nucleus) of hADSCs cultured on softer PEEU40 (PPDO:PCL = 40:60) fibers was lower than on stiffer fibers. The osteogenic differentiation of hADSCs was enhanced by culturing on stiffer fibers. Compared to PEEU40, a 73% increase of osteocalcin expression and a 34% enhancement of alkaline phosphatase (ALP) activity was observed in cells on PEEU70. These results demonstrated that the differentiation commitment of stem cells could be regulated via tailoring the mechanical properties of electrospun fibers.


Asunto(s)
Células Madre Mesenquimatosas/metabolismo , Nanofibras/química , Osteogénesis/genética , Polímeros/metabolismo , Diferenciación Celular , Humanos
15.
ACS Nano ; 13(4): 3858-3866, 2019 Apr 23.
Artículo en Inglés | MEDLINE | ID: mdl-30794379

RESUMEN

Block copolymer self-assembly has enabled the creation of a range of solution-phase nanostructures with applications from optoelectronics and biomedicine to catalysis. However, to incorporate such materials into devices a method that facilitates their precise manipulation and deposition is desirable. Herein we describe how optical tweezers can be used to trap, manipulate, and pattern individual cylindrical micelles and larger hybrid micellar materials. Through the combination of TIRF imaging and optical trapping we can precisely control the three-dimensional motion of individual cylindrical block copolymer micelles in solution, enabling the creation of customizable arrays. We also demonstrate that dynamic holographic assembly enables the creation of ordered customizable arrays of complex hybrid block copolymer structures. By creating a program which automatically identifies, traps, and then deposits multiple assemblies simultaneously we have been able to dramatically speed up this normally slow process, enabling the fabrication of arrays of hybrid structures containing hundreds of assemblies in minutes rather than hours.

16.
Metabolites ; 8(4)2018 Oct 31.
Artículo en Inglés | MEDLINE | ID: mdl-30384466

RESUMEN

It has become increasingly important to qualitatively and quantitatively assess the volatile metabolites in a range of bodily fluids for use in monitoring health. There has been relatively little work on the quantitative analysis of compounds, particularly with respect to the effects of ethnicity or geographic location. A novel method for the quantification of compounds in stool using 13C labelled compounds as internal standards is presented. Using thermal desorption gas chromatography mass spectrometry, stool samples from 38 healthy volunteers were analysed. The 13C labelled compounds, acetone, ethyl butanoate, ethanoic acid, butanoic acid, 3-methylbutanoic acid, and indole, were added as internal standards. This process mimics the solubility characteristics of the compounds and thus the method was able to quantify the compounds within the solid stool. In total, 15 compounds were quantified: Dimethyl sulphide (26⁻25,626 ng/g), acetone (442⁻3006 ng/g), ethyl butanoate (39⁻2468 ng/g), ethyl 2-methylbutanoate (0.3⁻180 ng/g), dimethyl disulphide (35⁻1303 ng/g), 1-octen-3-one (12 ng/g), dimethyl trisulphide (10⁻410 ng/g), 1-octen-3-ol (0.4⁻58 ng/g), ethanoic acid (672⁻12,963 ng/g), butanoic acid (2493⁻11,553 ng/g), 3-methylbutanoic acid (64⁻8262 ng/g), pentanoic acid (88⁻21,886 ng/g), indole (290⁻5477 ng/g), and 3-methyl indole (37⁻3483 ng/g). Moreover, by altering the pH of the stool to pH 13 in conjunction with the addition of 13C trimethylamine, the method was successful in detecting and quantifying trimethylamine for the first time in stool samples (range 40⁻5312 ng/g). Statistical analysis revealed that samples from U.K. origin had five significantly different compounds (ethyl butanoate, 1-octen-3-ol, ethanoic acid, butanoic acid, pentanoic acid, and indole) from those of South American origin. However, there were no significant differences between vegetarian and omnivore samples. These findings are supported by pre-existing literature evidence. Moreover, we have tentatively identified 12 compounds previously not reported as having been found in stool.

17.
Chemphyschem ; 19(16): 2078-2084, 2018 08 17.
Artículo en Inglés | MEDLINE | ID: mdl-29683553

RESUMEN

The implementation of shape-memory effects (SME) in polymeric micro- or nano-objects currently relies on the application of indirect macroscopic manipulation techniques, for example, stretchable molds or phantoms, to ensembles of small objects. Here, we introduce a method capable of the controlled manipulation and SME quantification of individual micro- and nano-objects in analogy to macroscopic thermomechanical test procedures. An atomic force microscope was utilized to address individual electro-spun poly(ether urethane) (PEU) micro- or nanowires freely suspended between two micropillars on a micro-structured silicon substrate. In this way, programming strains of 10±1% or 21±1% were realized, which could be successfully fixed. An almost complete restoration of the original free-suspended shape during heating confirmed the excellent shape-memory performance of the PEU wires. Apparent recovery stresses of σmax,app =1.2±0.1 and 33.3±0.1 MPa were obtained for a single microwire and nanowire, respectively. The universal AFM test platform described here enables the implementation and quantification of a thermomechanically induced function for individual polymeric micro- and nanosystems.

18.
J Breath Res ; 12(1): 016009, 2017 Dec 06.
Artículo en Inglés | MEDLINE | ID: mdl-29211690

RESUMEN

There have been a number of studies in which metal oxide sensors (MOS) have replaced conventional analytical detectors in gas chromatography systems. However, despite the use of these instruments in a range of applications including breath research the sensor responses (i.e. resistance changes w.r.t. concentration of VCs) remain largely unreported. This paper addresses that issue by comparing the response of a metal oxide sensor directly with a mass spectrometer (MS), whereby both detectors are interfaced to the same GC column using an s-swafer. It was demonstrated that the sensitivity of an in-house fabricated ZnO/SnO2 thick film MOS was superior to a modern MS for the detection of a wide range of volatile compounds (VCs) of different functionalities and masses. Better techniques for detection and quantification of these VCs is valuable, as many of these compounds are commonly reported throughout the scientific literature. This is also the first published report of a combined GC-MS sensor system. These two different detector technologies when combined, should enhance discriminatory abilities to aid disease diagnoses using volatiles from e.g. breath, and bodily fluids. Twenty-nine chemical standards have been tested using solid phase micro-extraction; 25 of these compounds are found on human breath. In all but two instances the sensor exhibited the same or superior limit of detection compared to the MS. Twelve stool samples from healthy participants were analysed; the sensor detected, on average 1.6 peaks more per sample than the MS. Similarly, analysing the headspace of E. coli broth cultures the sensor detected 6.9 more peaks per sample versus the MS. This greater sensitivity is primarily a function of the superior limits of detection of the metal oxide sensor. This shows that systems based on the combination of chromatography systems with solid state sensors shows promise for a range of applications.


Asunto(s)
Cromatografía de Gases y Espectrometría de Masas/instrumentación , Cromatografía de Gases y Espectrometría de Masas/métodos , Compuestos Orgánicos Volátiles/análisis , Escherichia coli/aislamiento & purificación , Heces/química , Humanos , Límite de Detección , Metales/química , Óxidos/química , Estándares de Referencia , Semiconductores , Soluciones
19.
Phys Rev Lett ; 119(24): 241601, 2017 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-29286728

RESUMEN

Magnetic monopoles, if they exist, would be produced amply in strong magnetic fields and high temperatures via the thermal Schwinger process. Such circumstances arise in heavy-ion collisions and in neutron stars, both of which imply lower bounds on the mass of possible magnetic monopoles. In showing this, we construct the cross section for pair production of magnetic monopoles in heavy-ion collisions, which indicates that they are particularly promising for experimental searches such as MoEDAL.

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