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1.
Biofouling ; : 1-13, 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38955544

RESUMO

Biofouling on marine surfaces causes immense material and financial harm for maritime vessels and related marine industries. Previous reports have shown the effectiveness of amphiphilic coating systems based on poly(dimethylsiloxane) (PDMS) against such marine foulers. Recent studies on biofouling mechanisms have also demonstrated acidic microenvironments in biofilms and stronger adhesion at low-pH conditions. This report presents the design and utilization of amphiphilic polymer coatings with buffer functionalities as an active disruptor against four different marine foulers. Specifically, this study explores both neutral and zwitterionic buffer systems for marine coatings, offering insights into coating design. Overall, these buffer systems were found to improve foulant removal, and unexpectedly were the most effective against the diatom Navicula incerta.

2.
ACS Appl Mater Interfaces ; 16(15): 19594-19604, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38588386

RESUMO

Polydimethylsiloxane (PDMS) has been widely used as a surface coating material, which has been reported to possess dynamic omniphobicity to a wide range of both polar and nonpolar solvents due to its high segmental flexibility and mobility. However, such high flexibility and mobility also enable penetration of small molecules into PDMS coatings, which alter the chemical and physical properties of the coating layers. To improve the anti-penetration properties of PDMS, a series of fluorinated alkyl segments are grafted to a diblock copolymer of polystyrene-block-poly(vinyl methyl siloxane) (PS-b-PVMS) using thiol-ene click reactions. This article reports the chemical characterization of these model fluorosilicone block copolymers and uses fluorescence measurements to investigate the dye penetration characteristics of polymer thin films. The introduction of longer fluorinated alkyl chains can gradually increase the anti-penetration properties as the time to reach the maximum fluorescence intensity (tpeak) gradually increases from 11 s of PS-b-PVMS to more than 1000 s of PS-b-P(n-C6F13-VMS). The improvement of anti-penetration properties is attributed to stronger inter-/intrachain interactions, phase segregation of ordered fluorinated side chains, and enhanced hydrophobicity caused by the grafting of fluorinated alkyl chains.

3.
Small ; 20(22): e2309040, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38334235

RESUMO

Designing smart (bio)interfaces with the capability to sense and react to changes in local environments offers intriguing possibilities for new surface-based sensing devices and technologies. Polymer brushes make ideal materials to design such adaptive and responsive interfaces given their large variety of functional and structural possibilities as well as their outstanding abilities to respond to physical, chemical, and biological stimuli. Herein, a practical sensory interface for glucose detection based on auto-fluorescent polymer brushes decorated with phenylboronic acid (PBA) receptors is presented. The glucose-responsive luminescent surfaces, which are capable of translating conformational transitions triggered by pH variations and binding events into fluorescent readouts without the need for fluorescent dyes, are grown from both nanopatterned and non-patterned substrates. Two-photon laser scanning confocal microscopy and atomic force microscopy (AFM) analyses reveal the relationship between the brush conformation and glucose concentration and confirm that the phenylboronic acid functionalized brushes can bind glucose over a range of physiologically relevant concentrations in a reversible manner. The combination of auto-fluorescent polymer brushes with synthetic receptors presents a promising avenue for designing innovative and robust sensing systems, which are essential for various biomedical applications, among other uses.


Assuntos
Ácidos Borônicos , Glucose , Polímeros , Propriedades de Superfície , Glucose/química , Polímeros/química , Ácidos Borônicos/química , Microscopia de Força Atômica , Técnicas Biossensoriais/métodos , Corantes Fluorescentes/química , Concentração de Íons de Hidrogênio
4.
Langmuir ; 40(1): 282-290, 2024 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-38131624

RESUMO

Polymeric zwitterions exhibit exceptional fouling resistance through the formation of a strongly hydrated surface of immobilized water molecules. While being extensively tested for their performance in biomedical, membrane, and, to a lesser extent, marine environments, few studies have investigated how the molecular design of the zwitterion may enhance its performance. Furthermore, while theories of zwitterion antifouling mechanisms exist for molecular-scale foulant species (e.g., proteins and small molecules), it remains unclear how molecular-scale mechanisms influence the micro- and macroscopic interactions of relevance for marine applications. The present study addresses these gaps through the use of a modular zwitterion chemistry platform, which is characterized by a combination of surface-sensitive sum frequency generation (SFG) vibrational spectroscopy and marine assays. Zwitterions with increasingly delocalized cations demonstrate improved fouling resistance against the green alga Ulva linza. SFG spectra correlate well with the assay results, suggesting that the more diffuse charges exhibit greater surface hydration with more bound water molecules. Hence, the number of bound interfacial water molecules appears to be more influential in determining the marine antifouling activities of zwitterionic polymers than the binding strength of individual water molecules at the interface.

5.
ACS Appl Mater Interfaces ; 15(47): 54942-54951, 2023 Nov 29.
Artigo em Inglês | MEDLINE | ID: mdl-37973616

RESUMO

Nanochannels with controllable gating behavior are attractive features in a wide range of nanofluidic applications including viral detection, particle sorting, and flow regulation. Here, we use selective sidewall functionalization of nanochannels with a polyelectrolyte brush to investigate the channel gating response to variations in solution pH and ionic strength. The conformational and structural changes of the interfacial brush layer within the channels are interrogated by specular and off-specular neutron reflectometry. Simultaneous fits of the specular and off-specular signals, using a dynamical theory model and a fitting optimization protocol, enable detailed characterization of the brush conformations and corresponding channel geometry under different solution conditions. Our results indicate a collapsed brush state under basic pH, equivalent to an open gate, and an expanded brush state representing a partially closed gate upon decreasing the pH and salt concentration. These findings open new possibilities in noninvasive in situ characterization of tunable nanofluidics and lab-on-chip devices with advanced designs and improved functionality.

6.
Macromol Rapid Commun ; 44(20): e2300304, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37585219

RESUMO

Understanding how small molecules penetrate and contaminate polymer films is of vital importance for developing protective coatings for a wide range of applications. To this end, rhodamine B fluorescent dye is visualized diffusing through polystyrene-polydimethylsiloxane block copolymer (BCP) coatings using confocal microscopy. The intensity of dye inside the coatings grows and decays non-monotonically, which is likely due to a combination of dye molecule transport occurring concurrently in different directions. An empirical fitting equation allows for comparing the contamination rates between copolymers, demonstrating that dye penetration is related to the chemical makeup and configuration of the BCPs. This work shows that confocal microscopy can be a useful tool to visualize the transport of a fluorophore in space and time through a coating.


Assuntos
Corantes Fluorescentes , Polímeros , Polímeros/química , Corantes Fluorescentes/química , Poliestirenos
7.
PLoS One ; 18(3): e0282500, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36862650

RESUMO

For dogs with oral tumors, cervical lymph node (LN) metastasis alters treatment and prognosis. It is therefore prudent to make an accurate determination of the clinical presence (cN+ neck) or absence (cN0 neck) of metastasis prior to treatment. Currently, surgical LN extirpation with histopathology is the gold standard for a diagnosis of metastasis. Yet, recommendations to perform elective neck dissection (END) for staging are rare due to morbidity. Sentinel lymph node (SLN) mapping with indirect computed tomography lymphangiography (ICTL) followed by targeted biopsy (SLNB) is an alternative option to END. In this prospective study, SLN mapping followed by bilateral END of all mandibular LNs (MLNs) and medial retropharyngeal LNs (MRLNs) was performed in 39 dogs with spontaneously occurring oral neoplasia. A SLN was identified by ICTL in 38 (97%) dogs. Lymphatic drainage patterns were variable although most often the SLN was identified as a single ipsilateral MLN. In the 13 dogs (33%) with histopathologically confirmed LN metastasis, ICTL correctly identified the draining lymphocentrum in all (100%). Metastasis was confined to the SLN in 11 dogs (85%); 2 dogs (15%) had metastasis beyond the SLN ipsilaterally. Contrast enhanced CT features had good accuracy in predicting metastasis, with short axis measurements less than 10.5 mm most predictive. ICTL imaging features alone were unable to predict metastasis. Cytologic or histopathologic SLN sampling is recommended prior to treatment to inform clinical decision-making. This is the largest study to show potential clinical utility of minimally invasive ICTL for cervical LN evaluation in canine oral tumors.


Assuntos
Linfografia , Neoplasias Bucais , Cães , Animais , Linfografia/veterinária , Estudos Prospectivos , Metástase Linfática/diagnóstico por imagem , Neoplasias Bucais/diagnóstico por imagem , Neoplasias Bucais/veterinária , Tomografia Computadorizada por Raios X
8.
ACS Appl Mater Interfaces ; 15(8): 11150-11162, 2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36802475

RESUMO

Two types of amphiphilic random terpolymers, poly(ethylene glycol methyl ether methacrylate)-ran-poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate)-ran-poly(polydimethyl siloxane methacrylate) (PEGMEMA-r-PTMA-r-PDMSMA), were synthesized and evaluated for antifouling (AF) and fouling-release (FR) properties using diverse marine fouling organisms. In the first stage of production, the two respective precursor amine terpolymers containing (2,2,6,6-tetramethyl-4-piperidyl methacrylate) units (PEGMEMA-r-PTMPM-r-PDMSMA) were synthesized by atom transfer radical polymerization using various comonomer ratios and two initiators: alkyl halide and fluoroalkyl halide. In the second stage, these were selectively oxidized to introduce nitroxide radical functionalities. Finally, the terpolymers were incorporated into a PDMS host matrix to create coatings. AF and FR properties were examined using the alga Ulva linza, the barnacle Balanus improvisus, and the tubeworm Ficopomatus enigmaticus. The effects of comonomer ratios on surface properties and fouling assay results for each set of coatings are discussed in detail. There were marked differences in the effectiveness of these systems against the different fouling organisms. The terpolymers had distinct advantages over monopolymeric systems across the different organisms, and the nonfluorinated PEG and nitroxide combination was identified as the most effective formulation against B. improvisus and F. enigmaticus.

9.
ACS Nano ; 16(12): 20714-20729, 2022 Dec 27.
Artigo em Inglês | MEDLINE | ID: mdl-36475656

RESUMO

Leveraging the self-assembling behavior of liquid crystals designed for controlling ion transport is of both fundamental and technological significance. Here, we have designed and prepared a liquid crystal that contains 2,5-bis(thien-2-yl)thieno[3,2-b]thiophene (BTTT) as mesogenic core and conjugated segment and symmetric tetra(ethylene oxide) (EO4) as polar side chains for ion-conducting regions. Driven by the crystallization of the BTTT cores, BTTT/dEO4 exhibits well-ordered smectic phases below 71.5 °C as confirmed by differential scanning calorimetry, polarized optical microscopy, temperature-dependent wide-angle X-ray scattering, and grazing incidence wide-angle X-ray scattering (GIWAXS). We adopted a combination of experimental GIWAXS and molecular dynamics (MD) simulations to better understand the molecular packing of BTTT/dEO4 films, particularly when loaded with the ion-conducting salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Ionic conduction of BTTT/dEO4 is realized by the addition of LiTFSI, with the material able to maintain smectic phases up to r = [Li+]/[EO] = 0.1. The highest ionic conductivity of 8 × 10-3 S/cm was attained at an intermedium salt concentration of r = 0.05. It was also found that ion conduction in BTTT/dEO4 is enhanced by forming a smectic layered structure with irregular interfaces between the BTTT and EO4 layers and by the lateral film expansion upon salt addition. This can be explained by the enhancement of the misalignment and configurational entropy of the side chains, which increase their local mobility and that of the solvated ions. Our molecular design thus illustrates how, beyond the favorable energetic interactions that drive the assembly of ion solvating domains, modulation of entropic effects can also be favorably harnessed to improve ion conduction.

10.
J Am Chem Soc ; 144(42): 19508-19520, 2022 10 26.
Artigo em Inglês | MEDLINE | ID: mdl-36208192

RESUMO

The resolution, line edge roughness, and sensitivity (RLS) trade-off has fundamentally limited the lithographic performance of chemically amplified resists. Production of next-generation transistors using extreme ultraviolet (EUV) lithography depends on a solution to this problem. A resist that simultaneously increases the effective reaction radius of its photogenerated acids while limiting their diffusion radius should provide an elegant solution to the RLS barrier. Here, we describe a generalized synthetic approach to phthalaldehyde derivatives using sulfur(VI) fluoride exchange click chemistry that dramatically expands usable chemical space by enabling virtually any non-ionic photoacid generator (PAG) to be tethered to phthalaldehyde. The resulting polymers represent the first ever PAG-tethered self-immolative resists in an architecture that simultaneously displays high contrast, extraordinary sensitivity, and low roughness under EUV exposure. We believe this class of resists will ultimately enable researchers to overcome the RLS trade-off.


Assuntos
Fluoretos , Polímeros , Polímeros/química , Ácidos/química , Difusão , Enxofre
11.
Am J Vet Res ; 83(12)2022 Oct 27.
Artigo em Inglês | MEDLINE | ID: mdl-36288199

RESUMO

OBJECTIVE: To measure the mitral annulus in dogs. Our hypothesis was that mitral measurement would be possible and consistent among observers using CT. SAMPLE: Thoracic CT scans of dogs without known heart disease. PROCEDURES: Five trained investigators measured 4 aspects of the mitral valve and the fourth thoracic vertebrae (T4) length using multiplanar reformatting tools. Ten randomly chosen animals were measured by all investigators to determine interobserver reliability. RESULTS: There were 233 CT scans eligible for inclusion. Dogs weighed 2 to 96 kg (mean, 28.1 kg), with a variety of breeds represented. Golden Retrievers (n = 28) and Labrador Retrievers (n = 37) were overrepresented. The intraclass correlations were all greater than 0.9, showing excellent agreement between observers. The means and SDs of each measurement were as follows: trigone-to-trigone distance, 17.2 ± 4.7 mm; the remaining circumference, 79.0 ± 17.5 mm; commissure-to-commissure distance, 30.8 ± 6.5 mm; septal leaflet-to-lateral leaflet distance, 26.3 ± 6.0 mm; T4 length, 16.9 ± 3.1 mm; and the total circumference normalized by T4, 5.7 ± 0.7 mm. CLINICAL RELEVANCE: This study provides information that may help in the development of future treatment for mitral valve dysfunction and subsequent annular enlargement.


Assuntos
Doenças do Cão , Insuficiência da Valva Mitral , Cães , Animais , Valva Mitral/diagnóstico por imagem , Insuficiência da Valva Mitral/diagnóstico por imagem , Insuficiência da Valva Mitral/veterinária , Reprodutibilidade dos Testes , Tomografia Computadorizada por Raios X/veterinária , Doenças do Cão/diagnóstico por imagem
12.
Am J Vet Res ; 83(7)2022 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-35930776

RESUMO

OBJECTIVE: To evaluate the enhancement accuracy of a triple-phase abdominal CT angiography (CTA) protocol in dogs and explore the patient, scan, and contrast parameters associated with accuracy of enhancement. ANIMALS: 233 client-owned dogs that underwent routine abdominal CTA. PROCEDURES: During each CTA study, the subjective timing accuracy (early, ideal, late) of the 3 obtained vascular phases (arterial, venous, delayed) was scored by consensus (2 reviewers) at 4 target organs (liver, pancreas, left kidney, and spleen). These scores were evaluated for statistical associations with 21 study variables (patient, scan, and contrast medium). The objective enhancement (HU) for each target organ was also compared statistically with subjective timing accuracy scores and the study variables. RESULTS: The study protocol performed best for the pancreas, moderately for the liver, and worse for the spleen and left kidney. Measurements of scan length and time were associated positively with phase lateness for most target organs and phases. Increased heart rate was the most significant patient factor associated positively with phase lateness within the liver (all phases), pancreas (arterial and venous phases), and kidney (arterial phase). Contrast medium variables were less associated with timing accuracy in this protocol. Objective enhancement (HU) correlated poorly with subjective phase timing accuracy and study variables. CLINICAL RELEVANCE: Scan time, scan length, and heart rate were the predominant variables contributing to lateness in this canine abdominal CTA protocol. The findings of this exploratory study may aid in protocol adjustment and choice of included anatomy for dogs undergoing routine abdominal CTA.


Assuntos
Angiografia por Tomografia Computadorizada , Meios de Contraste , Abdome/diagnóstico por imagem , Angiografia/veterinária , Animais , Angiografia por Tomografia Computadorizada/métodos , Angiografia por Tomografia Computadorizada/veterinária , Cães , Fígado
13.
ACS Macro Lett ; 11(9): 1049-1054, 2022 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-35948019

RESUMO

Conventional chemically amplified resists (CARs) rely on the usage of photoacid generators to serve as the source of chemical amplification. However, acid diffusion inevitably accompanies CARs and has led to the resolution, line edge roughness, and sensitivity (RLS) trade-off, which is the most challenging technical problem for modern photoresists. Herein, we take advantage of the self-immolative property of polyphthalaldehyde (PPA) derivatives to create end-cap enabled chain scissionable resists for extreme ultraviolet (EUV) lithography. The feasibility of this strategy was demonstrated under UV photodegradation experiments. The dose-to-clear (DTC) under EUV radiation was 90 mJ/cm2 for the most promising resist, representing more than a 100-fold improvement over previous PPA resists. Density functional theory (DFT) calculations were conducted to understand the structural origin of end-cap EUV sensitivity.


Assuntos
Impressão , Raios Ultravioleta , Ácidos/química , Difusão , Fotólise
14.
Biomacromolecules ; 23(6): 2697-2712, 2022 06 13.
Artigo em Inglês | MEDLINE | ID: mdl-35486708

RESUMO

Biofouling is a major disruptive process affecting the fuel efficiency and durability of maritime vessel coatings. Previous research has shown that amphiphilic coatings consisting of a siloxane backbone functionalized with hydrophilic moieties are effective marine antifouling and fouling-release materials. Poly(ethylene glycol) (PEG) has been the primary hydrophilic component used in such systems. Recently, the morpholine group has emerged as a promising compact alternative in antifouling membranes but is yet to be studied against marine foulants. In this work, the use of morpholine moieties to generate amphiphilicity in a poly(dimethylsiloxane) (PDMS)-based antifouling and fouling-release coating was explored. Two separate coating sets were investigated. The first set examined the incorporation of an N-substituted morpholine amine, and while these coatings showed promising fouling-release properties for Ulva linza, they had unusually high settlement of spores compared to controls. Based on those results, a second set of materials was synthesized using an N-substituted morpholine amide to probe the source of the high settlement and was found to significantly improve antifouling performance. Both coating sets included PEG controls with varying lengths to compare the viability of the morpholine structures as alternative hydrophilic groups. Surfaces were evaluated through a combination of bubble contact angle goniometry, profilometry, X-ray photoelectron spectroscopy (XPS), and marine bioassays against two soft fouling species, U. linza and Navicula incerta, known to have different adhesion characteristics.


Assuntos
Incrustação Biológica , Diatomáceas , Ulva , Incrustação Biológica/prevenção & controle , Morfolinas , Polietilenoglicóis/química , Propriedades de Superfície
15.
Vet Radiol Ultrasound ; 63(4): 430-435, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35188306

RESUMO

Sciatic and gluteal lymph nodes are present in multiple veterinary species, but these lymph nodes are explicitly stated to be absent in dogs. However, structures compatible with lymph nodes have been identified in the appropriate locations in some canine patients undergoing abdominopelvic CT, and the presence of such lymph nodes may have prognostic and therapeutic ramifications in canine patients with abdominopelvic disease. The purpose of this study was to determine the prevalence and characteristics of sciatic and gluteal lymph nodes in dogs on CT. Images of 121 dogs that underwent abdominopelvic CT between September 1, 2020 and December 31, 2020 were reviewed retrospectively by two readers to produce a consensus opinion regarding the presence or absence of sciatic and gluteal lymph nodes. Lymph nodes that were present were measured. Unilateral or bilateral sciatic lymph nodes were present in 19 of 121 dogs (prevalence 15.7%), and bilateral gluteal lymph nodes were identified in one of 121 patients (prevalence 0.8%). Recognition of the presence of sciatic and gluteal lymph nodes in some canine patients may play an important role in the staging of abdominopelvic disease, both in the identification of disease spread and in therapeutic planning.


Assuntos
Linfonodos , Tomografia Computadorizada por Raios X , Abdome , Animais , Cães , Linfonodos/diagnóstico por imagem , Pelve/diagnóstico por imagem , Estudos Retrospectivos , Tomografia Computadorizada por Raios X/métodos , Tomografia Computadorizada por Raios X/veterinária
16.
ACS Appl Mater Interfaces ; 14(5): 7340-7349, 2022 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-35089024

RESUMO

Polymers are commonly used in applications that require long-term exposure to water and aqueous mixtures, serving as water purification membranes, marine antifouling coatings, and medical implants, among many other applications. Because polymer surfaces restructure in response to the surrounding environment, in situ characterization is crucial for providing an accurate understanding of the surface chemistry under conditions of use. To investigate the effects of surface-active side chains on polymer surface chemistry and resultant interactions with interfacial water (i.e., water sorption), we present synchrotron ambient pressure X-ray photoelectron spectroscopy (APXPS) studies performed on poly(ethylene oxide) (PEO)- and poly(dimethylsiloxane) (PDMS)-based polymer surfaces modified with amphiphilic polypeptoid side chains, previously demonstrated to be efficacious in marine fouling prevention and removal. The polymer backbone and environmental conditions were found to affect polypeptoid surface presentation: due to the surface segregation of its fluorinated polypeptoid monomers under vacuum, the PEO-peptoid copolymer showed significant polypeptoid content in both vacuum and hydrated conditions, while the modified PDMS-based copolymer showed increased polypeptoid content only in hydrated conditions due to the hydrophilicity of the ether monomers and polypeptoid backbone. Polypeptoids were found to bind approximately 2.8 water molecules per monomer unit in both copolymers, and the PEO-peptoid surface showed substantial water sorption that suggests a surface with a more diffuse water/polymer interface. This work implies that side chains are ideal for tuning water affinity without altering the base polymer composition, provided that surface-driving groups are present to ensure activity at the interface. These types of systematic modifications will generate novel polymers that maximize bound interfacial water and can deliver surface-active groups to the surface to improve the effectiveness of polymer materials.

17.
J Vet Med Educ ; 49(6): 709-715, 2022 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-34310256

RESUMO

Learning the concepts of clinical radiology, including lesion identification and formulation of differential diagnosis lists, can be challenging for veterinary students. A series of educational puzzles with an overarching narrative was developed to help students learn the fundamental concepts of urogenital, thoracic, and spine imaging. Third-year veterinary students had the opportunity to use as many of the puzzles as they wished as a part of their studies in a semester-long imaging course, and students completed surveys to indicate which puzzle sections they used and provide their opinions of the activities. Graded performance in the course was correlated with how many puzzle activities students used. A small but statistically significant correlation was found between the number of puzzle sections used and midterm exam score, final exam score, and overall course score. Although most students who used the puzzles as a part of their studies enjoyed the activities, there was a dramatic decrease in usage over the semester, from 74% of survey respondents using the initial topic to a low of 27% utilization of the sixth topic, followed by a small rebound to 37% for the eighth topic (the review for the final exam). Thus, while developing a puzzle series is achievable and beneficial to student learning, possibly because of improved student engagement through increased variety in learning opportunities, further steps are necessary to encourage continued student engagement throughout the semester.


Assuntos
Educação em Veterinária , Animais , Diagnóstico por Imagem
18.
Macromol Rapid Commun ; 43(12): e2100629, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-34743391

RESUMO

Polymer-grafted nanoparticles (PGNs) receive great attention because they possess the advantages of both the grafted polymer and inorganic cores, and thus demonstrate superior optical, electronic, and mechanical properties. Thus, PGNs with tailorable interparticle interactions are indispensable for the formation of a superlattice with a defined and ordered structure. In this work, the synthesis of PGNs is reported which can form interparticle hydrogen-bonding to enhance the formation of well-defined 2D nanoparticle arrays. Various polymers, including poly(4-vinyl pyridine) (P4VP), poly(dimethyl aminoethyl acrylate) (PDMAEMA), and poly(4-acetoxy styrene) (PAcS), are attached to silica cores by a "grafting from" in a mini emulsion-like synthesis approach. SiO2 -PAcS brushes are deprotected by hydrazinolysis and converted into poly(4-vinyl phenol) (PVP), containing hydroxyl groups as potential hydrogen-bonding donor sites. Understanding and controlling interparticle interactions by varying grafting density in the range of 10-2 -10-3 chain nm-2 , and the formation of interparticle hydrogen bonding relevant for self-assembly of PGNs and potential formation of PGN superlattice structures are the motivations for this study.


Assuntos
Nanopartículas , Polímeros , Hidrogênio , Ligação de Hidrogênio , Nanopartículas/química , Polímeros/química , Dióxido de Silício/química , Propriedades de Superfície
19.
PLoS One ; 16(8): e0256139, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34403435

RESUMO

Quantitative analysis of computed tomography (CT) radiomic features is an indirect measure of tumor heterogeneity, which has been associated with prognosis in human lung carcinoma. Canine lung tumors share similar features to human lung tumors and serve as a model in which to investigate the utility of radiomic features in differentiating tumor type and prognostication. The purpose of this study was to correlate first-order radiomic features from canine pulmonary tumors to histopathologic characteristics and outcome. Disease-free survival, overall survival time and tumor-specific survival were calculated as days from the date of CT scan. Sixty-seven tumors from 65 dogs were evaluated. Fifty-six tumors were classified as primary pulmonary adenocarcinomas and 11 were non-adenocarcinomas. All dogs were treated with surgical resection; 14 dogs received adjuvant chemotherapy. Second opinion histopathology in 63 tumors confirmed the histologic diagnosis in all dogs and further characterized 53 adenocarcinomas. The median overall survival time was longer (p = 0.004) for adenocarcinomas (339d) compared to non-adenocarcinomas (55d). There was wide variation in first-order radiomic statistics across tumors. Mean Hounsfield units (HU) ratio (p = 0.042) and median mean HU ratio (p = 0.042) were higher in adenocarcinomas than in non-adenocarcinomas. For dogs with adenocarcinoma, completeness of excision was associated with overall survival (p<0.001) while higher mitotic index (p = 0.007) and histologic score (p = 0.037) were associated with shorter disease-free survival. CT-derived tumor variables prognostic for outcome included volume, maximum axial diameter, and four radiomic features: integral total, integral total mean ratio, total HU, and max mean HU ratio. Tumor volume was also significantly associated with tumor invasion (p = 0.044). Further study of radiomic features in canine lung tumors is warranted as a method to non-invasively interrogate CT images for potential predictive and prognostic utility.


Assuntos
Neoplasias Pulmonares/diagnóstico por imagem , Neoplasias Pulmonares/patologia , Tomografia Computadorizada de Emissão/métodos , Adenocarcinoma/patologia , Animais , Carcinoma Pulmonar de Células não Pequenas/patologia , Bases de Dados Factuais , Bases de Dados Genéticas , Intervalo Livre de Doença , Cães , Feminino , Pulmão/patologia , Neoplasias Pulmonares/veterinária , Masculino , Prognóstico , Estudos Retrospectivos , Tomografia Computadorizada de Emissão/veterinária , Tomografia Computadorizada por Raios X/métodos , Carga Tumoral
20.
Vet Radiol Ultrasound ; 62(6): 711-719, 2021 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-34448312

RESUMO

Tumor heterogeneity is a well-established marker of biologically aggressive neoplastic processes and is associated with local recurrence and distant metastasis. Quantitative analysis of CT textural features is an indirect measure of tumor heterogeneity and therefore may help predict malignant disease. The purpose of this retrospective, secondary analysis study was to quantitatively evaluate CT heterogeneity in dogs with histologically confirmed liver masses to build a predictive model for malignancy. Forty dogs with liver tumors and corresponding histopathologic evaluation from a previous prospective study were included. Triphasic image acquisition was standardized across dogs and whole liver and liver mass were contoured on each precontrast and delayed postcontrast dataset. First-order and second-order indices were extracted from contoured regions. Univariate analysis identified potentially significant indices that were subsequently used for top-down model construction. Multiple quadratic discriminatory models were constructed and tested, including individual models using both postcontrast and precontrast whole liver or liver mass volumes. The best performing model utilized the CT features voxel volume and uniformity from postcontrast mass contours; this model had an accuracy of 0.90, sensitivity of 0.67, specificity of 1.0, positive predictive value of 1.0, negative predictive value of 0.88, and precision of 1.0. Heterogeneity indices extracted from delayed postcontrast CT hepatic mass contours were more informative about tumor type compared to indices from whole liver contours, or from precontrast hepatic mass and whole liver contours. Results demonstrate that CT radiomic feature analysis may hold clinical utility as a noninvasive method of predicting hepatic malignancy and may influence diagnostic or therapeutic approaches.


Assuntos
Doenças do Cão , Neoplasias Hepáticas , Animais , Doenças do Cão/diagnóstico por imagem , Cães , Neoplasias Hepáticas/diagnóstico por imagem , Neoplasias Hepáticas/veterinária , Aprendizado de Máquina , Valor Preditivo dos Testes , Estudos Retrospectivos , Tomografia Computadorizada por Raios X/veterinária
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