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1.
J Biol Chem ; 298(8): 102134, 2022 08.
Artigo em Inglês | MEDLINE | ID: mdl-35709985

RESUMO

Extra-large stimulatory Gα (XLαs) is a large variant of G protein αs subunit (Gαs) that uses an alternative promoter and thus differs from Gαs at the first exon. XLαs activation by G protein-coupled receptors mediates cAMP generation, similarly to Gαs; however, Gαs and XLαs have been shown to have distinct cellular and physiological functions. For example, previous work suggests that XLαs can stimulate inositol phosphate production in renal proximal tubules and thereby regulate serum phosphate levels. In this study, we show that XLαs directly and specifically stimulates a specific isoform of phospholipase Cß (PLCß), PLCß4, both in transfected cells and with purified protein components. We demonstrate that neither the ability of XLαs to activate cAMP generation nor the canonical G protein switch II regions are required for PLCß stimulation. Furthermore, this activation is nucleotide independent but is inhibited by Gßγ, suggesting a mechanism of activation that relies on Gßγ subunit dissociation. Surprisingly, our results indicate that enhanced membrane targeting of XLαs relative to Gαs confers the ability to activate PLCß4. We also show that PLCß4 is required for isoproterenol-induced inositol phosphate accumulation in osteocyte-like Ocy454 cells. Taken together, we demonstrate a novel mechanism for activation of phosphoinositide turnover downstream of Gs-coupled receptors that may have a critical role in endocrine physiology.


Assuntos
Subunidades alfa Gs de Proteínas de Ligação ao GTP , Fosfatos de Inositol , Fosfolipase C beta , Membrana Celular/metabolismo , Subunidades alfa Gs de Proteínas de Ligação ao GTP/metabolismo , Fosfatos de Inositol/metabolismo , Isoenzimas/metabolismo , Isoproterenol/farmacologia , Fosfolipase C beta/metabolismo
2.
Annu Rev Phys Chem ; 73: 141-162, 2022 04 20.
Artigo em Inglês | MEDLINE | ID: mdl-34936809

RESUMO

Surface-enhanced Raman scattering (SERS), a powerful technique for trace molecular detection, depends on chemical and electromagnetic enhancements. While recent advances in instrumentation and substrate design have expanded the utility, reproducibility, and quantitative capabilities of SERS, some challenges persist. In this review, advances in quantitative SERS detection are discussed as they relate to intermolecular interactions, surface selection rules, and target molecule solubility and accessibility. After a brief introduction to Raman scattering and SERS, impacts of surface selection rules and enhancement mechanisms are discussed as they relate to the observation of activation and deactivation of normal Raman modes in SERS. Next, experimental conditions that can be used to tune molecular affinity to and density near SERS substrates are summarized and considered while tuning these parameters is conveyed. Finally, successful examples of quantitative SERS detection are discussed, and future opportunities are outlined.


Assuntos
Análise Espectral Raman , Reprodutibilidade dos Testes , Análise Espectral Raman/métodos
3.
Langmuir ; 37(16): 4891-4899, 2021 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-33861606

RESUMO

The plasmonic properties of carboxylated gold nanostars distributed on amidoximated polyacrylonitrile (AO PAN) electrospun polymer films scale with surface-enhanced Raman scattering (SERS) intensities for coordinated uranium(VI) oxide (uranyl) species. This two-step plasmonic sensor first isolates uranyl from solution using functionalized polymers; then carboxylated gold nanostars are subsequently deposited for SERS. Spatially resolved localized surface plasmon resonance (LSPR) and SERS facilitate correlated nanostar optical density and uranyl quantification. To reduce sampling bias, gold nanostars are deposited in an inverted drop-coating geometry and measurements are conducted inside resulting nanoparticle coffee rings that form on the polymer substrates. This approach naturally preserves the plasmonic properties of gold nanostars while reducing the deposition of nanoparticle aggregates in active sensing regions, thereby maximizing both the accuracy and the precision of SERS measurements. Several advances are made. First, second-derivative analysis of LSPR spectra facilitates the quantification of local nanostar density across large regions of the sensor substrate by reducing background variations caused by the polymeric and gold materials. Second, local nanostar densities ranging from 140 to 200 pM·cm are shown to result in uranyl signals that are independent of nanostar concentration. Third, the Gibbs free energy of uranyl adsorption to carboxylated nanostars is estimated at 8.4 ± 0.2 kcal/mol. Finally, a linear dynamic range from ∼0.3 to 3.4 µg U/mg polymer is demonstrated. Signals vary by 10% or less. As such, the uniformity of the plasmonic activity of distributed gold nanostars and the employment of spatially resolved spectroscopic measurements on the composite nanomaterial sensor interface facilitate the quantitative detection of uranyl while also reducing the dependence on user expertise and the selected sampling region. These important advances are critical for the development of a user-friendly SERS-based sensor for uranyl.

4.
Angew Chem Int Ed Engl ; 60(9): 4464-4469, 2021 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-33166014

RESUMO

The synthesis of peri-fused acenes (peri-acenes) with two or more rows is challenging due to their intrinsic open-shell diradical character. Herein, we report the isolation of a derivative (4) of [4,3]peri-acene in crystalline form. The parent [4,3]peri-acene, containing three rows of tetracene, has a large diradical character (y0 =94.8 %) originating from aromatic stabilization. Due to kinetic blocking, 4 showed a reasonable stability with a half-life time of ≈157 h under ambient conditions. Its structure was determined by X-ray crystallographic analysis, and bond-length analysis revealed eight localized Clar's sextets. 4 exhibited an open-shell singlet ground state with a narrow electrochemical energy gap (1.13 eV) and a small singlet-triplet energy gap (-0.57 kcal mol-1 from SQUID measurements). Its electronic properties are compared with previously reported peri-tetracene and teranthene derivatives.

5.
J Am Chem Soc ; 142(25): 11022-11031, 2020 06 24.
Artigo em Inglês | MEDLINE | ID: mdl-32456437

RESUMO

An olympicenyl radical, a spin 1/2 hydrocarbon radical with C2v symmetry and uneven spin distribution, remains elusive despite the considerable theoretical research interest. Herein, we report syntheses of two air-stable olympicenyl radical derivatives, OR1 and OR2, with half-life times (τ1/2) in air-saturated solution of 7 days and 34 days. The high stability was ascribed to kinetic blocking of reactive sites with high spin densities. X-ray crystallographic analysis revealed unique 20-center-2-electron head-to-tail π-dimer structures with intermolecular distances shorter than the sum of van der Waals radius of carbon. The ground state of the π-dimers was found to be singlet, with singlet-triplet energy gaps estimated to be -2.34 kcal/mol and -3.28 kcal/mol for OR1 and OR2, respectively, by variable-temperature electron spin resonance (ESR) spectroscopy. The monomeric radical species were in equilibrium with the π-dimer in solution, and the optical and electrochemical properties of the monomers and π-dimers in solution were investigated by UV-vis-NIR spectroscopy and cyclic voltammetry, revealing a concentration-dependent nature. Theoretical calculations illustrated that upon formation of a π-dimer the local aromaticity of each monomer was enhanced, and spatial ring current between the monomers was present, which resulted in an increment of aromaticity of the interior of the π-dimer.

6.
Chemistry ; 26(67): 15613-15622, 2020 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-32614108

RESUMO

Helicenes and extended helical π-conjugated compounds have been widely studied, but most of the systems contain only aromatic benzene or heterocyclic rings, showing local aromatic character. Herein, new S-shaped double [6]helicene 1, which has two embedded para-quinodimethane (p-QDM) units, is reported. Due to the existence of a proaromatic quinoidal substructure, it has open-shell diradical character. Its model compound, C-shaped single [6]helicene 2 containing one p-QDM unit, was also synthesized and compared. Their ground-state structures and electronic properties were systematically studied by a combination of various experimental methods assisted by theoretical calculations. Compound 1 has a double-helical structure in the crystal, with the two terminal [6]helicene units bent in opposite directions (i.e., anti form). However, an anti/syn isomerization process with a moderate interconversion energy barrier was observed on the NMR timescale. Compound 1 shows amphoteric redox behavior. It also exhibits open-shell diradical character (y0 =12.1 %) and a small singlet-triplet gap. On the other hand, compound 2 has a typical closed-shell nature. The dication and dianion of 1 also show open-shell diradical character. The dianion of 2 and the tetraanion of 1 exhibit similar electronic structures to their respective isoelectronic structures, that is, [6]helicene and a double [6]helicene. This work provides some insights into the design and synthesis of stable helical π systems with open-shell diradical character and magnetic activity.

7.
J Org Chem ; 85(1): 234-240, 2020 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-31711284

RESUMO

We report the synthesis and characterization of sulfur-doped dibenzoheptazethrene (DBHZ-2S) and dibenzooctazethrene (DBOZ-2S) dications. Their neutral precursors 9a/9b were synthesized by acid-mediated intramolecular cyclization reaction of sulfoxides and the dications were prepared by treating 9a/9b with NOSbF6 or AgSbF6, respectively. Both dications displayed open-shell singlet ground state with a moderate diradical character (y0 = 0.44 for DBHZ-2S and 0.66 for DBOZ-2S) and a small singlet-triplet energy gap (ΔES-T = -3.9 kcal/mol for DBHZ-2S and -3.2 kcal/mol for DBOZ-2S). The open-shell singlet diradical nature of DBHZ-2S and DBOZ-2S were supported by electronic absorption spectroscopy, electron spin resonance spectroscopy, variable-temperature NMR studies, together with spin-unrestricted density functional theory calculations. However, synthesis and isolation of the sulfur-doped heptazethrene (HZ-2S) and octazethrene (OZ-2S) dications upon chemical oxidation of their corresponding neutral precursors 5a/5b were not successful owing to their high reactivity.

8.
Angew Chem Int Ed Engl ; 59(24): 9727-9735, 2020 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-32187780

RESUMO

Synthesis of fully conjugated cyclophanes containing large-size polycyclic aromatics is challenging. Now, three benzidine-linked, hexa-peri-hexabenzocoronene (superbenzene)-based ortho-, para-, and meta-cyclophanes are synthesized through intermolecular Yamamoto coupling reaction of structurally pre-organized precursors. Subsequent oxidative dehydrogenation gave the corresponding quinoidal benzidine-linked cyclophanes. Their geometries were confirmed by X-ray crystallographic analysis and their electronic properties were investigated by electronic absorption, cyclic voltammetry, and DFT calculations. The quinoidal benzidine-linked cyclophanes show thermally populated paramagnetic activity with a relatively large singlet-triplet energy gap. Two enantiomers for the ortho-cyclophanes (1-NH and 1-N) were isolated and their chiral figure-of-eight macrocyclic structures were identified. The cage-like cyclophanes 2-NH and 3-NH with concave surface can selectively encapsulate fullerene C70 .

9.
Mol Pharmacol ; 96(6): 826-834, 2019 12.
Artigo em Inglês | MEDLINE | ID: mdl-31645376

RESUMO

Regulator of G protein signaling 2 (RGS2) plays a role in reducing vascular contraction and promoting relaxation due to its GTPase accelerating protein activity toward Gαq. Previously, we identified four human loss-of-function (LOF) mutations in RGS2 (Q2L, D40Y, R44H, and R188H). This study aimed to investigate whether those RGS2 LOF mutations disrupt the ability of RGS2 to regulate vascular reactivity. Isolated mesenteric arteries (MAs) from RGS2-/- mice showed an elevated contractile response to 5 nM angiotensin II and a loss of acetylcholine (ACh)-mediated vasodilation. Reintroduction of a wild-type (WT) RGS2-GFP plasmid into RGS2-/- MAs suppressed the vasoconstrictor response to angiotensin II. RGS2 LOF mutants failed to suppress the angiotensin II constriction response compared with RGS2 WT. In contrast, ACh-mediated vasoconstriction was restored by expression of RGS2 WT, D40Y, and R44H but not by RGS2 Q2L or R188H. Phosphorylation of RGS2 D40Y and R44H by protein kinase G (PKG) may explain their maintained function to support relaxation in MAs. This is supported by phosphomimetic mutants and suppression of vasorelaxation mediated by RGS2 D40Y by a PKG inhibitor. These results demonstrate that RGS2 attenuates vasoconstriction in MAs and that RGS2 LOF mutations cannot carry out this effect. Among them, the Q2L and R188H mutants supported less relaxation to ACh, whereas relaxation mediated by the D40Y and R44H mutant proteins was equal to that with WT protein. Phosphorylation of RGS2 by PKG appears to contribute to this vasorelaxation. These results provide insights for precision medicine targeting the rare individuals carrying these RGS2 mutations. SIGNIFICANCE STATEMENT: Regulator of G protein signaling 2 (RGS2) has been implicated in the control of blood pressure; rare mutations in the RGS2 gene have been identified in large-scale human gene sequencing studies. Four human mutations in RGS2 that cause loss of function (LOF) in cell-based assays were examined in isolated mouse arteries for effects on both vasoconstriction and vasodilation. All mutants showed the expected LOF effects in suppressing vasoconstriction. Surprisingly, the D40Y and R44H mutant RGS2 showed normal control of vasodilation. We propose that this is due to rescue of the mislocalization phenotype of these two mutants by nitric oxide-mediated/protein kinase G-dependent phosphorylation. These mechanisms may guide drug discovery or drug repurposing efforts for hypertension by enhancing RGS2 function.


Assuntos
Mutação com Perda de Função/fisiologia , Proteínas RGS/genética , Proteínas RGS/metabolismo , Vasoconstrição/fisiologia , Vasoconstritores/farmacologia , Animais , Aorta/efeitos dos fármacos , Aorta/fisiologia , Células CHO , Cricetinae , Cricetulus , Relação Dose-Resposta a Droga , Células HEK293 , Humanos , Mutação com Perda de Função/efeitos dos fármacos , Masculino , Camundongos , Camundongos Endogâmicos C57BL , Camundongos Knockout , Estrutura Secundária de Proteína , Proteínas RGS/química , Vasoconstrição/efeitos dos fármacos
10.
J Am Chem Soc ; 141(1): 62-66, 2019 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-30539629

RESUMO

We report the challenging synthesis of two very long bis(anthraoxa)quinodimethanes with nine (ABA) and ten (ANA) consecutively fused six-membered rings. The former is stable with negligible diradical character, while the latter with a moderate diradical character ( y0 = 25.0%) is reactive and an unexpected trifluoroacetic substituted product (ANA-TFA) was isolated. X-ray crystallographic analysis revealed a planar backbone with a typical quinoidal character for both. Their dications can be regarded as the isoelectronic structures of the respective nonacene and decacene. The dication ABA2+ and dianion ABA2- are open-shell singlet diradicaloids, while the longer dication ANA-TFA2+ and dianion ANA2- have closed-shell ground state, which can be explained by the different intramolecular Coulomb interactions. Both dianions have a bent backbone and can be considered as an isoelectronic structure of the tetraanion of nonacene and decacene, respectively.

11.
Molecules ; 24(8)2019 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-31013683

RESUMO

We report a new boron dipyrromethene (BODIPY)-bridged bisphenoxyl diradicaloid (2), which showed closed-shell diamagnetic character in less polar solvents such as dichloromethane but open-shell diradical character with paramagnetic activity in the very polar solvent N,N-dimethylformamide. X-ray crystallographic analysis of 2 revealed an anti-parallel stacked dimer structure via intermolecular dipole-dipole interaction, and the observed solvent-dependent diradical character can be explained by the different dihedral angles between the phenoxyl units and the BODIPY bridge, and structural flexibility of the molecule in different solvents. Compound 2 also exhibited solvent-dependent optical and electrochemical properties.


Assuntos
Compostos de Boro/química , Modelos Moleculares , Porfobilinogênio/análogos & derivados , Cristalografia por Raios X , Estrutura Molecular , Porfobilinogênio/química
12.
Angew Chem Int Ed Engl ; 58(41): 14467-14471, 2019 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-31322792

RESUMO

A complete experimental and theoretical study has been carried out for aromatic and quinoidal perylene-based bridges substituted with bis(diarylamine) and bis(arylimine) groups respectively. The through-bridge inter-redox site electronic couplings (VAB ) have been calculated for their respective mixed-valence radical cation and radical anion species. The unusual similitudes of the resulting VAB values for the given structures reveal the intervention of molecular shapes with balanced semi-quinoidal/semi-aromatic structures in the charge delocalization. An identical molecular object equally responding to the injection of either positive or negative charges is rare in the field of organic π-conjugated molecules. However, once probed herein for perylene-based systems, it can be extrapolated to other π-conjugated bridges. As a result, this work opens the door to the rational design of true ambipolar bulk and molecular conductors.

13.
J Am Chem Soc ; 140(43): 14054-14058, 2018 Oct 31.
Artigo em Inglês | MEDLINE | ID: mdl-30264999

RESUMO

Laterally extended zethrenes can be regarded as Z-shaped nanographenes with four zigzag edges, but their synthesis is very challenging. Herein, we report the successful synthesis of by far the largest zethrene molecule, a superoctazethrene (SOZ) derivative SOZ-Cl, in crystalline form. Although the parent SOZ is calculated to have a very large diradical character ( y0 = 81.0%), SOZ-Cl shows reasonable stability ( t1/2 = 64 h under ambient conditions) and can be purified by silica gel column chromatography. It exhibits a small electrochemical energy gap ( Eg = 1.01 eV) and characteristics for open-shell singlet diradicaloids. Compared with a previously reported octazethrene derivative (OZ-TIPS), SOZ-Cl shows much larger diradical character ( y0 = 76.3% vs 43.4%) and smaller singlet-triplet gap (Δ ES-T = -2.30 kcal/mol vs -3.87 kcal/mol). Calculations also demonstrate global aromatic character of SOZ, but the smaller size octazethrene shows local aromaticity.

14.
Anal Chem ; 90(11): 6766-6772, 2018 06 05.
Artigo em Inglês | MEDLINE | ID: mdl-29741873

RESUMO

Reproducible detection of uranyl, an important biological and environmental contaminant, from complex matrixes by surface-enhanced Raman scattering (SERS) is successfully achieved using amidoximated-polyacrylonitrile (AO-PAN) mats and carboxylated gold (Au) nanostars. SERS detection of small molecules from a sample mixture is traditionally limited by nonspecific adsorption of nontarget species to the metal nanostructures and subsequent variations in both the vibrational frequencies and intensities. Herein, this challenge is overcome using AO-PAN mats to extract uranyl from matrixes ranging in complexity including HEPES buffer, Ca(NO3)2 and NaHCO3 solutions, and synthetic urine. Subsequently, Au nanostars functionalized with carboxyl-terminated alkanethiols are used to enhance the uranyl signal. The detected SERS signals scale with uranyl uptake as confirmed using liquid scintillation counting. SERS vibrational frequencies of uranyl on both hydrated and lyophilized polymer mats are largely independent of sample matrix, indicating less complexity in the uranyl species bound to the surface of the mats vs in solution. These results suggest that matrix effects, which commonly limit the use of SERS for complex sample analysis, are minimized for uranyl detection. The presented synergistic approach for isolating uranyl from complex sample matrixes and enhancing the signal using SERS is promising for real-world sample detection and eliminates the need of radioactive tracers and extensive sample pretreatment steps.


Assuntos
Resinas Acrílicas/química , Ouro/química , Nanopartículas Metálicas/química , Urânio/análise , Análise Espectral Raman , Propriedades de Superfície
15.
Chemistry ; 24(38): 9499-9503, 2018 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-29671910

RESUMO

A star-shaped hexaquinocyclohexane molecule 4 c is reported, which turns out to be a closed-shell extended [6]radialene with a twisted-boat conformation according to X-ray crystallographic analysis. It was formed by an unusually slow decay of its in situ generated open-shell valence isomer, the hexa-radicaloid 4 o, with a half-life time of about 156 min at room temperature. Reaction progress kinetic analysis revealed a large energy barrier of about 95.5±4.3 kJ mol-1 at room temperature from the hexa-radical form 4 o to the contorted [6]radialene form 4 c, because the transformation needs to overcome large steric repulsion between the neighboring phenoxyl units. Compound 4 c can be chemically reduced to radical anion and dianion, and the dianion is actually a diradical dianion, with a calculated diradical character of 71.9 %. This study demonstrates the unique chemical bonding nature of contorted quinoidal π-conjugated molecules and a very unusual valence isomerization process.

16.
Chemistry ; 24(19): 4944-4951, 2018 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-29396877

RESUMO

The synthesis of stable open-shell singlet diradicaloids is critical for their practical material application. So far, most reported examples are based on carbon-centered radicals, which are intrinsically reactive, and there are very few examples of stable nitrogen-centered diradicaloids. In this full paper, a series of soluble and stable bis(imino)rylenes up to octarylene were synthesized on the basis of newly developed dibromorylene intermediates. It was found that from hexarylene onward, these quinoidal rylenes showed open-shell singlet ground states and could be thermally populated to paramagnetic triplet aminyl diradicals. They are stable due to efficient spin delocalization onto the rylene backbone as well as kinetic blocking of the aminyl sites by the bulky and electron-deficient 2,4,6-trichlorophenyl groups. They exhibited very different electronic structures, diradical character, excited-state dynamics, one-photon absorption, two-photon absorption, and electrochemical properties from their respective aromatic rylene counterparts. These bis(imino)rylenes represent a rare class of stable, neutral, nitrogen-centered aminyl diradicaloids.

17.
Inorg Chem ; 57(9): 5183-5193, 2018 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-29668269

RESUMO

Homoleptic complexes [Fe(L n)]X2 (L1 = 1,1'-(α,α'- o-xylyl)-2,2'-biimidazole, L2 = 1,1'-(α,α'-3,4-dibromo- o-xylyl)-2,2'-biimidazole, L3 = 1,1'-(α,α'-2,5-dimethoxy- o-xylyl)-2,2'-biimidazole; X = BF4- or ClO4-) were synthesized by direct reactions of the Fe(II) precursor salts and bidentate ligands L1, L2, or L3. All mononuclear complexes undergo gradual temperature-driven spin-crossover (SCO) between the high-spin (HS, S = 2) and low-spin (LS, S = 0) states. Complexes with ligands L1 and L2 synthesized in methanol exhibit complete SCO with the midpoint of the LS↔HS conversion varying from 233 to 313 K, while complexes with ligand L3, crystallized from an ethanol/dichloromethane mixture, exhibit incomplete SCO with the residual HS/LS ratio of ∼1:4 for [Fe(L3)3](BF4)2 and ∼1:1 for [Fe(L3)3](ClO4)2. Complexes with L1 can also be recrystallized from ethanol/dichloromethane, in which case they exhibit very gradual and incomplete SCO, similar to those of the complexes with L3. The differences in magnetic behavior have been traced back to peculiarities of molecular packing observed in the corresponding crystal structures. Density-functional theoretical calculations provide justification to the SCO behavior of these complexes, as compared to the HS-only behavior observed for the parent [Fe(bim)3]2+ complex with nonalkylated 2,2'-biimidazole (bim).

18.
Anal Bioanal Chem ; 410(24): 6113-6123, 2018 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-29748758

RESUMO

Unwanted nanoparticle aggregation and/or agglomeration may occur when anisotropic nanoparticles are dispersed in various solvents and matrices. While extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory has been successfully applied to predict nanoparticle stability in solution, this model fails to accurately predict the physical stability of anisotropic nanostructures; thus limiting its applicability in practice. Herein, DLVO theory was used to accurately predict gold nanostar stability in solution by investigating how the choice of the nanostar dimension considered in calculations influences the calculated attractive and repulsive interactions between nanostructures. The use of the average radius of curvature of the nanostar tips instead of the average radius as the nanostar dimension of interest increases the accuracy with which experimentally observed nanoparticle behavior can be modeled theoretically. This prediction was validated by measuring time-dependent localized surface plasmon resonance (LSPR) spectra of gold nanostars suspended in solutions with different ionic strengths. Minimum energy barriers calculated from collision theory as a function of nanoparticle concentration were utilized to make kinetic predictions. All in all, these studies suggest that choosing the appropriate gold nanostar dimension is crucial to fully understanding and accurately predicting the stability of anisotropic nanostructures such as gold nanostars; i.e., whether the nanostructures remain stable and can be used reproducibly, or whether they aggregate and exhibit inconsistent results. Thus, the present work provides a deeper understanding of internanoparticle interactions in solution and is expected to lead to more consistent and efficient analytical and bioanalytical applications of these important materials in the future. Graphical abstract ᅟ.

19.
Sensors (Basel) ; 18(3)2018 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-29534014

RESUMO

In this paper, we report on the design, simulation, and experimental analysis of a miniaturized device that can generate multiple circulated jet flows. The device is actuated by a lead zirconate titanate (PZT) diaphragm. The flows in the device were studied using three-dimensional transient numerical simulation with the programmable open source OpenFOAM and was comparable to the experimental result. Each flow is verified by two hotwires mounted at two positions inside each consisting chamber. The experiment confirmed that the flow was successfully created, and it demonstrated good agreement with the simulation. In addition, a prospective application of the device as an angular rate sensor is also demonstrated. The device is robust, is minimal in size, and can contribute to the development of multi-axis fluidic inertial sensors, fluidic amplifiers, gas mixing, coupling, and analysis.

20.
Sensors (Basel) ; 18(1)2018 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-29361776

RESUMO

Rice is a major staple food for nearly half of the world's population and has a considerable contribution to the global agricultural economy. While spaceborne Synthetic Aperture Radar (SAR) data have proved to have great potential to provide rice cultivation area, few studies have been performed to provide practical information that meets the user requirements. In rice growing regions where the inter-field crop calendar is not uniform such as in the Mekong Delta in Vietnam, knowledge of the start of season on a field basis, along with the planted rice varieties, is very important for correct field management (timing of irrigation, fertilization, chemical treatment, harvest), and for market assessment of the rice production. The objective of this study is to develop methods using SAR data to retrieve in addition to the rice grown area, the sowing date, and the distinction between long and short cycle varieties. This study makes use of X-band SAR data from COSMO-SkyMed acquired from 19 August to 23 November 2013 covering the Chau Thanh and Thoai Son districts in An Giang province, Viet Nam, characterized by a complex cropping pattern. The SAR data have been analyzed as a function of rice parameters, and the temporal and polarization behaviors of the radar backscatter of different rice varieties have been interpreted physically. New backscatter indicators for the detection of rice paddy area, the estimation of the sowing date, and the mapping of the short cycle and long cycle rice varieties have been developed and assessed. Good accuracy has been found with 92% in rice grown area, 96% on rice long or short cycle, and a root mean square error of 4.3 days in sowing date. The results have been discussed regarding the generality of the methods with respect to the rice cultural practices and the SAR data characteristics.

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