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1.
Appl Opt ; 61(12): 3312-3318, 2022 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-35471426

RESUMO

We report the successful picosecond laser welding of AlSi and YAG. This material combination is of significant interest to the field of laser design and construction. Parameter maps are presented that demonstrate the impact of pulse energy and focal position on the resultant weld. Weld performance relevant to industrial applications is measured, i.e., shear strength, process yield, and absolute thermal resistance are presented.

2.
Appl Opt ; 56(16): 4873-4881, 2017 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-29047628

RESUMO

We report systematic analysis and comparison of ps-laser microwelding of industry relevant Al6082 parts to SiO2 and BK7. Parameter mapping of pulse energy and focal depth on the weld strength is presented. The welding process was found to be strongly dependent on the focal plane but has a large tolerance to variation in pulse energy. Accelerated lifetime tests by thermal cycling from -50° to +90°C are presented. Welds in Al6082-BK7 parts survive over the full temperature range where the ratio of thermal expansion coefficients is 3.4:1. Welds in Al6082-SiO2 parts (ratio 47.1:1) survive only a limited temperature range.

3.
Biosecur Bioterror ; 12(1): 49-62, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24552362

RESUMO

Abrin is a heterodimeric toxin present in the seeds of the Abrus precatorius plant. The easily obtainable seeds can yield a highly toxic product that can be used in various types of biocrimes and terrorism-related activities, including "white-powder" letters. Although the vast majority of these threats are hoaxes, the lack of rapid and reliable detection assays for abrin, such as lateral flow assays (LFAs), can be an impediment to accurate and rapid hazard assessment. One of the complicating factors associated with LFAs is the use of antibodies of poor affinity and specificity that cross-react with near neighbors or that bind to plant lectins, which are capable of nonspecifically cross-linking the capture and detector antibodies. Because of the critical need to promote public safety and public health, we conducted a comprehensive laboratory evaluation of a commercial LFA for the rapid detection of abrin. This study was conducted using comprehensive inclusivity and exclusivity panels of abrin and near-neighbor plant materials, along with panels of lectins, related proteins, white powders, and environmental background material, to determine the sensitivity, specificity, limit of detection, dynamic range, and repeatability of the assay for the specific intended use of evaluating suspicious white powders and environmental samples for the presumptive presence of abrin.


Assuntos
Abrina/isolamento & purificação , Pós/química , Kit de Reagentes para Diagnóstico/normas , Terrorismo Químico , Pós/intoxicação , Fitas Reagentes , Sensibilidade e Especificidade , Estados Unidos
4.
Biosecur Bioterror ; 11(4): 237-50, 2013 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-24320219

RESUMO

Ricin, a heterodimeric toxin that is present in the seeds of the Ricinus communis plant, is the biothreat agent most frequently encountered by law enforcement agencies in the United States. Even in untrained hands, the easily obtainable seeds can yield a highly toxic product that has been used in various types of threats, including "white-powder" letters. Although the vast majority of these threats are hoaxes, an impediment to accurate hazard assessments by first responders is the unreliability of rapid detection assays for ricin, such as lateral flow assays (LFAs). One of the complicating factors associated with LFAs is the incorporation of antibodies of poor specificity that cross-react with near-neighbors or with plant lectins that are capable of nonspecifically cross-linking the capture and detector antibodies. Because of the compelling and critical need to promote the interests of public safety and public health, the Department of Homeland Security conducted a comprehensive laboratory evaluation study of a commercial LFA for the rapid detection of ricin. This study was conducted using comprehensive inclusivity and exclusivity panels of ricin and near-neighbor plant materials, along with panels of lectins and "white-powders," to determine the specificity, sensitivity, limits of detection, dynamic range, and repeatability of the assay for the specific intended use of evaluating suspicious white powders and environmental samples in the field.


Assuntos
Substâncias para a Guerra Química/análise , Cromatografia de Afinidade/métodos , Ricina/análise , Filtros de Ar , Meio Ambiente , Humanos , Laboratórios , Limite de Detecção , Extratos Vegetais/análise , Lectinas de Plantas/análise , Pós/química , Reprodutibilidade dos Testes
5.
J Org Chem ; 78(17): 8297-304, 2013 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-23952066

RESUMO

(1)H NMR, ESI-MS, and DFT calculations with the M062X/6-31G* method show that, in water, the bistetrafluoroborate salt of N,N'-dimethyl-2,6-diaza-9,10-anthraquinonediium dication (DAAQ·2BF4(-)) exists in equilibrium with both its gem-diol and several aggregates (from dimers to at least octamers). With high concentrations of HCl (e.g., 1.2-1.5 M), all aggregates break up and the keto-to-gem-diol equilibrium is shifted quantitatively toward the quinone form. The same effect is observed with 1.5 mol equiv of cucurbit[7]uril, CB[7], with which all equilibria are shifted toward the quinone form, which undergoes slow exchange with the CB[7] cavity as both the free and the CB[7]-intercalated quinone (DAAQ@CB[7]) are observed simultaneously by (1)H NMR. The affinity of DAAQ for the CB[7] cavity (Keq = 4 × 10(6) M(-1)) is in the range found for tricyclic dyes (0.4-5.4 × 10(6) M(-1)), and among the highest observed to date. A computational comparative study of the corresponding CB[7] complex of the N,N'-dimethyl-4,4'-bipyridinium dication (N,N'-dimethyl viologen, MeV) suggests that the higher binding constant for intercalation of DAAQ may be partially attributed to a lesser distortion of CB[7] (required to maximize favorable nonbonding interactions) as a result of the flat geometry of DAAQ.


Assuntos
Álcoois/química , Hidrocarbonetos Aromáticos com Pontes/química , Imidazóis/química , Isoquinolinas/química , Cetonas/química , Quinonas/química , Cátions/química , Cristalografia por Raios X , Modelos Moleculares , Estrutura Molecular , Teoria Quântica
6.
Mol Vis ; 14: 615-24, 2008 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-18385797

RESUMO

PURPOSE: Anterior chamber-associated immune deviation (ACAID) is a form of peripheral tolerance achieved via intracameral antigen inoculation. It is well known that ACAID effectively down-regulates potentially destructive immunities such as delayed-type hypersensitivity (DTH) at extraorbital sites. However, what has not been specifically addressed is whether local intraocular tissues are negatively affected from intracamerally placed antigen. Thus, the current study was undertaken to detect and characterize potential pathological effects on intraocular tissues following intracameral inoculation with alloantigen. METHODS: ACAID induced in C57BL/6 hosts via intracameral inoculation with allogeneic (BALB/c) splenocytes was confirmed by the absence of DTH reactivity in the periphery. Injuries to the anterior segment and neuroretina following intracameral inoculation were evaluated pathologically via histological evaluation, molecularly via upregulation of glial fibrillary acidic protein (GFAP), and functionally via assessment of photoreceptor degeneration and electroretinogram (ERG) out to 24 days. In all experiments, intracamerally inoculated mice were compared to sham-operated, and controlled lens-punctured mice--a procedure that elicits intracameral inflammation for positive identification of immunopathological changes. RESULTS: Inflammation of anterior segment tissues persisted out to eight days, despite evidence that significant clearance of allogeneic cells took place within 6 h. In the neuroretina, a transient loss in ERG B-wave amplitudes was detected, but photoreceptor degeneration and GFAP upregulation were not. CONCLUSIONS: Intracameral inoculation with alloantigen leads to anterior segment inflammation and ERG dysfunction; however, this was markedly reduced and transient when compared to strong anterior segment inflammation induced by a more serious lens-puncture wound.


Assuntos
Câmara Anterior/imunologia , Olho/imunologia , Olho/patologia , Tolerância Imunológica , Isoantígenos/imunologia , Animais , Segmento Anterior do Olho/patologia , Eletrorretinografia , Gliose/imunologia , Gliose/patologia , Inflamação/imunologia , Inflamação/patologia , Injeções , Isoantígenos/administração & dosagem , Cristalino/lesões , Camundongos , Camundongos Endogâmicos BALB C , Camundongos Endogâmicos C57BL , Células Fotorreceptoras/patologia , Retina/imunologia , Retina/fisiopatologia , Baço/imunologia , Fatores de Tempo , Ferimentos Penetrantes/patologia
7.
J Org Chem ; 67(21): 7501-10, 2002 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-12375985

RESUMO

In anhydrous CH3CN a series of nine 4-(4-substituted-benzoyl)-N-methylpyridinium cations (substituent: -OCH3, -CH3, -H, -SCH3, -Br, -Ctbd1;CH, -CHO, -NO2, and -(+)S(CH3)2) demonstrate two chemically reversible, well-separated one-electron (1-e) reductions in the same potential range as other main stream redox catalysts such as quinones and viologens. Hammett linear free energy plots yield excellent correlation between the E(1/2) values of both waves and the substituent constants sigma(p)(-)(X). The reaction constants for the two 1-e reductions are rho(1) = 2.60 and rho(2) = 3.31. The lower rho(1) value is associated with neutralization of the pyridinium ring, and the higher rho(2) value with the negative charge developing during the 2nd-e reduction. Structure-function correlations point to a purely inductive role for substitution in both 1-e reductions. The case of the 4-(4-nitrobenzoyl)-N-methylpyridinium cation is particularly noteworthy, because the 4-nitrobenzoyl moiety undergoes reduction before the 2nd reduction of the 4-benzoyl-N-methylpyridinium system. Correlation of the third wave of this compound with the 2nd-e reduction of the others yields sigma(p)(-NO)2*- = -0.97 +/- 0.02, thus placing the -NO2-* group among the strongest electron donors. Solvent deuterium isotope effects and maps of the electrostatic potential (via PM3 calculations) as a function of substitution support that 2-e reduced forms develop H-bonding with proton donors (e.g., CH3OH) via the O-atom. The average number of CH3OH molecules entering the H-bonding association increases with e-donating substituents. H-bonding shifts the 2nd reduction wave closer to the first one. This has important practical implications, because it increases the equilibrium concentration of the 2-e reduced form from disproportionation of the 1-e reduced form.


Assuntos
Compostos de Piridínio/química , Compostos de Piridínio/síntese química , Cátions , Eletroquímica/métodos , Elétrons , Ligação de Hidrogênio , Oxirredução , Termodinâmica
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