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1.
Proc Natl Acad Sci U S A ; 117(15): 8398-8403, 2020 04 14.
Artigo em Inglês | MEDLINE | ID: mdl-32229555

RESUMO

How predictable are life trajectories? We investigated this question with a scientific mass collaboration using the common task method; 160 teams built predictive models for six life outcomes using data from the Fragile Families and Child Wellbeing Study, a high-quality birth cohort study. Despite using a rich dataset and applying machine-learning methods optimized for prediction, the best predictions were not very accurate and were only slightly better than those from a simple benchmark model. Within each outcome, prediction error was strongly associated with the family being predicted and weakly associated with the technique used to generate the prediction. Overall, these results suggest practical limits to the predictability of life outcomes in some settings and illustrate the value of mass collaborations in the social sciences.


Assuntos
Ciências Sociais/normas , Adolescente , Criança , Pré-Escolar , Estudos de Coortes , Família , Feminino , Humanos , Lactente , Vida , Aprendizado de Máquina , Masculino , Valor Preditivo dos Testes , Ciências Sociais/métodos , Ciências Sociais/estatística & dados numéricos
2.
Plasmonics ; 12(3): 743-750, 2017 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-28503102

RESUMO

Solution-deposited nanoscale films of RuO2 ("nanoskins") are effective transparent conductors once calcined to 200 °C. Upon heating the nanoskins to higher temperature the nanoskins show increased transmission at 550 nm. Electronic microscopy and X-ray diffraction show that the changes in the optical spectrum are accompanied by the formation of rutile RuO2 nanoparticles. The mechanism for the spectral evolution is clearly observed with ultrafast optical measurements. Following excitation at 400 nm, nanoskins calcined at higher temperatures show increased transmission above 650 nm, consistent with the photobleaching of a surface-plasmon resonance (SPR) band. Calculations based on the optical constants of RuO2 substantiate the presence of SPR absorption. Sheet resistance and transient terahertz photoconductivity measurements establish that the nanoskins electrically de-wire into separated particles. The plasmonic behavior of the nanoskins has implications their use in a range of optical and electrochemical applications.

3.
Secur Inform ; 3(1): 4, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-26594609

RESUMO

We demonstrate how one can generate predictions for several thousand incidents of Latin American civil unrest, often many days in advance, by surfacing informative public posts available on Twitter and Tumblr. The data mining system presented here runs daily and requires no manual intervention. Identification of informative posts is accomplished by applying multiple textual and geographic filters to a high-volume data feed consisting of tens of millions of posts per day which have been flagged as public by their authors. Predictions are built by annotating the filtered posts, typically a few dozen per day, with demographic, spatial, and temporal information. Key to our textual filters is the fact that social media posts are necessarily short, making it possible to easily infer topic by simply searching for comentions of typically unrelated terms within the same post (e.g. a future date comentioned with an unrest keyword). Additional textual filters then proceed by applying a logistic regression classifier trained to recognize accounts belonging to organizations who are likely to announce civil unrest. Geographic filtering is accomplished despite sparsely available GPS information and without relying on sophisticated natural language processing. A geocoding technique which infers non-GPS-known user locations via the locations of their GPS-known friends provides us with location estimates for 91,984,163 Twitter users at a median error of 6.65km. We show that announcements of upcoming events tend to localize within a small geographic region, allowing us to forecast event locations which are not explicitly mentioned in text. We annotate our forecasts with demographic information by searching the collected posts for demographic specific keywords generated by hand as well as with the aid of DBpedia. Our system has been in production since December 2012 and, at the time of this writing, has produced 4,771 distinct forecasts for events across ten Latin American nations. Manual examination of 2,859 posts surfaced by our method revealed that only 108 were discussing topics unrelated to civil unrest. Examination of 2,596 forecasts generated between 2013-07-01 and 2013-11-30 found 1,192 (45.9%) matched exactly the date and within a 100 km radius of a civil unrest event reported in traditional news media.

4.
Phys Rev Lett ; 103(20): 205001, 2009 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-20365985

RESUMO

Coherent broadband radiation in the form of Rabi sidebands is observed when a ps probe laser propagates through a weakly ionized, electronically excited microplasma generated in the focus of an intense pump beam. The sidebands arise from the interaction of the probe beam with pairs of excited states of a constituent neutral atom via the probe-induced Rabi oscillation. Sideband shifting of >90 meV from the probe carrier frequency results in an effective bandwidth of 200 meV. The sidebands are controlled by the intensity and temporal profile of the probe pulse; with amplitude and shift in agreement with the predictions of a time-dependent generalized Rabi cycling model.

5.
J Phys Chem A ; 109(49): 11304-11, 2005 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-16331915

RESUMO

The low-lying electronic states of O3 and SO2 in their bent and cyclic isomers up to about 10 eV are calculated using the multireference configuration interaction (MRCI) method with a standard Gaussian correlation consistent polarized triple-zeta (cc-pVTZ) basis set. The vertical excitation energies, electron configurations, and oscillator strengths of these states are reported. The molecular orbital structures and excited states of the cyclic isomers are discussed in relation to the bent ones. Coherent anti-Stokes Raman spectroscopy (CARS) schemes for detecting the synthesis of the cyclic isomers are suggested.

6.
J Biomed Mater Res B Appl Biomater ; 75(1): 6-17, 2005 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-16044465

RESUMO

In this research, electron paramagnetic resonance (EPR) spin-trapping was utilized to determine if surface radical chemistries occur for gamma (gamma)-sterilized orthopedic materials-ultra-high molecular weight polyethylene (UHMWPE) and the novel, hybrid, diurethane dimethacrylate (DUDMA)-based RHAKOSS. The materials' ability to competitively chelate catalytic ferrous ions (Fe(2+)) or readily reduce ferric ions (Fe(3+)), and hydrogen peroxide (H(2)O(2)) directly, in facilitating the Fenton reaction (FR), is indicative of cytotoxicity. Validations with a radical scavenger aids to confirm a radical mechanism. In conjunction, materials were thermally annealed and characterized by attenuated total reflectance-Fourier-transform infrared (ATR-FTIR) spectroscopy in order to explore accelerated oxidative degradation induced by residual radicals evolving from gamma-sterilization. Particularly, there was a significant decrease in spin-adduct peak areas obtained from the reduction of H(2)O(2) in the presence of RHAKOSS or UHMWPE, evaluated against their respective controls. Additionally, chelated Fe(2+) accelerated the rate of FR. This phenomenon suggests that the materials are not better chelators than the Fe-activating chelator, edta. Neither material had the propensity to readily reduce Fe(3+) to the relevant Fe(2+), as certified by a nonradical mechanism. Alternatively, the false spin-adduct signal acquired when chelated Fe(3+) is employed arises via the nucleophilic addition of water onto the DMPO spin trap. Residual radicals in UHMWPE did not recombine/terminate following thermal annealing in an inert atmosphere. The radicals in RHAKOSS, however, did recombine under mild heating in an oxidizing or inert atmosphere. Both materials displayed quenching of ( )OH; however, for UHMWPE, this mechanism was jointly accountable for its accelerated degradation, evidenced by ATR-FTIR. Quenching of ( )OH by the silica found in RHAKOSS manifested in a competing effect that counterbalanced the observed FR. Implanted RHAKOSS is not likely to promote cytotoxicity and should not degrade, but the damaging effect of gamma sterilization on UHMWPE is a serious dilemma confronting its long-term durability and biocompatibility.


Assuntos
Inflamação/etiologia , Teste de Materiais , Equipamentos Ortopédicos/efeitos adversos , Polietilenos/química , Polietilenos/toxicidade , Esterilização , Materiais Biocompatíveis/análise , Materiais Biocompatíveis/química , Espectroscopia de Ressonância de Spin Eletrônica , Raios gama , Inflamação/induzido quimicamente , Estrutura Molecular , Polietilenos/efeitos da radiação , Propriedades de Superfície/efeitos da radiação
7.
J Biomed Mater Res B Appl Biomater ; 72(1): 146-55, 2005 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-15384073

RESUMO

Hydroxyl radical (*OH)-induced inflammation is a primary mode for in vivo cytotoxicity. A legitimate concern is whether particulate wear debris from orthopedic composites can stimulate inflammation via ferrous ion (Fe2+)-mediated production of *OH. The purpose of this research was to utilize electron paramagnetic resonance (EPR) spin trapping in investigating and comparing the potential for postsurgical cytotoxicity induced specifically by *OH in the presence of two composites: Simplex P and the novel, hybrid, CORTOSS. Cytotoxicity is evaluated based on the composites competitively chelating catalytic Fe2+ or readily reducing ferric ions (Fe3+), in facilitating the Fenton reaction (FR). *OH that are produced were then validated by a radical scavenger to confirm a genuine radical signal and mechanism. Spin adduct peak areas decreased in the presence of CORTOSS as opposed to increasing in the presence of Simplex P, evaluated against their respective controls. A plausible theory elucidating this finding is that CORTOSS may sequester the Fe form, by virtue of its monomers. Principally, direct comparison of composites indicated that Simplex P had greater tendency to produce *OH, yielding 25.6 and 48.7% greater spin adduct peak areas when chelated and non-chelated Fe2+ are used, respectively. Moreover, the rate of FR accelerated when chelated Fe2+ was used, leading to the formation of a ternary complex with the composites. This was more prominent in Simplex P, as coordination of chelated Fe2+ occurs on its surface via an electrostatic attraction to allow a seventh coordination site for ligand exchange in the ternary complex, stabilized by Ba2+. Conversely, the silica found in CORTOSS possesses radical quenching abilities that deactivate generated *OH in impeding the efficiency of FR. Neither composite demonstrated a capacity to readily reduce Fe3+ to the relevant Fe2+, as validated by a non-radical pathway. Instead, the artificial spin adduct signal attained when employing chelated Fe3+ was due to the nucleophilic addition of water onto DMPO. Simplex P may also serve as a template for surface catalysis of the nucleophilic addition of water onto DMPO involving chelated Fe3+. CORTOSS is thought not to induce cytotoxicity, whereas the propensity of Simplex P in promoting Fenton chemistry is a serious issue that must be addressed.


Assuntos
Resinas Compostas/toxicidade , Radical Hidroxila/metabolismo , Equipamentos Ortopédicos/efeitos adversos , Espectroscopia de Ressonância de Spin Eletrônica , Radical Hidroxila/toxicidade , Estrutura Molecular
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