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Plasmon-enhanced coherent Raman scattering microscopy has reached single-molecule detection sensitivity. Due to the different driven fields, there are significant differences between a coherent Raman scattering process and its plasmon-enhanced derivative. The commonly accepted line shapes for coherent anti-Stokes Raman scattering and stimulated Raman scattering do not hold for the plasmon-enhanced condition. Here, we present a theoretical model that describes the spectral line shapes in plasmon-enhanced coherent anti-Stokes Raman scattering (PECARS). Experimentally, we measured PECARS and plasmon-enhanced stimulated Raman scattering (PESRS) spectra of 4-mercaptopyridine adsorbed on the self-assembled Au nanoparticle (NP) substrate and aggregated Au NP colloids. The PECARS spectra show a nondispersive line shape, while the PESRS spectra exhibit a dispersive line shape. PECARS shows a higher signal to noise ratio and a larger enhancement factor than PESRS from the same specimen. It is verified that the nonresonant background in PECARS originates from the photoluminescence of nanostructures. The decoupling of background and the vibrational resonance component results in the nondispersive line shape in PECARS. More local electric field enhancements are involved in the PECARS process than in PESRS, which results in a higher enhancement factor in PECARS. The current work provides new insight into the mechanism of plasmon-enhanced coherent Raman scattering and helps to optimize the experimental design for ultrasensitive chemical imaging.
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Vibrationally excited reaction of Cl + D2 (v = 1, j = 0) â DCl + D was investigated by a high-resolution crossed beam experiment, with D2 molecules in the vibrationally excited state prepared by the scheme of stimulated Raman pumping. Differential cross sections (DCSs) were obtained at three collision energies of 4.03, 4.93, and 5.68 kcal/mol. Backward scattering is dominant for both DCl (v' = 0) and DCl (v' = 1) products, and no forward scattering signal was observed at these three collision energies. Collision-energy-dependent DCS in the backward scattering direction was measured at collision energies between 3.62 and 5.97 kcal/mol. Comparing with the DCSs from the vibrational ground state, it is found that the vibrational excitation of D2 molecules significantly enhances the reactivity because of the later barrier nature of the reaction. No obvious oscillatory structure was found in the collision-energy-dependent DCS in the backward scattering direction, suggesting that the title reaction proceeds via a direct abstraction mechanism.
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The reaction of fluorine atom with vibrationally excited H2 at v = 1 has been studied using a high resolution crossed molecular beam apparatus at collision energies of 0.52 and 0.90 kcal/mol. Product HF rotational state-resolved differential cross sections (DCSs) were measured at v' = 2, 3, 4 levels. The product angular distributions are predominantly backward scattered except for a small forward signal of HF(v' = 4) at 0.90 kcal/mol. At the collision energy of 0.52 kcal/mol, the forward scattering peak of the HF(v' = 2) product, which arises in F + H2(v = 0) reaction from the Feshbach resonances, disappears in F + H2(v = 1) reaction. Oscillatory structures do not appear in the backward direction of the scattering as the collision energy increases from 0.4 to 2.0 kcal/mol, indicating there are no explicit reaction resonances in the F + H2(v = 1, j = 0) â HF + H reaction in the studied energy range. Quantum dynamics calculations on a highly accurate potential energy surface are in good agreement with the experimental results and reveal that the reaction occurs via likely a direct abstraction mechanism, not via long-lived reactive resonances.
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Objective: This study aimed to investigate the association between weight-adjusted waist index (WWI), a novel adiposity index, and kidney stone (KS). Methods: Data were obtained from the National Health and Nutrition Examination Survey 2007-2018. According to the history of KS, participants were divided into the non-stone group and the stone group. Weighted multivariable logistic regression analyses were used to evaluate the correlation between WWI and KS in unadjusted, partially adjusted, and all-adjusted models. A restricted cubic spline (RCS) analysis assessed the association between continuous WWI and KS risk and obtained the risk function inflection point. Then, subgroup analysis based on the risk function inflection point was conducted to dissect the association in specific subgroups. In addition, the above analyst methods were repeatedly performed in populations after propensity score matching (PSM). The receiver operating characteristic (ROC) curve was applied to compare the ability to predict KS occurrence among WWI, visceral adiposity index (VAI), and body mass index (BMI). Results: Weighted multivariable logistic regression analyses found a positive association between continuous WWI and KS risk in the all-adjusted model [odds ratio (OR) = 1.03; 95% confidence interval (CI), 1.02-1.04; P < 0.001]. In further analysis, the Q4 WWI group was linked to the highest KS risk when compared to the Q1-Q3 group (OR = 1.06; 95% CI, 1.05-1.08, P < 0.001). RCS analysis found a linear significant correlation between continuous WWI and KS risk, and the risk function inflection point is 11.08 cm/âkg. Subgroup analysis confirmed that WWI was associated with KS risk in different groups. After PSM, increased WWI was still related to a high risk of KS. Moreover, the ROC curve demonstrated that WWI has a higher predictive ability of KS occurrence than VAI and BMI (area under curve, 0.612 vs. 0.581 vs. 0.569). Conclusion: In the US adult population, elevated WWI value was associated with an increased risk of KS. Furthermore, WWI was a better predictor of KS occurrence than VAI and BMI.
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Índice de Masa Corporal , Cálculos Renales , Encuestas Nutricionales , Puntaje de Propensión , Humanos , Masculino , Femenino , Cálculos Renales/epidemiología , Cálculos Renales/etiología , Persona de Mediana Edad , Adulto , Circunferencia de la Cintura , Factores de Riesgo , Peso Corporal , Adiposidad , AncianoRESUMEN
High-efficiency excitation of a molecular beam is critical for investigating state-selected chemistry. However, achieving vibrational excitation of the entire beam for Raman-active molecules such as H2 proves extremely challenging, primarily because laser pulses are much shorter than the molecular beam. In this study, we achieve a total excitation efficiency of over 20% by employing stimulated Raman pumping (SRP) in a slow, narrow-pulsed molecular beam. Through optimizing the intensity and spot shape of the SRP lasers, we attain saturated excitation within the laser crossing region. Furthermore, by reducing the beam velocity and narrowing the beam pulse using a cold valve and a fast chopper, we significantly enhance the total excitation yield. COMSOL simulation and a newly developed model reveal that a critical velocity allows the chopper to block unexcited molecules and reserve most of the excited ones from the beam, resulting in the highest overall excitation yield. This innovative setup opens new possibilities for state-selected experiments in surface science and ion-molecule reaction dynamics, particularly involving weak transitions and pulsed lasers.
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Prealigning nonpolar reacting molecules leads to large stereodynamical effects because of their weak steering interaction en route to the reaction barrier. However, experimental limitations in preparing aligned molecules efficiently have hindered the investigation of steric effects in bimolecular reactions involving hydrogen. Here, we report a high-resolution crossed-beam study of the reaction H + HD(v = 1, j = 2) â H2(v', j') + D at collision energies of 0.50, 1.20, and 2.07 electron volts in which the vibrationally excited hydrogen deuteride (HD) molecules were prepared in two collision configurations, with their bond preferentially aligned parallel and perpendicular to the relative velocity of collision partners. Notable stereodynamical effects in differential cross sections were observed. Quantum dynamics calculations revealed that strong constructive interference in the perpendicular configuration plays an important role in the stereodynamical effects observed.
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PURPOSE: The suctioning access sheath (SAS) is a novel access sheath connected to a negative pressure suction device and absorbs fragments. Some comparative studies have reported SAS with a higher stone-free rate and lower operative time. However, no higher-level evidence was published to support SAS. Hence, this systematic review and meta-analysis aimed to assess the clinical safety and efficacy of SAS versus traditional access sheath (TAS) for the treatment of renal stones in mini-percutaneous nephrolithotomy (MPCNL). MATERIALS AND METHODS: A systematic review of the literature was conducted using Pubmed, Embase(Ovid), Medlineï¼EBSCOï¼, Cochrane central register of controlled trials, and Sinomed to search comparative studies as recent as December 2020 that assessed the safety and effectiveness of SAS in PCNL. The quality of retrospective case-control studies (RCCs) and randomized controlled trials (RCTs) were evaluated by the Newcastle-Ottawa Scale (NOS) and the Cochrane risk of bias tool, respectively. The Oxford center set up evidence-based medicine was used to assess the level of evidence (LE). Statistical analyses were performed by the comprehensive meta-analysis program. RESULTS: Seven studies, with a total of 1655 patients, were included. Compared with the TAS group, the SAS group had a shorter operative time (MD= -17.30; 95%CI:-23.09,-11.51; Pï¼.00001), higher stone-free rate (OR=2.37;95%CI:1.56,3.61;P<.0001), fewer total complication rate (OR=0.50;95%CI:0.35,0.70;P<.0001), lower auxiliary procedures rate (OR=0.48;95%CI:0.36,0.64; P<.00001), and lower postoperative fever rate (OR=0.46;95%CI:0.34,0.62;Pï¼.00001). CONCLUSION: The SAS can significantly improve MPCNL in the stone-free rate, operative time, and total complication rate, especially for auxiliary procedures and postoperative fever rates.
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Cálculos Renales , Nefrolitotomía Percutánea , Humanos , Cálculos Renales/cirugía , Nefrolitotomía Percutánea/efectos adversos , Nefrolitotomía Percutánea/métodos , Tempo Operativo , Succión/efectos adversos , Resultado del TratamientoRESUMEN
BACKGROUND: The management of aspirin before transrectal prostate puncture-guided biopsy continues to be controversial. The conclusions in newly published studies differ from the published guideline. Therefore, an updated meta-analysis was performed to assess the safety of continuing to take aspirin when undergoing a transrectal ultrasound-guided prostate biopsy (TRUS-PB). METHODS: We searched the following databases for relevant literature from their inception to October 30, 2020: PubMed, EMBASE, Cochrane Central Register of Controlled Trials, Medline, Web of Science, Sinomed, Chinese National Knowledge Internet, and WANGFANG. Studies that compared the bleeding rates between aspirin that took aspirin and non-aspirin groups were included. The quality of all included studies was evaluated using the Newcastle-Ottawa Scale. Revman Manger version 5.2 software was employed to complete the meta-analysis to assess the risk of hematuria, hematospermia, and rectal bleeding. RESULTS: Six articles involving 3373 patients were included in this meta-analysis. Our study revealed that compared with the non-aspirin group, those taking aspirin exhibited a higher risk of rectal bleeding after TRUS-PB (risk ratio [RR]â=â1.27, 95% confidence interval [CI] [1.09-1.49], Pâ=â.002). Also, the meta-analysis results did not reveal any significant difference between the 2 groups for the risk of hematuria (RRâ=â1.02, 95%CI [0.91-1.16], Pâ=â.71) and hematospermia (RRâ=â0.93, 95%CI [0.82-1.06], Pâ=â.29). CONCLUSION: Taking aspirin does not increase the risk of hematuria and hematospermia after TRUS-PB. However, the risk of rectal bleeding, which was slight and self-limiting, did increase. We concluded that it was not necessary to stop taking aspirin before undergoing TRUS-PB.
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Aspirina/efectos adversos , Biopsia con Aguja/efectos adversos , Inhibidores de Agregación Plaquetaria/efectos adversos , Aspirina/administración & dosificación , Ensayos Clínicos como Asunto , Hemorragia Gastrointestinal/inducido químicamente , Hemorragia Gastrointestinal/etiología , Hematuria/inducido químicamente , Hematuria/etiología , Hematospermia/inducido químicamente , Hematospermia/etiología , Humanos , Masculino , Inhibidores de Agregación Plaquetaria/administración & dosificación , Próstata/patología , Neoplasias de la Próstata/patología , Ultrasonografía IntervencionalRESUMEN
We have built a high-energy, narrow-bandwidth, nanosecond light source for efficient preparation of vibrationally excited molecules in a molecular beam. It consists of an injection-seeded optical parametric oscillator and two optical parametric amplifiers. Pumped by the second harmonic of a commercial injection-seeded Nd:YAG laser, it can generate pulse energies up to 377 mJ at 655 nm with a bandwidth smaller than 200 MHz. Its stability is excellent, with a standard deviation of pulse energy of 5.2 mJ and a wavelength stability of 0.001 cm-1. We demonstrated this light source in a crossed-molecular-beam experiment of the H + D2 (v = 2, j = 0) â HD + D reaction, in which it was used for overtone excitation of D2 molecules from (v = 0, j = 0) to (v = 2, j = 0) with an overall excitation efficiency of 2.5%.
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Understanding quantum interferences is essential to the study of chemical reaction dynamics. Here, we provide an interesting case of quantum interference between two topologically distinct pathways in the H + HD â H2 + D reaction in the collision energy range between 1.94 and 2.21 eV, manifested as oscillations in the energy dependence of the differential cross section for the H2 (v' = 2, j' = 3) product (where v' is the vibrational quantum number and j' is the rotational quantum number) in the backward scattering direction. The notable oscillation patterns observed are attributed to the strong quantum interference between the direct abstraction pathway and an unusual roaming insertion pathway. More interestingly, the observed interference pattern also provides a sensitive probe of the geometric phase effect at an energy far below the conical intersection in this reaction, which resembles the Aharonov-Bohm effect in physics, clearly demonstrating the quantum nature of chemical reactivity.