Visualizing ultrafast photothermal dynamics with decoupled optical force nanoscopy.

The photothermal effect in nanomaterials, resulting from resonant optical absorption, finds wide applications in biomedicine, cancer therapy, and microscopy. Despite its prevalence, the photothermal effect in light-absorbing nanoparticles has typically been assessed using bulk measurements, neglecting near-field effects. Beyond standard imaging and therapeutic uses, nanosecond-transient photothermal effects have been harnessed for bacterial inactivation, neural stimulation, drug delivery, and chemical synthesis. While scanning probe microscopy and electron microscopy offer single-particle imaging of photothermal fields, their slow speed limits observations to milliseconds or seconds, preventing nanoscale dynamic investigations. Here, we introduce decoupled optical force nanoscopy (Dofn), enabling nanometer-scale mapping of photothermal forces by exploiting unique phase responses to temporal modulation. We employ the photothermal effect's back-action to distinguish various time frames within a modulation period. This allows us to capture the dynamic photothermal process of a single gold nanorod in the nanosecond range, providing insights into non-stationary thermal diffusion at the nanoscale.

Site-selective modification of metallic nanoparticles.

Surface patterning of inorganic nanoparticles through site-selective functionalization with mixed-ligand shells or additional inorganic material is an intriguing approach to developing tailored nanomaterials with potentially novel and/or multifunctional properties. The unique physicochemical properties of such nanoparticles are likely to impact their behavior and functionality in biological environments, catalytic systems, and electronics applications, making it vital to understand how we can achieve and characterize such regioselective surface functionalization. This Feature Article will review methods by which chemists have selectively modified the surface of colloidal nanoparticles to obtain both two-sided Janus particles and nanoparticles with patchy or stripey mixed-ligand shells, as well as to achieve directed growth of mesoporous oxide materials and metals onto existing nanoparticle templates in a spatially and compositionally controlled manner. The advantages and drawbacks of various techniques used to characterize the regiospecificity of anisotropic surface coatings are discussed, as well as areas for improvement, and future directions for this field.

Anisotropic silica coating on gold nanorods boosts their potential as SERS sensors.

Gold nanorods are well-known surface-enhanced Raman scattering substrates. Under longitudinal plasmonic excitation, the ends of the nanorods experience larger local electric fields compared to the sides of the rods, suggesting that Raman-active molecules would be best detected if the molecules could preferentially bind to the ends of the nanorods. Coating the tips of gold nanorods with anionic mesoporous silica caps enabled surface-enhanced Raman scattering (SERS) detection of the cationic dye methylene blue at lower concentrations than observed for the corresponding silica coating of the entire rod. By analyzing the intensity ratio of two Raman active modes of methylene blue and the surface plasmon resonance peak shift of the gold nanorod composites, it can be inferred that at a low concentration of methylene blue, molecules adsorb to the tips of the tip coated silica gold nanorods. Functionalization of the anionic silica endcaps with cationic groups eliminates the SERS enhancement for the cationic methylene blue, demonstrating the electrostatic nature of the adsorption process in this case. These results show that anisotropic silica coatings can concentrate analytes at the tips of gold nanorods for improvements in chemical sensing and diagnostics.

External Validation of Postpartum Hemorrhage Prediction Models Using Electronic Health Record Data.

OBJECTIVE: A recent study leveraging machine learning methods found that postpartum hemorrhage (PPH) can be predicted accurately at the time of labor admission in the U.S. Consortium for Safe Labor (CSL) dataset, with a C-statistic as high as 0.93. These CSL models were developed in older data (2002-2008) and used an estimated blood loss (EBL) of ≥1,000 mL to define PPH. We sought to externally validate these models using a more recent cohort of births where blood loss was measured using quantitative blood loss (QBL) methods. STUDY DESIGN: Using data from 5,261 deliveries between February 1, 2019 and May 11, 2020 at a single tertiary hospital, we mapped our electronic health record (EHR) data to the 55 predictors described in previously published CSL models. PPH was defined as QBL ≥1,000 mL within 24 hours after delivery. Model discrimination and calibration of the four CSL models were measured using our cohort. In a secondary analysis, we fit new models in our study cohort using the same predictors and algorithms as the original CSL models. RESULTS: The original study cohort had a substantially lower rate of PPH, 4.8% (7,279/228,438) versus 25% (1,321/5,261), possibly due to differences in measurement. The CSL models had lower discrimination in our study cohort, with a C-statistic as high as 0.57 (logistic regression). Models refit in our study cohort achieved better discrimination, with a C-statistic as high as 0.64 (random forest). Calibration improved in the refit models as compared with the original models. CONCLUSION: The CSL models' accuracy was lower in a contemporary EHR where PPH is assessed using QBL. As institutions continue to adopt QBL methods, further data are needed to understand the differences between EBL and QBL to enable accurate prediction of PPH. KEY POINTS: · Machine learning methods may help predict PPH.. · EBL models do not generalize when QBL is used.. · Blood loss estimation alters model accuracy..

Regulating and Directionally Controlling Electron Emission from Gold Nanorods with Silica Coatings.

Dielectric coatings offer a versatile means of manipulating hot carrier emission from nanoplasmonic systems for emerging nanocatalysis and photocathode applications, with uniform coatings acting as regulators and nonuniform coatings providing directional photocurrent control. However, the mechanisms for electron emission through dense and mesoporous silica (SiO2) coatings require further examination. Here, we present a systematic investigation of photoemission from single gold nanorods as a function of dense versus mesoporous silica coating thicknesses. Studies with dense coatings on gold nanostructures clarify the short (∼1 nm) attenuation length responsible for severely reduced transmission through the silica conduction band. By contrast, mesoporous silica is much more transmissive, and a simple geometric model quantitatively recapitulates the electron escape probability through nanoscopic porous channels. Finally, photoelectron velocity map imaging (VMI) studies of nanorods with coating defects verify that photoemission occurs preferentially through the thinner regions, illustrating new opportunities for designing photocurrent distributions on the nanoscale.

Controlling the Spatial and Momentum Distributions of Plasmonic Carriers: Volume vs Surface Effects.

Spatial and momentum distributions of excited charge carriers in nanoplasmonic systems depend sensitively on optical excitation parameters and nanoscale geometry, which therefore control the efficiency and functionality of plasmon-enhanced catalysts, photovoltaics, and nanocathodes. Growing appreciation over the past decade for the different roles of volume- vs surface-mediated excitation in such systems has underscored the need for explicit separation and quantification of these pathways. Toward these ends, we utilize angle-resolved photoelectron velocity map imaging to distinguish these processes in gold nanorods of different aspect ratios down to the spherical limit. Despite coupling to the longitudinal surface plasmon, we find that resonantly excited nanorods always exhibit transverse (sideways) multiphoton photoemission distributions due to photoexcitation within volume field enhancement regions rather than at the tip hot spots. This behavior is accurately reproduced via ballistic Monte Carlo modeling, establishing that volume-excited electrons primarily escape through the nanorod sides. Furthermore, we demonstrate optical control over the photoelectron angular distributions via a screening-induced transition from volume (transverse/side) to surface (longitudinal/tip) photoemission with red detuning of the excitation laser. Frequency-dependent cross sections are separately quantified for these mechanisms by comparison with theoretical calculations, combining volume and surface velocity-resolved photoemission modeling. Based on these results, we identify nanomaterial-specific contributions to the photoemission cross sections and offer general nanoplasmonic design principles for controlling photoexcitation/emission distributions via geometry- and frequency-dependent tuning of the volume vs surface fields.

Use of a Novel Electronic Maternal Surveillance System and the Maternal Early Warning Criteria to Detect Severe Postpartum Hemorrhage.

BACKGROUND: A leading cause of preventable maternal death is related to delayed response to clinical warning signs. Electronic surveillance systems may improve detection of maternal morbidity with automated notifications. This retrospective observational study evaluates the ability of an automated surveillance system and the Maternal Early Warning Criteria (MEWC) to detect severely morbid postpartum hemorrhage (sPPH) after delivery. METHODS: The electronic health records of adult obstetric patients of any gestational age delivering between April 1, 2017 and December 1, 2018 were queried to identify scheduled or unscheduled vaginal or cesarean deliveries. Deliveries complicated by sPPH were identified and defined by operative management of postpartum hemorrhage, transfusion of ≥4 units of packed red blood cells (pRBCs), ≥2 units of pRBCs and ≥2 units of fresh-frozen plasma, transfusion with >1 dose of furosemide, or transfer to the intensive care unit. The test characteristics of automated pages and the MEWC for identification of sPPH 24 hours after delivery were determined and compared using sensitivity, specificity, positive predictive value (PPV), and negative predictive value (NPV) and their 95% confidence intervals (CIs). McNemar test was used to compare these estimates for both early warning systems. RESULTS: The average age at admission was 30.7 years (standard deviation [SD] = 5.1 years), mean gestational age 38 weeks 4 days, and cesarean delivery accounted for 30.0% of deliveries. Of 7853 deliveries, 120 (1.5%) were complicated by sPPH. The sensitivity of automated pages for sPPH within 24 hours of delivery was 60.8% (95% CI, 52.1-69.6), specificity 82.5% (95% CI, 81.7-83.4), PPV 5.1% (95% CI, 4.0-6.3), and NPV 99.3% (95% CI, 99.1-99.5). The test characteristics of the MEWC for sPPH were sensitivity 75.0% (95% CI, 67.3-82.7), specificity 66.3% (95% CI, 65.2-67.3), PPV 3.3% (95% CI, 2.7-4.0), and NPV 99.4% (95% CI, 99.2-99.6). There were 10 sPPH cases identified by automated pages, but not by the MEWC. Six of these cases were identified by a page for anemia, and 4 cases were the result of vital signs detected by the bedside monitor, but not recorded in the patient's medical record by the bedside nurse. Therefore, the combined sensitivity of the 2 systems was 83.3% (95% CI, 75.4-89.5). CONCLUSIONS: The automated system identified 10 of 120 deliveries complicated by sPPH not identified by the MEWC. Using an automated alerting system in combination with a labor and delivery unit's existing nursing-driven early warning system may improve detection of sPPH.

Virus-Sized Gold Nanorods: Plasmonic Particles for Biology.

Plasmons, collective oscillations of conduction-band electrons in nanoscale metals, are well-known phenomena in colloidal gold and silver nanocrystals that produce brilliant visible colors in these materials that depend on the nanocrystal size and shape. Under illumination at or near the plasmon bands, gold and silver nanocrystals exhibit properties that enable fascinating biological applications: (i) the nanocrystals elastically scatter light, providing a straightforward way to image them in complex aqueous environments; (ii) the nanocrystals produce local electric fields that enable various surface-enhanced spectroscopies for sensing, molecular diagnostics, and boosting of bound fluorophore performance; (iii) the nanocrystals produce heat, which can lead to chemical transformations at or near the nanocrystal surface and can photothermally destroy nearby cells. While all the above-mentioned applications have already been well-demonstrated in the literature, this Account focuses on several other aspects of these nanomaterials, in particular gold nanorods that are approximately the size of viruses (diameters of ∼10 nm, lengths up to 100 nm). Absolute extinction, scattering, and absorption properties are compared for gold nanorods of various absolute dimensions, and references for how to synthesize gold nanorods with four different absolute dimensions are provided. Surface chemistry strategies for coating nanocrystals with smooth or rough shells are detailed; specific examples include mesoporous silica and metal-organic framework shells for porous (rough) coatings and polyelectrolyte layer-by-layer wrapping for "smooth" shells. For self-assembled-monolayer molecular coating ligands, the smoothest shells of all, a wide range of ligand densities have been reported from many experiments, yielding values from less than 1 to nearly 10 molecules/nm2 depending on the nanocrystal size and the nature of the ligand. Systematic studies of ligand density for one particular ligand with a bulky headgroup are highlighted, showing that the highest ligand density occurs for the smallest nanocrystals, even though these ligand headgroups are the most mobile as judged by NMR relaxation studies. Biomolecular coronas form around spherical and rod-shaped nanocrystals upon immersion into biological fluids; these proteins and lipids can be quantified, and their degree of adsorption depends on the nanocrystal surface chemistry as well as the biophysical characteristics of the adsorbing biomolecule. Photothermal adsorption and desorption of proteins on nanocrystals depend on the enthalpy of protein-nanocrystal surface interactions, leading to light-triggered alteration in protein concentrations near the nanocrystals. At the cellular scale, gold nanocrystals exert genetic changes at the mRNA level, with a variety of likely mechanisms that include alteration of local biomolecular concentration gradients, changes in mechanical properties of the extracellular matrix, and physical interruption of key cellular processes-even without plasmonic effects. Microbiomes, both organismal and environmental, are the likely first point of contact of nanomaterials with natural living systems; we see a major scientific frontier in understanding, predicting, and controlling microbe-nanocrystal interactions, which may be augmented by plasmonic effects.

Consumer-Facing Data, Information, And Tools: Self-Management Of Health In The Digital Age.

Consumers have greater access to data, information, and tools to support the management of their health than ever before. While the sheer quantity of these resources has increased exponentially over the past decade, the accuracy of consumer-facing resources is variable, and the value to the individual consumer remains uncertain. In general, the quality of these resources has improved, mostly because of improvements in web and mobile technologies and efforts to restructure health care delivery to be more patient centered. We describe the major initiatives that have led to consumers' increased access to both their own health data and performance data for health care providers and hospitals. We explore how search engines and crowdsourced review websites help and hinder the dissemination of medically accurate information. We highlight emerging examples of websites and apps that enable consumers to make medical decisions more in concert with their preferences. We conclude by describing key limitations of consumer-facing resources and making recommendations for how they may best be curated and regulated.

Measuring efficiency among US federal hospitals.

This study evaluates the efficiency of federal hospitals, specifically those hospitals administered by the US Department of Veterans Affairs and the US Department of Defense. Hospital executives, health care policymakers, taxpayers, and federal hospital beneficiaries benefit from studies that improve hospital efficiency. This study uses data envelopment analysis to evaluate a panel of 165 federal hospitals in 2007 and 157 of the same hospitals again in 2011. Results indicate that overall efficiency in federal hospitals improved from 81% in 2007 to 86% in 2011. The number of federal hospitals operating on the efficiency frontier decreased slightly from 25 in 2007 to 21 in 2011. The higher efficiency score clearly documents that federal hospitals are becoming more efficient in the management of resources. From a policy perspective, this study highlights the economic importance of encouraging increased efficiency throughout the health care industry. This research examines benchmarking strategies to improve the efficiency of hospital services to federal beneficiaries. Through the use of strategies such as integrated information systems, consolidation of services, transaction-cost economics, and focusing on preventative health care, these organizations have been able to provide quality service while maintaining fiscal responsibility. In addition, the research documented the characteristics of those federal hospitals that were found to be on the Efficiency Frontier. These hospitals serve as benchmarks for less efficient federal hospitals as they develop strategies for improvement.