Subjective Health and Physical-Activity Engagement across Adulthood: Distinguishing between Within-Person and Between-Person Associations.

INTRODUCTION: It is assumed that age-related increases in loss (e.g., health decline) motivate behavioral changes (e.g., prevention of health decline) across adulthood. This assumption has rarely been directly tested in empirical research, and the current study seeks to fill this gap. METHODS: By performing random intercept cross-lagged panel model and multilevel modeling analyses on a three-wave longitudinal dataset from the Midlife in the United States survey (N = 7,108; 51.6% female; between 20 and 75 years at T1), we examined the between-person and the within-person associations between subjective health and engagement in physical activity. Chronic conditions, difficulty in performing daily activities, and demographic variables were controlled for. RESULTS: At the between-person level, subjective (i.e., self-rated) health was positively associated with physical activity in the whole sample and the older subgroup (T1 age >55 years), but not in the younger subgroup (T1 age <35 years). At the within-person level, the association between subjective health and subsequent physical activity was negative in the whole sample and the older subgroup, but nonsignificant (between T1 and T2) or positive (between T2 and T3) in the younger subgroup. DISCUSSION: This study revealed various associations between subjective health and engagement in physical activity across levels (the within- vs. between-person level) and across age groups (younger vs. older group). The finding contributes to a better understanding of people's health behavior in reaction to health decline at different ages. It also supports the proposition that age-related intraindividual increases in losses (e.g., health decline) motivate behaviors that counteract such losses (e.g., physical activity that protects health).

"Youth-focused" versus "whole-family" screen rules: Associations with social media difficulties and moderation by impulsivity.

Many parents attempt to limit adolescents' screen time without changing their own habits. We examined whether "whole-family" versus "youth-focused" restrictions differentially predict social media-related difficulties (procrastination and problematic use), and whether adolescents' impulsive social media behaviors moderated these relationships. Among 183 Chinese early adolescents (58.5% female), whole-family rules negatively predicted procrastination. Impulsivity moderated associations between rulemaking approaches and social media difficulties; youth-focused rules negatively predicted procrastination and problematic use for highly impulsive adolescents, while whole-family rules held no associations or predicted increased difficulties. For less impulsive adolescents, however, whole-family rules negatively predicted social media difficulties and youth-focused rules positively predicted problematic use. Results suggest that setting the implementation of screen rules should involve parental participation and consideration of individual differences.

A point-of-care urine test to predict adverse maternal and neonatal outcomes in Asian women with suspected preeclampsia.

OBJECTIVES: To assess clinical utility of the urine Congo red dot test (CRDT) in predicting composite adverse maternal and neonatal outcomes in women with suspected preeclampsia (PE). METHODS: CRDT result and pregnancy outcomes were prospectively documented in women with new onset or pre-existing hypertension, new or pre-existing proteinuria, PE symptoms and suspected PE-related fetal growth restriction or abnormal Doppler presenting from 20 weeks' gestation between January 2020 and December 2022. Participants and clinicians were blinded to the CRDT result and managed according to internally agreed protocols. Composite maternal outcome was defined as PE, postpartum hemorrhage, intensive care unit admission, and maternal death. Composite neonatal outcome was defined as small for gestational age, preterm birth, 5-min Apgar score < 7, neonatal intensive care unit admission, and neonatal death. RESULTS: Two hundred and forty-four women out of two hundred and fifty-one (97.2%) had a negative CRDT. All seven women with positive CRDT had both adverse maternal and neonatal outcomes, giving positive predictive values (PPV) of 100%. Rates of composite adverse maternal and neonatal outcomes in CDRT negative women were 103/244 [42.2%, 95% confidence interval (CI) 36.2%-48.5%] and 170/244 (69.7%, 95% CI 63.6%-75.1%), respectively. CRDT negative predictive values (NPV) for adverse maternal and neonatal outcomes were, respectively, 141/244 (57.8%, 95% CI 48.6%-68.2%) and 74/244 (30.3%, 95% CI 23.8%-38.1%). CONCLUSION: CRDT had low NPV but high PPV for adverse maternal and neonatal outcomes in women with suspected PE. Its role in clinical management and triage of women with suspected PE is limited as it cannot identify those at low risk of developing adverse outcomes.

Comparison of the quality of life changes of patients receiving sagittal split ramus osteotomy or intraoral vertical subsigmoid osteotomy for mandibular prognathism.

OBJECTIVE: To investigate and compare the effect of two orthognathic procedures for mandibular setback, namely, sagittal split ramus osteotomy (SSRO) and intraoral vertical ramus osteotomy (IVRO), on oral health, mental- and physical health-related quality of life across time. MATERIALS AND METHODS: Patients with mandibular prognathism and planned for orthognathic surgery were recruited in this study. Patients were randomized into two groups (IVRO and SSRO groups). Quality of life (QoL) was assessed with the 14-item Short-Form Oral Health Impact Profile (OHIP-14) and the 36-item Short-Form Health Survey (SF-36) preoperatively (T0), postoperative 2 weeks (T1), 6 weeks (T2), 3 months (T3), 6 months (T4), 12 months (T5), and 24 months (T6). A comparison of OHIP-14 and SF-36 scores between two groups was conducted. RESULTS: Ninety-eight patients (49 SSRO group, 49 IVRO group) participated in this study. There was no significant difference in OHIP-14 scores between SSRO and IVRO throughout the treatment process. SSRO group had significant reduction of OHIP-14 score (i.e., improving oral health-related QoL) since postoperative 2 weeks, whereas IVRO group had significant reduction since postoperative 6 weeks. Starting from postoperative 3 months, the oral health-related QoL of both groups was already significantly better than the baseline level and continued to steadily improve afterwards. For SF-36, both groups had increased physical health summary score starting from postoperative 2 weeks, indicating an early and gradual recovery of physical health-related QoL. The mental health summary score of the SSRO group began to increase from postoperative 2 weeks, but that of the IVRO group only began to increase from postoperative 6 weeks. Patient age at the time of surgery was positively correlated with OHIP scores in the postoperative period. CONCLUSIONS: The study concludes that both SSRO and IVRO contributed to the improvement of QoL in the long term, but oral health- and mental health-related QoL of SSRO groups showed earlier improvement. CLINICAL RELEVANCE: Undergoing orthognathic surgery at early ages is advised, as older age of patients appeared to have worse QoL. TRIAL REGISTRATION: Clinical trial registration number: HKUCTR-1985. Date of Registration: 14 Apr 2015.

Acute Liver Failure Etiology Is an Independent Predictor of Waitlist Outcome but Not Posttransplantation Survival in a National Cohort.

The impact of acute liver failure (ALF) etiology on waitlist (WL) and posttransplantation outcomes, independent of severity of illness, is incompletely characterized. All adults (n = 1691) listed for primary liver transplantation (LT) between 2002 and 2019 with ALF due to acetaminophen toxicity (APAP), drug-induced liver injury (DILI), autoimmune hepatitis (AIH), and hepatitis B virus (HBV) were identified in the United Network for Organ Sharing database. ALF etiology was evaluated as an independent predictor of WL mortality and spontaneous survival (SS; versus outcome of LT), as well as post-LT overall survival, graft survival, and in-hospital mortality using multivariable models accounting for differences in clinical parameters at listing. Accounting for severity of illness at listing, WL mortality and SS for DILI, AIH, and HBV were each lower than those for APAP toxicity (adjusted relative risk ratio <1 in all analyses with P < 0.001 for both outcomes). ALF etiology was not associated with adjusted overall survival after LT (P = 0.09) or graft survival (P = 0.13). Inpatient mortality rate after LT was high at 9.0%. While ALF etiology was also not associated with adjusted inpatient mortality (P = 0.42), cause of death (COD) was different. For example, the rate of post-LT brain death was 5.3% for APAP toxicity, 3.0% for other DILI, 1.1% for AIH, and 3.0% for HBV (P = 0.02). ALF etiology is an independent predictor of WL outcome, even after adjusting for severity of illness, but is not associated with post-LT outcomes with the exception of COD. The majority of post-LT deaths for all ALF etiologies studied occurred during the index hospital stay, suggesting a continued need for enhanced prognostic tools to ensure efficient organ utilization and ALF- and etiology-specific post-LT care to prevent brain death.

Photostability of the deprotonated forms of the UV filters homosalate and octyl salicylate: molecular dissociation versus electron detachment following UV excitation.

While common molecular anions show a strong propensity to undergo electron detachment upon UV excitation, this process often occurs in competition with molecular ion dissociation. The factors that affect the balance between these two major possible decay pathways have not been well understood to date. Laser photodissociation spectroscopy of the deprotonated forms of the UV filter molecules, Homosalate (HS) and Octyl Salicylate (OS), i.e. [HS - H]- and [OS - H]-, was used to acquire gas-phase UV absorption spectra for [HS - H]- and [OS - H]-via photodepletion from 3.0-5.8 eV. No photofragmentation (i.e. dissociation of the ionic molecular framework) was observed for either [HS - H]- and [OS - H]- following photoexcitation, revealing that electron loss entirely dominates the electronic decay pathways for these systems. High-level quantum chemical calculations were used to map out the excited states associated with [HS - H]- and [OS - H]-, revealing that the minimum-energy crossing points (MECPs) between the S1 and S0 states are located in elevated regions of the potential energy surface, making internal conversion unlikely. These results are consistent with our experimental observation that electron detachment out-competes hot ground state molecular fragmentation. More generally, our results reveal that the competition between molecular dissociation and electron detachment following anion photoexcitation can be determined by the magnitude of the energy gap between the excitation energy and the MECPs, rather than being a simple function of whether the excitation energy lies above the anion's vertical detachment energy.

Probing the electronic relaxation pathways and photostability of the synthetic nucleobase Z via laser interfaced mass spectrometry.

The photostability of synthetic (unnatural) nucleobases is important in establishing the integrity of new genetic alphabets, and critical for developing healthy semisynthetic organisms. Here, we report the first study to explore the photostability and electronic decay pathways of the synthetic nucleobase, Z (6-amino-5-nitro-2(1H)-pyridone), combining UV laser photodissociation and collisional dissociation measurements to characterise the decay pathways across the region from 3.1-4.9 eV. Photoexcitation across this region produced the m/z 138 ion as the dominant photofragment, mirroring the dominant fragment produced upon higher-energy collisional excitation. Analysis of the ion-yield production curve profile for the m/z 138 ion indicates that it is produced following ultrafast excited state decay with boil off of the OH functional group of Z from the hot electronic ground state. Electronic structure calculations provide physical insight into why this is the dominant fragmentation pathway, since a node in the electron density along the C-OH bond is found for all tautomers of Z. While the dominant decay pathway for Z is consistent with ultrafast excited state decay, we also identify several minor dissociative photochemistry decay pathways, associated with intrinsic photoinstability. The results presented here can be used to guide the development of more photostable synthetic nucleobases.

Three-dimensional assessment of facial asymmetry in Class III subjects. Part 1: a retrospective study evaluating postsurgical outcomes.

OBJECTIVE: The present study aimed to determine the site and severity of maxillomandibular asymmetry before and after orthognathic surgery in asymmetric patients. MATERIALS AND METHODS: Presurgery and postsurgery cone beam computed tomography (CBCT) data of 21 facial asymmetry patients (7 males and 14 females, mean age: 23.0 ± 3.36 years) with soft tissue chin deviation ≥ 3 mm who had undergone bimaxillary surgery were evaluated. Seven midline and twenty bilateral hard tissue landmarks were identified for the evaluation of facial asymmetry and outcomes were assessed against age- and gender-matched control subjects. RESULTS: In the asymmetry group, bilateral landmarks exhibited significant deviation in the mandible and midface regions. Before surgery, asymmetry was more severe at the mandibular midline and sites close to it, in the asymmetry group. Bimaxillary surgery proved to be highly effective, with a significant correction of the menton to a clinically normal value (2.90 mm, p < 0.001). After surgery, significant residual asymmetry was observed at the mental foramen (p = 0.001) in the R-L direction. Moreover, significant asymmetry persisted at the sigmoid notch (p = 0.001) in the S-I direction. CONCLUSIONS: Mandibular midline landmarks and chin peripheral regions contribute significantly to overall facial asymmetry characteristics. Despite significant correction after bimaxillary surgery, asymmetry persisted at several sites, thereby requiring secondary correction. Comprehensive 3D presurgical planning is central for asymmetry correction in a single surgery. CLINICAL RELEVANCE: The present study specifies the location of residual asymmetry sites and advocates the correction of those sites during initial surgery.

The non-transparent usage and reporting of the Edinburgh Handedness Inventory in functional magnetic resonance imaging literature: a survey of studies published since 2013.

Subject handedness is an important parameter to be evaluated and accounted for in neuroscience studies dealing with laterality. The aim of this study was to survey for the details of how researchers administered the Edinburgh handedness inventory (EHI) to assess subject handedness. Web of Science and PubMed databases was searched on 3 August 2021 to identify functional magnetic resonance imaging (fMRI) articles published since 2013 using the EHI or citing Oldfield, the original paper that introduced the EHI. Articles not actually using the EHI and/or its variants were excluded. Two reviewers performed the screening independently and disagreements were solved by mutual consensus. Most of the 406 studies using the EHI did not report details regarding the number of items (94.1%), identity of items (96.1%), response format (97.0%), and cutoff score for right-handedness (87.2%). Items were found dropped or replaced, with response format and cutoff score changed without citing references that justified the modifications. A clearer reporting of the details of the EHI as an assessment tool for determining subject handedness should be encouraged.

Prenatal Diagnosis and Pregnancy Outcomes of Fetuses With Orofacial Cleft: A Retrospective Cohort Study in Two Centres in Hong Kong.

OBJECTIVE: To evaluate the local incidence of orofacial cleft (OFC) encountered in fetal morphology scan and prenatal diagnosis, genetic etiology of fetuses with or without other structural abnormalities, and their pregnancy outcomes. DESIGN: Retrospective cohort study. SETTING: Two maternal fetal medicine units, tertiary hospitals, Hong Kong. PARTICIPANTS: All pregnant women with antenatal diagnosis of fetal OFC between January 2016 and December 2020 (N = 66). RESULTS: OFC has an incidence of 0.13% among pregnancies in Hong Kong and 28.8% (19/66) were syndromic cleft that exhibited other fetal structural anomalies. There were 55 cases (84.6%) who opted for invasive prenatal diagnostic testing. Genetic defects were identified in 25.8% (17/66) of this cohort, including 14 pathogenic variants. The detection rate in the syndromic cases is 68.4% (13/19) which was significantly higher than 8.5% (4/47) among non-syndromic cases. Aneuploidies would be the most common cause, accounting for 9.1% (6/66). Chromosomal microarray analysis (CMA) provided an incremental diagnostic yield of 6.1% compared to conventional karyotyping. A total of 29 live births including 3 cases of a variant of uncertain significance and 26 cases without genetic abnormalities detected have continued pregnancy to birth. There were 87.5% (21/24) without detectable pathogenic genetic abnormality reported good long-term outcomes. The chance of OFC fetuses having a good long-term outcome was significantly higher if no genomic variant was detected (P < .001). CONCLUSIONS: Invasive prenatal tests with CMA should be offered to pregnancies with OFC regardless of the type. It has provided incremental diagnostic yield over conventional karyotyping and helped in prenatal and genetic counseling. A negative result in non-syndromic OFC favors couples to keep the pregnancy.

Photochemical Degradation of the UV Filter Octyl Methoxy Cinnamate Probed via Laser-Interfaced Mass Spectrometry.

Octyl methoxycinnamate (OMC) is a common UVA and UVB filter molecule that is widely used in commercial sunscreens. Here, we used gas-phase laser photodissociation spectroscopy to characterise the intrinsic photostability and photodegradation products of OMC by studying the system in its protonated form, i.e., [OMC·H]+. The major photofragments observed were m/z 179, 161, and 133, corresponding to fragmentation on either side of the ether oxygen of the ester group (m/z 179 and 161) or the C-C bond adjacent to the ester carbonyl group. Additional measurements were obtained using higher-energy collisional dissociation mass spectrometry (HCD-MS) to identify fragments that resulted from the breakdown of the vibrationally hot electronic ground state. We found that the m/z 179 and 161 ions were the main fragments produced by this route. Notably, the m/z 133 ion was not observed through HCD-MS, revealing that this product ion is only produced through a photochemical route. Our results demonstrate that UV photoexcitation of OMC is able to access a dissociative excited-state surface that uniquely leads to the rupture of the C-C bond adjacent to the key ester carbonyl group.

Transplant center experience influences spontaneous survival and waitlist mortality in acute liver failure: An analysis of the UNOS database.

Transplant centers coordinate complex care in acute liver failure (ALF), for which liver transplant (LT) can be lifesaving. We studied associations between waitlist outcomes and center (1) ALF waitlist volume (low: <20; medium: 20-39; high: 40+ listings) and (2) total LT volume (<600, 600-1199, 1200+ LTs) in a retrospective cohort of 3248 adults with ALF listed for LT at 92 centers nationally from 2002 to 2019. Predicted outcome probabilities (LT, died/too sick, spontaneous survival [SS]) were obtained with multinomial regression, and observed-to-expected ratios were calculated. Median center outcome rates were 72.6% LT, 18.2% died/too sick, and 6.1% SS. SS was significantly higher with greater center ALF volume (median 0% for low-, 5.9% for medium-, and 8.6% for high-volume centers; P = .039), while waitlist mortality was highest at low-volume centers (median 21.4%, IQR: 16.1%-26.7%; P = .042). Significant heterogeneity in center performance was observed for waitlist mortality (observed-to-expected ratio range: 0-4.1) and particularly for SS (0-6.4), which persisted despite accounting for recipient case mix. This novel study demonstrates that increased center experience is associated with greater SS and reduced waitlist mortality for ALF. More-focused management pathways are needed to improve ALF outcomes at less-experienced centers and to identify opportunities for improvement at large.

Measurement of the Population of Electrosprayed Deprotomers of Coumaric Acids Using UV-Vis Laser Photodissociation Spectroscopy.

The measurement of deprotonation sites in multifunctional molecules following electrospray ionization is important to better inform a wide range of spectroscopic and photophysical studies that use electrospray to prepare molecular species for study in the gas phase. We demonstrate that low-resolution UV-vis laser photodissociation spectroscopy can be applied in situ to identify the deprotomers of three coumaric acids, trans-para-coumaric acid (CMA), trans-caffeic acid (CA), and trans-ferulic acid (FA), formed via electrospray. Electronic absorption spectra of the deprotonated coumaric acids are recorded via photodepletion and photofragmentation following electrospray from solutions of ethanol and acetonitrile. By comparing the experimental spectra to wave function theory calculations, we are able to confirm the presence of phenoxide and carboxylate deprotomers upon electrospray for all three coumaric acids, when sprayed from both protic and aprotic solvents. Ratios of the phenoxide:carboxylate deprotomers are obtained by generating summed theoretical absorption spectra that reproduce the experimental spectra. We find that choice of electrospray solvent has little effect on the ratio of deprotomers obtained for deprotonated CMA and CA but has a greater impact for FA. Our results are in excellent agreement with previous work conducted on deprotonated CMA using IR spectroscopy and demonstrate that UV photodissociation spectroscopy of electrosprayed ions has potential as a diagnostic tool for identifying deprotomeric species.

Photodegradation of Riboflavin under Alkaline Conditions: What Can Gas-Phase Photolysis Tell Us about What Happens in Solution?

The application of electrospray ionisation mass spectrometry (ESI-MS) as a direct method for detecting reactive intermediates is a technique of developing importance in the routine monitoring of solution-phase reaction pathways. Here, we utilise a novel on-line photolysis ESI-MS approach to detect the photoproducts of riboflavin in aqueous solution under mildly alkaline conditions. Riboflavin is a constituent of many food products, so its breakdown processes are of wide interest. Our on-line photolysis setup allows for solution-phase photolysis to occur within a syringe using UVA LEDs, immediately prior to being introduced into the mass spectrometer via ESI. Gas-phase photofragmentation studies via laser-interfaced mass spectrometry of deprotonated riboflavin, [RF - H]-, the dominant solution-phase species under the conditions of our study, are presented alongside the solution-phase photolysis. The results obtained illustrate the extent to which gas-phase photolysis methods can inform our understanding of the corresponding solution-phase photochemistry. We determine that the solution-phase photofragmentation observed for [RF - H]- closely mirrors the gas-phase photochemistry, with the dominant m/z 241 condensed-phase photoproduct also being observed in gas-phase photodissociation. Further gas-phase photoproducts are observed at m/z 255, 212, and 145. The value of exploring both the gas- and solution-phase photochemistry to characterise photochemical reactions is discussed.

Empirical assessment of changing sample-characteristics in task-fMRI over two decades: An example from gustatory and food studies.

Over the past two decades, functional neuroimaging has not only grown into a large field of research, but also substantially evolved. Here we provide a quantitative assessment of these presumed in sample composition and data analysis, using fMRI studies on food/taste research published between 1998 and 2019 as an exemplary case in which the scientific objectives themselves have remained largely stable. A systematic search for papers written in English was done using multiple databases and identified 426 original articles that were subsequently analyzed. The median sample size significantly increased from 11.5 to 35.5 while the ratio of male to female subjects remained stable. There were, however, more papers involving female subjects only, rather than male subjects only, since 2003. There was a decline in uncorrected results and statistical correction by false-discovery rate. Reflecting a trend toward more conservative thresholding, the number of foci reported per paper did not change significantly and sample size (power) did not correlate with the number of reported foci. The median journal impact factor and the normalized number of citations (citations per year) of the papers, in turn, showed a significantly decreasing trend. Number of citations negatively correlated to sample size, publication year but positively correlated to journal impact factor, and was also influenced by statistical correction method. There was a decreasing trend in studies recruiting both left-handed and right-handed subjects. In summary, the present paper quantifies several large-scale trends that have often been anecdotally discussed and reveals the changing nature of neuroimaging studies that may be considered when pursuing meta-analytic approaches.

Direct Measurement of the Visible to UV Photodissociation Processes for the PhotoCORM TryptoCORM.

PhotoCORMs are light-triggered compounds that release CO for medical applications. Here, we apply laser spectroscopy in the gas phase to TryptoCORM, a known photoCORM that has been shown to destroy Escherichia coli upon visible-light activation. Our experiments allow us to map TryptoCORM's photochemistry across a wide wavelength range by using novel laser-interfaced mass spectrometry (LIMS). LIMS provides the intrinsic absorption spectrum of the photoCORM along with the production spectra of all of its ionic photoproducts for the first time. Importantly, the photoproduct spectra directly reveal the optimum wavelengths for maximizing CO ejection, and the extent to which CO ejection is compromised at redder wavelengths. A series of comparative studies were performed on TryptoCORM-CH3 CN which exists in dynamic equilibrium with TryptoCORM in solution. Our measurements allow us to conclude that the presence of the labile CH3 CN facilitates CO release over a wider wavelength range. This work demonstrates the potential of LIMS as a new methodology for assessing active agent release (e.g. CO, NO, H2 S) from light-activated prodrugs.

Sodium cationization can disrupt the intramolecular hydrogen bond that mediates the sunscreen activity of oxybenzone.

A key decay pathway by which organic sunscreen molecules dissipate harmful UV energy involves excited-state hydrogen atom transfer between proximal enol and keto functional groups. Structural modifications of this molecular architecture have the potential to block ultrafast decay processes, and hence promote direct excited-state molecular dissociation, profoundly affecting the efficiency of an organic sunscreen. Herein, we investigate the binding of alkali metal cations to a prototype organic sunscreen molecule, oxybenzone, using IR characterization. Mass-selective IR action spectroscopy was conducted at the free electron laser for infrared experiments, FELIX (600-1800 cm-1), on complexes of Na+, K+ and Rb+ bound to oxybenzone. The IR spectra reveal that K+ and Rb+ adopt binding positions away from the key OH intermolecular hydrogen bond, while the smaller Na+ cation binds directly between the keto and enol oxygens, thus breaking the intramolecular hydrogen bond. UV laser photodissociation spectroscopy was also performed on the series of complexes, with the Na+ complex displaying a distinctive electronic spectrum compared to those of K+ and Rb+, in line with the IR spectroscopy results. TD-DFT calculations reveal that the origin of the changes in the electronic spectra can be linked to rupture of the intramolecular bond in the sodium cationized complex. The implications of our results for the performance of sunscreens in mixtures and environments with high concentrations of metal cations are discussed.

Unravelling the Keto-Enol Tautomer Dependent Photochemistry and Degradation Pathways of the Protonated UVA Filter Avobenzone.

Avobenzone (AB) is a widely used UVA filter known to undergo irreversible photodegradation. Here, we investigate the detailed pathways by which AB photodegrades by applying UV laser-interfaced mass spectrometry to protonated AB ions. Gas-phase infrared multiple-photon dissociation (IRMPD) spectra obtained with the free electron laser for infrared experiments, FELIX, (600-1800 cm-1) are also presented to confirm the geometric structures. The UV gas-phase absorption spectrum (2.5-5 eV) of protonated AB contains bands that correspond to selective excitation of either the enol or diketo forms, allowing us to probe the resulting, tautomer-dependent photochemistry. Numerous photofragments (i.e., photodegradants) are directly identified for the first time, with m/z 135 and 161 dominating, and m/z 146 and 177 also appearing prominently. Analysis of the production spectra of these photofragments reveals that that strong enol to keto photoisomerism is occurring, and that protonation significantly disrupts the stability of the enol (UVA active) tautomer. Close comparison of fragment ion yields with the TD-DFT-calculated absorption spectra give detailed information on the location and identity of the dissociative excited state surfaces, and thus provide new insight into the photodegradation pathways of avobenzone, and photoisomerization of the wider class of ß-diketone containing molecules.

The imperative for an updated cirrhosis surgical risk score.

The burden of cirrhosis is increasing, as is the need for surgeries in patients with cirrhosis. These patients have increased surgical risk relative to non-cirrhotic patients. Unfortunately, currently available cirrhosis surgical risk prediction tools are non-specific, poorly calibrated, limited in scope, and/or outdated. The Mayo score is the only dedicated tool to provide discrete post-operative mortality predictions for patients with cirrhosis, however it has several limitations. First, its single-center nature does not reflect institution-specific practices that may impact surgical risk. Second, it pre-dates major surgical changes that have changed the landscape of patient selection and surgical risk. Third, it has been shown to overestimate risk in external validation. Finally, and perhaps most importantly, the score does not account for differences in risk based on surgery type. The clinical consequences of inaccurate prediction and risk overestimation are significant, as patients with otherwise acceptable risk may be denied elective surgical procedures, thereby increasing their future need for higher-risk emergent procedures. Confident evaluation of the risks and benefits of surgery in this growing population requires an updated, generalizable, and accurate cirrhosis surgical risk calculator that incorporates the type of surgery under consideration.

Fighting COVID-19 in Hong Kong: The effects of community and social mobilization.

The globalized world economy has been affected by the COVID-19 pandemic since early February 2020. In the midst of this global public health crisis, a prompt review of the counterinsurgencies that have occurred in different jurisdictions is helpful. This article examines the experience of Hong Kong (HKSAR), which successfully limited its number of confirmed cases to approximately 1100 until early June 2020. Considering the limited actions that the government has taken against the pandemic, we emphasize the prominent role of Hong Kong's civil society through highlighting the strong and spontaneous mobilization of its local communities originating from their experiences during the SARS outbreak in 2003 and the social unrest in 2019, as well as their doubts regarding the pandemic assessments and recommendations of the HKSAR and WHO authorities. This article suggests that the influence of civil society should not be overlooked in the context of pandemic management.