Cryogenic Photoelectron Spectroscopic and Theoretical Study of the Electronic and Geometric Structures of Undercoordinated Osmium Chloride Anions OsCln- (n = 3-5).

A series of anionic transition metal halides, OsCln- (n = 3-5), have been investigated using a newly developed, home-constructed, cryogenic anion cluster photoelectron spectroscopy. The target anionic species are generated through collision-induced dissociation in a two-stage ion funnel. The measured vertical detachment energies (VDEs) are 3.48, 4.54, and 4.81 eV for n = 3, 4, and 5, respectively. Density functional theory calculations at the B3LYP-D3(BJ)//aug-cc-pVTZ(-pp) level predict the lowest energy structures of the atomic form of OsCln- (n = 3-5) to be a quintet triangle, quartet square, and quintet square-based pyramid, respectively. The CCSD(T)-calculated VDEs and corresponding adiabatic detachment energies agree well with our experimental measurements. Analysis of the corresponding frontier molecular orbitals and charge density differences suggests that the d-orbitals of the transition metal Os play a primary role in the single-photon detachment processes, and the detached electrons originating from different molecular orbitals are distinguishable.

Construction and validation of a risk prediction model for postoperative ICU admission in patients with colorectal cancer: clinical prediction model study.

BACKGROUND: Transfer to the ICU is common following non-cardiac surgeries, including radical colorectal cancer (CRC) resection. Understanding the judicious utilization of costly ICU medical resources and supportive postoperative care is crucial. This study aimed to construct and validate a nomogram for predicting the need for mandatory ICU admission immediately following radical CRC resection. METHODS: Retrospective analysis was conducted on data from 1003 patients who underwent radical or palliative surgery for CRC at Ningxia Medical University General Hospital from August 2020 to April 2022. Patients were randomly assigned to training and validation cohorts in a 7:3 ratio. Independent predictors were identified using the least absolute shrinkage and selection operator (LASSO) and multivariate logistic regression in the training cohort to construct the nomogram. An online prediction tool was developed for clinical use. The nomogram's calibration and discriminative performance were assessed in both cohorts, and its clinical utility was evaluated through decision curve analysis (DCA). RESULTS: The final predictive model comprised age (P = 0.003, odds ratio [OR] 3.623, 95% confidence interval [CI] 1.535-8.551); nutritional risk screening 2002 (NRS2002) (P = 0.000, OR 6.129, 95% CI 2.920-12.863); serum albumin (ALB) (P = 0.013, OR 0.921, 95% CI 0.863-0.982); atrial fibrillation (P = 0.000, OR 20.017, 95% CI 4.191-95.609); chronic obstructive pulmonary disease (COPD) (P = 0.009, OR 8.151, 95% CI 1.674-39.676); forced expiratory volume in 1 s / Forced vital capacity (FEV1/FVC) (P = 0.040, OR 0.966, 95% CI 0.935-0.998); and surgical method (P = 0.024, OR 0.425, 95% CI 0.202-0.891). The area under the curve was 0.865, and the consistency index was 0.367. The Hosmer-Lemeshow test indicated excellent model fit (P = 0.367). The calibration curve closely approximated the ideal diagonal line. DCA showed a significant net benefit of the predictive model for postoperative ICU admission. CONCLUSION: Predictors of ICU admission following radical CRC resection include age, preoperative serum albumin level, nutritional risk screening, atrial fibrillation, COPD, FEV1/FVC, and surgical route. The predictive nomogram and online tool support clinical decision-making for postoperative ICU admission in patients undergoing radical CRC surgery. TRIAL REGISTRATION: Despite the retrospective nature of this study, we have proactively registered it with the Chinese Clinical Trial Registry. The registration number is ChiCTR2200062210, and the date of registration is 29/07/2022.

Transient Valence Charge Localization in Strong-Field Dissociative Ionization of HCl Molecules.

Probing transient charge localization in the innershell orbital of atoms and molecules has been made possible by the recent progress of advanced light sources. Here, we demonstrate that the ultrafast electron tunneling ionization by an intense femtosecond laser pulse could induce an asymmetric transient charge localization in the valence shell of the HCl molecule during the dissociative ionization process. The transient charge localization is encoded in the laser impulse acquired by the outgoing ionic fragments, and the asymmetry is revealed by carefully examining the electron tunneling-site distinguished momentum angular distribution of the ejected H^{+} fragments. Our work proposes a way to visualize the transient valence charge motion and will stimulate further investigations of the tunneling-site-sensitive ultrafast dynamics of molecules in strong laser fields.

High-order above-threshold dissociation of molecules.

Electrons bound to atoms or molecules can simultaneously absorb multiple photons via the above-threshold ionization featured with discrete peaks in the photoelectron spectrum on account of the quantized nature of the light energy. Analogously, the above-threshold dissociation of molecules has been proposed to address the multiple-photon energy deposition in the nuclei of molecules. In this case, nuclear energy spectra consisting of photon-energy spaced peaks exceeding the binding energy of the molecular bond are predicted. Although the observation of such phenomena is difficult, this scenario is nevertheless logical and is based on the fundamental laws. Here, we report conclusive experimental observation of high-order above-threshold dissociation of H2 in strong laser fields where the tunneling-ionized electron transfers the absorbed multiphoton energy, which is above the ionization threshold to the nuclei via the field-driven inelastic rescattering. Our results provide an unambiguous evidence that the electron and nuclei of a molecule as a whole absorb multiple photons, and thus above-threshold ionization and above-threshold dissociation must appear simultaneously, which is the cornerstone of the nowadays strong-field molecular physics.

Prevalence, genotypes and risk factors for Toxoplasma gondii contamination in marine bivalve shellfish in offshore waters in eastern China.

We conducted a large-scale epidemiological investigation to detect the prevalence of Toxoplasma gondii in four marine bivalve shellfish species collected from six representative coastal regions of Weihai, eastern China. Between January 2018 and December 2018, 14,535 marine bivalve shellfish pooled into 2907 samples were randomly collected and examined for T. gondii DNA by a nested PCR assay targeting B1 gene. The results showed that 2.8% (82) of the 2907 pooled samples were tested positive for T. gondii DNA. Two T. gondii genotype (ToxoDB Genotype #9 and ToxoDB Genotype #1) were identified PCR-restriction fragment length polymorphism analysis. Factors that were found significantly associated with the presence of T. gondii DNA in marine bivalve shellfish included the source of samples (being wild) (odds ratio [OR], 3.34; 95% confidence interval [CI], 2.00-5.84; p < 0.01), surface runoff near the sampling site (OR, 2.64; 95% CI, 1.47-4.72; p < 0.01), and presence of cats near the sampling site (OR, 1.77; 95% CI, 1.02-3.07; p = 0.04). Moreover, the prevalence of T. gondii DNA in marine bivalve shellfish correlated with temperature (Pearson's correlation: R = 0.75, p = 0.0049) and precipitation (R = 0.87, p = 0.00021). These findings provide new insights into the presence of T. gondii DNA in marine bivalve shellfish and highlight the impact of human activity on marine pollution by such an important terrestrial pathogen pollutant.

Rotational Echoes as a Tool for Investigating Ultrafast Collisional Dynamics of Molecules.

We show that recently discovered rotational echoes of molecules provide an efficient tool for studying collisional molecular dynamics in high-pressure gases. Our study demonstrates that rotational echoes enable the observation of extremely fast collisional dissipation, at timescales of the order of a few picoseconds, and possibly shorter. The decay of the rotational alignment echoes in CO_{2} gas and CO_{2}-He mixture up to 50 bar was studied experimentally, delivering collision rates that are in good agreement with the theoretical expectations. The suggested measurement protocol may be used in other high-density media, and potentially in liquids.

Timing Dissociative Ionization of H_{2} Using a Polarization-Skewed Femtosecond Laser Pulse.

We experimentally observe the bond stretching time of one-photon and net-two-photon dissociation pathways of singly ionized H_{2} molecules driven by a polarization-skewed femtosecond laser pulse. By measuring the angular distributions of the ejected photoelectron and nuclear fragments in coincidence, the cycle-changing polarization of the laser field enables us to clock the photon-ionization starting time and photon-dissociation stopping time, analogous to a stopwatch. After the single ionization of H_{2}, our results show that the produced H_{2}^{+} takes almost the same time in the one-photon and net-two-photon dissociation pathways to stretch to the internuclear distance of the one-photon coupled dipole-transition between the ground and excited electronic states. The spatiotemporal mapping character of the polarization-skewed laser field provides us a straightforward route to clock the ultrafast dynamics of molecules with sub-optical-cycle time resolution.

Deoxygenative Arylation of Carboxylic Acids by Aryl Migration.

An unprecedented deoxygenative arylation of aromatic carboxylic acids has been achieved, allowing the construction of an enhanced library of unsymmetrical diaryl ketones. The synergistic photoredox catalysis and phosphoranyl radical chemistry allows for precise cleavage of a stronger C-O bond and formation of a weaker C-C bond by 1,5-aryl migration under mild reaction conditions. This new protocol is independent of substrate redox-potential, electronic, and substituent effects. It affords a general and promising access to 60 examples of synthetically versatile o-amino and o-hydroxy diaryl ketones under redox-neutral conditions. Furthermore, it also brings one concise route to the total synthesis of quinolone alkaloid, (±)-yaequinolone A2, and a viridicatin derivative in satisfying yields.

Synergistic Catalysis for the Umpolung Trifluoromethylthiolation of Tertiary Ethers.

The first transition-metal-free, site-specific umpolung trifluoromethylthiolation of tertiary alkyl ethers has been developed, achieving the challenging tertiary C(sp3 )-SCF3 coupling under redox-neutral conditions. The synergism of organophotocatalyst 4CzIPN and BINOL-based phosphorothiols can site-selectively cleave tertiary sp3 C(sp3 )-O ether bonds in complex molecules initiated by a polarity-matching hydrogen-atom-transfer (HAT) event. The incorporation of several competing benzylic and methine C(sp3 )-H bonds in alkyl ethers has little influence on the regioselectivity. Selective difluoromethylthiolation of C-O bonds has also been achieved. This represents not only an important step forward in trifluoromethylthiolation but also a promising means for site-selective C-O bond functionalization of unsymmetrical tertiary alkyl ethers.

Orientation-dependent strong-field dissociative single ionization of CO.

The dissociative ionization of CO in orthogonally polarized femtosecond laser pulses are studied in a pump-probe scheme. The ionization of CO by the pump pulse and the dissociation of the created CO+ by the probe pulse can be fully disentangled by identifying the photoelectron momentum distributions. Different from the dissociative ionization by a single pulse in which the CO molecule mostly breaks along the field polarization, in this pump-probe strategy, the CO+ ion created from ionization by the pump pulse is favored to dissociate when it orients orthogonal to the polarization direction of the probe pulse. It is attributed to the laser-coupling of various electronic states of the molecular ion in the dissociation process, supported by the numerical simulation of a modeled time-dependent Schrödinger equation.

Rotated echoes of molecular alignment: fractional, high order and imaginary.

We report experimental observations of rotated echoes of alignment induced by a pair of time-delayed and polarization-skewed femtosecond laser pulses interacting with an ensemble of molecular rotors. Rotated fractional echoes, rotated high order echoes and rotated imaginary echoes are directly visualized by using the technique of coincident Coulomb explosion imaging. We show that the echo phenomenon not only exhibits temporal recurrences but also spatial rotations determined by the polarization of the time-delayed second pulse. The dynamics of echo formation is well described by the laser-induced filamentation in rotational phase space. The quantum-mechanical simulation shows good agreements with the experimental results.

Energy-Resolved Ultrashort Delays of Photoelectron Emission Clocked by Orthogonal Two-Color Laser Fields.

A phase-controlled orthogonal two-color (OTC) femtosecond laser pulse is employed to probe the time delay of photoelectron emission in the strong-field ionization of atoms. The OTC field spatiotemporally steers the emission dynamics of the photoelectrons and meanwhile allows us to unambiguously distinguish the main and sideband peaks of the above-threshold ionization spectrum. The relative phase shift between the main and sideband peaks, retrieved from the phase-of-phase of the photoelectron spectrum as a function of the laser phase, gradually decreases with increasing electron energy, and becomes zero for the fast electron which is mainly produced by the rescattering process. Furthermore, a Freeman resonance delay of 140±40 attoseconds between photoelectrons emitted via the 4f and 5p Rydberg states of argon is observed.

Visualizing and Steering Dissociative Frustrated Double Ionization of Hydrogen Molecules.

We experimentally visualize the dissociative frustrated double ionization of hydrogen molecules by using few-cycle laser pulses in a pump-probe scheme, in which process the tunneling ionized electron is recaptured by one of the outgoing nuclei of the breaking molecule. Three internuclear distances are recognized to enhance the dissociative frustrated double ionization of molecules at different instants after the first ionization step. The recapture of the electron can be further steered to one of the outgoing nuclei as desired by using phase-controlled two-color laser pulses. Both the experimental measurements and numerical simulations suggest that the Rydberg atom is favored to emit to the direction of the maximum of the asymmetric optical field. Our results on the one hand intuitively visualize the dissociative frustrated double ionization of molecules, and on the other hand open the possibility to selectively excite the heavy fragment ejected from a molecule.

Comparison Study of Strong-Field Ionization of Molecules and Atoms by Bicircular Two-Color Femtosecond Laser Pulses.

We experimentally investigate the single and double ionization of N_{2} and O_{2} molecules in bicircular two-color femtosecond laser pulses, and compare with their companion atoms of Ar and Xe with comparable ionization thresholds. Electron recollision assisted enhanced ionization is observed in N_{2} and Ar by controlling the helicity and field ratio between the two colors, whereas the enhanced ionization via the recollision is almost absent in O_{2} and Xe. Our S-matrix simulations clearly reveal the crucial role of the detailed electronic structures of N_{2} and O_{2} on the two-dimensional recollision of the electrons driven by the bicircular two-color laser fields. As compared to Ar, the resonant multiphoton excitation dominates the double ionization of Xe.

Photon Energy Deposition in Strong-Field Single Ionization of Multielectron Molecules.

Molecules exposed to strong laser fields may coherently absorb multiple photons and deposit the energy into electrons and nuclei, triggering the succeeding dynamics as the primary stage of the light-molecule interaction. We experimentally explore the electron-nuclear sharing of the absorbed photon energy in above-threshold multiphoton single ionization of multielectron molecules. Using CO as a prototype, vibrational and orbital resolved electron-nuclear sharing of the photon energy is observed. Different from the simplest one- or two-electron systems, the participation of the multiple orbitals and the coupling of various electronic states in the strong-field ionization and dissociation processes alter the photon energy deposition dynamics of the multielectron molecule. The population of numerous vibrational states of the molecular cation as the energy reservoir in the ionization process plays an important role in photon energy sharing between the emitted electron and the nuclear fragments.

Coded Cooperation for Multiway Relaying in Wireless Sensor Networks.

Wireless sensor networks have been considered as an enabling technology for constructing smart cities. One important feature of wireless sensor networks is that the sensor nodes collaborate in some manner for communications. In this manuscript, we focus on the model of multiway relaying with full data exchange where each user wants to transmit and receive data to and from all other users in the network. We derive the capacity region for this specific model and propose a coding strategy through coset encoding. To obtain good performance with practical codes, we choose spatially-coupled LDPC (SC-LDPC) codes for the coded cooperation. In particular, for the message broadcasting from the relay, we construct multi-edge-type (MET) SC-LDPC codes by repeatedly applying coset encoding. Due to the capacity-achieving property of the SC-LDPC codes, we prove that the capacity region can theoretically be achieved by the proposed MET SC-LDPC codes. Numerical results with finite node degrees are provided, which show that the achievable rates approach the boundary of the capacity region in both binary erasure channels and additive white Gaussian channels.

Recurrent Syncope Episodes during Spinal Anesthesia for Perianal Abscess Drainage: A Case Report Emphasizing Pain as a Trigger.

BACKGROUND Vasovagal syncope is a loss of consciousness caused by decreased arterial pressure and cerebral blood flow. The characteristic features of vasovagal syncope include cardiovascular inhibition caused by neural reflexes, accompanied by vasodilation and bradycardia. To date, there is little literature to report several episodes of syncope under spinal anesthesia during the perioperative period for drainage of an anal abscess. The purpose of this article is to alert clinical practitioners to the early identification of the underlying causes of vasovagal syncope and to facilitate timely and effective management strategies. CASE REPORT We present the case of a 44-year-old man with a perianal abscess who was scheduled for an incision and drainage procedure for the abscess under spinal anesthesia. Preoperative assessment revealed no history of cardiac disease, neurological disorders, or drug allergies. During the perioperative period, the patient experienced 3 episodes of syncope: 1 episode during puncture of spinal anesthesia, and the others at 6.5 h and 8.5 h after the procedure. The patient was discharged 4 days later, and a 30-day postoperative follow-up showed good recovery, without any episodes of syncope. CONCLUSIONS We described a case of 3 episodes of vasovagal syncope occurring in a patient during the perioperative period of drainage of perianal abscess under spinal anesthesia. Pain may have been the main cause of vasovagal syncope in this patient. To avoid vasovagal syncope, it is best for anesthesiologists to choose the lateral position to perform spinal anesthesia and to provide good perioperative pain management for these patients.

Establishment and Validation of a Postoperative VTE Prediction Model in Patients with Colorectal Cancer Undergoing Radical Resection: CRSPOT Nomogram.

Venous thromboembolism (VTE) is a life-threatening postoperative complication of malignant tumors. We identified risk factors for postoperative VTE in patients undergoing radical resection of colorectal cancer (CRC) and constructed and validated a clinical prediction model. Clinical data of 982 patients undergoing radical resection of CRC from September 1, 2020, to March 31, 2022, in Ningxia Medical University General Hospital were analyzed retrospectively. Patients were randomly divided into training (n = 617) and validation groups (n = 264). Data included baseline characteristics, preoperative complications, examination results, and intraoperative and postoperative indicators. Logistic regression analysis was used to determine risk factors, build a predictive model, and draw a predictive nomogram (CRSPOT). Receiver operating characteristics (ROC) curve was used to calculate the area under the curve (AUC) for evaluating the model's predictive ability. Independent risk factors for postoperative VTE were as follows: postoperative hemoglobin of <10 g/L (odds ratio [OR] 0.413, 95% confidence interval [CI] 0.220-0.777), postoperative D-dimer of ≥3.5µg/mL (OR 2.156, 95% CI 1.145-4.061), BMI of ≥25 kg/m2 (OR 2.313, 95% CI 1.225-4.369), operation time of ≥4 h (OR 2.292, 95% CI 1.232-4.262), lower extremity varicose veins (OR 4.499, 95% CI 1.764-11.476), postoperative ileus (OR 5.760, 95% CI 2.031-16.337), and postoperative hypoxemia (OR 9.230, 95% CI 4.562-18.672). The nomogram's AUC was 0.826, demonstrating a reliable predictive ability. The CRSPOT nomogram reliably predicts postoperative VTE in patients undergoing radical resection of CRC, identifying high-risk patients early, allowing early implementation of antithrombotic strategies, and helping to reduce the incidence and mortality of postoperative VTE.

Regional transportation and influence of atmospheric aerosols triggered by Tonga volcanic eruption.

A cataclysmic submarine volcano at Hunga Tonga-HungaHa'apai (HTHH) near Tonga, erupted violently on 15 January 2022, which injected a plume of ash cloud soaring into the upper atmosphere. In this study, we examined the regional transportation and potential influence of atmospheric aerosols triggered by HTHH volcano, based on active and passive satellite products, ground-based observations, multi-source reanalysis datasets and atmospheric radiative transfer model. The results indicated that about 0.7 Tg (1 Tg = 109 kg) sulfur dioxide (SO2) gas were emitted into stratosphere from the HTHH volcano, and were lifted to an altitude of 30 km. The regional averaged SO2 columnar content over the western Tonga increased by 10-36 Dobson Units (DU), and the mean aerosol optical thickness (AOT) retrieved from satellite products increased to 0.25-0.34. The stratospheric AOT values caused by HTHH emissions increased to 0.03, 0.20, and 0.23 on 16, 17, and 19 January, respectively, accounting for 1.5%, 21.9%, and 31.1% of total AOT. Ground-based observations also showed an AOT increase of 0.25-0.43, with the maximum daily average of 0.46-0.71 appeared on 17 January. The volcanic aerosols were remarkably dominated by fine-mode particles and posed strong light-scattering and hygroscopic abilities. Consequently, the mean downward surface net shortwave radiative flux was reduced by 2.45-11.9 Wm-2 on different regional scales, and the surface temperature decreased by 0.16-0.42 K. The maximum aerosol extinction coefficient was 0.51 km-1 appeared at 27 km, which resulted in an instantaneous shortwave heating rate of 1.80 Khour-1. These volcanic materials stayed stable in the stratosphere and completed one circle around the earth within 15 days. This would exert a profound influence on the energy budget, water vapor and ozone exchange in the stratosphere, which deserves to be further studied.

A systematic review, meta-analysis and meta-regression of the global prevalence of foodborne Vibrio spp. infection in fishes: A persistent public health concern.

Human vibriosis, caused by pathogenic Vibrio spp., such as Vibrio parahaemolyticus, Vibrio cholerae and Vibrio vulnificus, has been increasing worldwide, mediated by increasing consumption of seafood. The present study was conducted to examine the global prevalence of V. vulnificus, V. parahaemolyticus and V. cholerae in fishes. We searched PubMed, Web of Science, Scopus, and CNKI for peer-reviewed articles and dissertations prior to December 31, 2021. A total of 24,831 articles were retrieved, and 82 articles contained 61 fish families were included. The global pooled prevalence of V. cholerae, V. parahaemolyticus and V. vulnificus in fishes was 9.56 % (95 % CI: 2.12-20.92), 24.77 % (95 % CI: 17.40-32.93) and 5.29 % (95 % CI: 0.38-13.61), respectively. Subgroup and meta-regression analyses showed that study-level covariates, including temperature, country, continent, origin and detection methods partly explained the between-study heterogeneity. These heterogeneities were underpinned by differences of the three Vibrio spp. in fishes at geographical and climatic scales. These results reveal a high global prevalence of pathogenic Vibrio spp. in fishes and highlight the need for implementation of more effective prevention and control measures to reduce food-borne infection in humans.