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Disulfide bonds are pivotal for the structure, function, and stability of proteins, and understanding ultraviolet (UV)-induced S-S bond cleavage is highly relevant for elucidating the fundamental mechanisms underlying protein photochemistry. Here, the near-UV photodecomposition mechanisms in gas-phase dimethyl disulfide, a prototype system with a S-S bond, are probed by ultrafast transient X-ray absorption spectroscopy. The evolving electronic structure during and after the dissociation is simultaneously monitored at the sulfur L1,2,3-edges and the carbon K-edge with 100 fs (FWHM) temporal resolution using the broadband soft X-ray spectrum from a femtosecond high-order harmonics light source. Dissociation products are identified with the help of ADC and RASPT2 electronic-structure calculations. Rapid dissociation into two CH3S radicals within 120 ± 30 fs is identified as the major relaxation pathway after excitation with 267 nm radiation. Additionally, a 30 ± 10% contribution from asymmetric CH3S2 + CH3 dissociation is indicated by the appearance of CH3 radicals, which is, however, at least partly the result of multiphoton excitation.

Rare-earth-containing materials featuring rare-earth–chalcogen (RE–E) coordination are of interest as optical and magnetic materials with enhanced properties over their counterparts with O-coordination. Herein, a series of rare-earth chalcogenidotetrachloride complexes of the general formula [η5-Cp*RE(μ-Cl)(THF)]3(μ3-Cl)(μ3-E) (RE3ECl4: RE = Dy, Gd, Y; E = S, Se, Te; Cp* = pentamethylcyclopentadienide) were reported. Apart from for the identity of the rare-earth and chalcogen elements, these clusters share a common core motif composed of triangularly arranged RE atoms with one chloro ligand bridging each neighboring pair of RE atoms; the trimetallic plane is additionally capped by triply bridging chloro and chalcogenide ligands, one for each kind. Each RE atom is further coordinated with one Cp* and one THF ligand. Comparative magnetic and luminescence studies revealed fine but definitive differences due to using different metal and chalcogen elements. Experimental and computational studies have been used to gain insights into the dipolar and super-exchange interactions for the magnetically active Dy- and Gd-based clusters. [ABSTRACT FROM AUTHOR]

Background: The rearranged during transfection (RET) proto-oncogene fusion is common in papillary thyroid cancer (PTC), varying across ethnic groups. However, comprehensive comparisons of RET fusion types are limited. This study aims to identify predominant RET fusions and analyze their clinicopathological characteristics in a cohort of Chinese thyroid cancer cases. Methods: This single-center retrospective cohort study analyzed thyroid cancer data, utilizing next-generation sequencing on formalin-fixed, paraffin-embedded tissue samples. Detailed clinicopathological data of thyroid cancer cases with RET fusions were collected. Results: Among 2300 thyroid cancer cases, RET fusions were exclusively found in PTC or differentiated high-grade thyroid carcinoma (DHGTC) cases (2234 cases), absent in other types (66 cases). Of the 2234 PTC or DHGTC cases, 113 (5.06%) exhibited RET fusions, including 100 primary cases. Coiled-coil domain containing 6 (CCDC6)-RET fusions predominated (78.0%, 78/100), with nuclear receptor coactivator 4 (NCOA4)-RET fusions representing 22.0% (22/100). NCOA4-RET fusions were more prevalent in patients aged 45 years and older (54.5% vs. 28.2%, p = 0.021) and DHGTC cases (p < 0.05) and associated with higher rates of lymph node metastases (90.9% vs. 67.9%, p = 0.032). CCDC6-RET fusion exhibited a higher prevalence of Hashimoto's thyroiditis (HT) (67.9% vs. 22.7%, p < 0.001) and elevated thyroglobulin antibody levels (14.11 [1.86–174.32] IU/mL vs. 2.01 [1.14–15.41] IU/mL, p = 0.018). Moreover, CCDC6-RET fusion predominantly occurred in classical PTC (56.4%, 44/78) and infiltrative follicular PTC (17.9%, 14/78), whereas NCOA4-RET fusion was more frequent in classical PTC (36.4%, 8/22), solid PTC (27.3%, 6/22), and DHGTC (27.3%, 6/22). RET fusions with compound mutations were associated with older age (≥45 years) and bilateral thyroid involvement. Follow-up data showed a higher recurrence rate in the RET fusion group compared with the BRAFV600E mutation group (5.0% vs. 0.0%, p = 0.018). Although the NCOA4-RET group showed a numerically higher recurrence rate compared with CCDC6-RET (9.1% vs. 3.8%), this difference was not statistically significant (p = 0.559). Conclusions:RET fusions are specific to PTC or DHGTC cases among Chinese thyroid cancer cases. CCDC6-RET and NCOA4-RET fusions exhibited distinct clinicopathological features, with NCOA4-RET being more aggressive. [ABSTRACT FROM AUTHOR]

A fundamental chlorine-containing radical, CH2Cl, is generated by the ultrafast photodissociation of CH2ICl at 266 nm and studied at both the carbon K edge (∼284 eV) and chlorine L2,3 edge (∼200 eV) by femtosecond X-ray transient absorption spectroscopy. The electronic structure of CH2Cl radical is characterized by a prominent new carbon 1s X-ray absorption feature at lower energy, resulting from a transition to the half-filled frontier carbon 2p orbital (singly occupied molecular orbital of the radical; SOMO). Shifts of other core-to-valence absorption features upon photodissociation of CH2ICl to yield ·CH2Cl indicate changes in the energies of core-level transitions of carbon and chlorine to the σ*(C-Cl) valence orbital. When the C-I bond breaks, loss of the electron-withdrawing iodine atom donates electron density back to carbon and shields the carbon 1s core level, resulting in a ∼0.8 eV red shift of the carbon 1s to σ*(C-Cl) transition. Meanwhile, the 2p inner shell of the chlorine atom in the radical is less impacted by the iodine atom removal, as demonstrated by the observation of a ∼0.6 eV blue shift of the transitions at the chlorine L2,3 edges, mainly due to the stronger C-Cl bond and the increased energy of the σ*(C-Cl) orbital. The results suggest that the shift in the carbon 1s orbital is greater than the shift in the σ*(C-Cl) orbital upon going from the closed-shell molecule to the radical. Ab initio calculations using the equation of motion coupled-cluster theory establish rigorous assignment and positions of the X-ray spectral features in the parent molecule and the location of the SOMO in the CH2Cl radical.

The ultraviolet-induced photochemistry of five-membered heterocyclic rings often involves ring opening as a prominent excited-state relaxation pathway. The identification of this particular photoinduced mechanism, however, presents a challenge for many experimental methods. We show that femtosecond X-ray transient absorption spectroscopy at the carbon K-edge (∼284 eV) provides core-to-valence spectral fingerprints that enable the unambiguous identification of ring-opened isomers of organic heterocycles. The unique differences in the electronic structure between a carbon atom bonded to the oxygen in the ring versus a carbon atom set free of the oxygen in the ring-opened product are readily apparent in the X-ray spectra. Ultrafast ring opening via C-O bond fission occurs within ∼350 fs in 266-nm photoexcited furfural, as evidenced by fingerprint core (carbon 1s) electronic transitions into a nonbonding orbital of the open-chain carbene intermediate at 283.3 eV. The lack of recovery of the 1sπ* ground-state depletion in furfural at 286.4 eV indicates that internal conversion to the ground state is a minor channel. These experimental results, augmented by recent advances in the generation of isolated attosecond pulses at the carbon K-edge, will pave the way for probing ring-opened conical intersection dynamics in the future.

Sulfur mustard is a chemical warfare agent that poses a significant threat to public health and national security owing to its ease of preparation, high stability, and potential to cause incapacitation. Effective detection of sulfur mustard has been the main focus in the field of chemical defense. Fluorescence visual detection of sulfur mustard has been widely used in the research and development of detection devices for individual soldiers and real-time environmental monitoring, mainly owing to its high selectivity, high sensitivity, low cost, and user-friendly operation. The development of fluorescent sensors is vital for advancing fluorescence-based detection technology in sulfur mustard detection. In this paper, an overview of recent achievements in the study of fluorescent sensors for sulfur mustard detection is presented and insights into future developments in this field is provided. [ABSTRACT FROM AUTHOR]

Background and purpose The clinical significance of carbon dioxide combining power (CO2CP) in ischaemic cerebrovascular disease is not well established, and the role of CO2CP in the prognosis of acute ischaemic stroke (AIS) or transient ischaemic attack (TIA) has not been reported. The objective of the study was to investigate the associations between CO2CP and clinical outcomes in patients with AIS or TIA.Methods Data were derived from the China National Stroke Registry III. Patients were classified into five groups by quintiles of CO2CP levels and three groups according to the normal range of CO2CP (23–29 mmol/L). Multivariable Cox and logistic regressions were adopted to explore the associations of CO2CP levels with all-cause death and poor functional outcomes (modified Rankin Scale (mRS) 3–6/2–6) at 3 months and 1 year.Results Among 9531 patients included in the study, the median (IQR) CO2CP was 24.9 (23.0–27.0) mmol/L. After adjustment for potential confounders, patients in the first CO2CP quintile (21.1–23.3 mmol/L) had higher risk of all-cause death and poor functional outcomes (mRS score of 3–6/2–6) (HR or OR with 95% CI 2.37 (1.32 to 4.25), 1.49 (1.20 to 1.83) and 1.21 (1.03 to 1.42), respectively) compared with those in the fourth quintile. Similar results were found for outcomes at 1 year. Furthermore, all associations were also significant when CO2CP was

Thrombosis, induced by abnormal coagulation or fibrinolytic systems, is the most common pathology associated with many life-threatening cardio-cerebrovascular diseases. However, first-line anticoagulant drugs suffer from rapid drug elimination and risk of hemorrhagic complications. Here, we developed an in situ formed depot of elastin-like polypeptide (ELP)-hirudin fusion protein with a prodrug-like feature for long-term antithrombotic therapy. Highly secretory expression of the fusion protein was achieved with the assistance of the Ffu312 tag. Integration of hirudin, ELP, and responsive moiety can customize fusion proteins with properties of adjustable in vivo retention and controllable recovery of drug bioactivity. After subcutaneous injection, the fusion protein can form a reservoir through temperature-induced coacervation of ELP and slowly diffuse into the blood circulation. The biological activity of hirudin is shielded due to the N-terminal modification, while the activated key proteases upon thrombus occurrence trigger the cleavage of fusion protein together with the release of hirudin, which has antithrombotic activity to counteract thrombosis. We substantiated that the optimized fusion protein produced long-term antithrombotic effects without the risk of bleeding in multiple animal thrombosis models. [ABSTRACT FROM AUTHOR]

Invasive alien plants (IAPs) have serious environmental and economic impacts, especially in vulnerable areas of China. However, IAP richness distribution patterns, their driving factors, and the dynamic shifts in potential distribution areas remain elusive. We assessed IAP richness distribution patterns and drivers using 402 IAPs recorded in China at 88 926 occurrence points, and then predicted their potential distribution areas. The results show that IAP hotspots were mainly located in southeastern China, especially coastal areas of the South and East and large inland cities. Population density, gross domestic product (GDP), and four climate variables associated with precipitation and temperature jointly influenced the richness distribution pattern of all IAPs. Specifically, population density and GDP impacted the richness distribution pattern of narrow‐range IAPs, and population density, GDP, distance to the nearest national highway, and five climate variables affected the richness distribution pattern of widespread IAPs. Only GDP contributed significantly to the richness distribution pattern of the top 5% hotspot grid cells, whereas population density, GDP, and precipitation in the driest month (BIO14) significantly influenced the richness distribution patterns of hotspots for both the top 10% and top 20%. Prediction analysis demonstrated that southeastern China would have particularly high invasion risk under both current and future climate scenarios. Regions with increases in predicted species richness are more common (44.83–64.97%) than those with decreases, except under the Representative Concentration Pathway (RCP) 4.5 scenario. Climate change will contribute greatly to the expansion of potential IAP distribution areas under both optimistic (RCP 2.5) and pessimistic scenarios (RCP 8.5). The results of this study provide insights into the priority management of IAPs by developing promising strategies for the control and prevention of IAP invasion. [ABSTRACT FROM AUTHOR]