TEMPO/O2 Synergistically Mediated BiBrO-Photocatalyzed Decarboxylative Phosphorylation of N-Arylglycines.

With both TEMPO and O2 (in air) as the homogeneous redox mediators, BiBrO as the heterogeneous semiconductor photocatalyst, the first example of semi-heterogeneous photocatalytic decarboxylative phosphorylation of N-arylglycines with diarylphosphine oxides was established. A series of α-amino phosphinoxides were efficiently synthesized.

Recyclable V2O5/g-C3N4 Heterojunction-Catalyzed Visible-Light-Promoted C3-H Trifluoromethylation of Quinoxalin-2-(1H)-ones.

A visible-light-initiated C-H trifluoromethylation of quinoxalin-2(1H)-ones was established using a Z-scheme V2O5/g-C3N4 heterojunction as a recyclable photocatalyst in an inert atmosphere at room temperature under additive-free and mild conditions. A variety of trifluoromethylated quinoxalin-2-(1H)-one derivatives were heterogeneously generated in moderate to high yields, exhibiting good functional group tolerance. Remarkably, the recyclable V2O5/g-C3N4 catalyst could be reused five times with a slight loss of catalytic activity.

Electrochemical Multicomponent Cascade Reaction for the Synthesis of Selenazol-2-amines with Elemental Selenium.

The first example of an electrochemical multicomponent synthesis of selenium-containing compounds with inexpensive and abundant elemental selenium as the selenating reagent was developed. A variety of selenazol-2-amines were constructed in high yields with good functional group tolerance under metal-free and chemical oxidant-free conditions.

Paired Electrolysis-Enabled Arylation of Quinoxalin-2(1H)-ones.

The first paired electrolysis-enabled arylation of quinoxalin-2(1H)-ones was achieved using cyanoarenes as the arylation reagents. A variety of 3-arylquinoxalin-2(1H)-ones with various important functional groups were obtained in moderate to good yields under metal- and chemical oxidant-free conditions. With a pair of reductive and oxidative processes occurring among the substrates and reaction intermediates, the power consumption can be dramatically reduced.

Use of extreme gradient boosting, light gradient boosting machine, and deep neural networks to evaluate the activity stage of extraocular muscles in thyroid-associated ophthalmopathy.

PURPOSE: To develop a machine learning model to evaluate the activity stage of extraocular muscles in thyroid-associated ophthalmopathy (TAO). METHODS: This study retrospectively analysed data from patients with TAO who underwent contrast-enhanced magnetic resonance imaging (MRI) from 2015 to 2022. Three independent machine learning models, namely, extreme gradient boosting (XGBoost), light gradient boosting machine (LightGBM), and deep neural networks (DNNs), were constructed using common clinical features. The performance of these models was compared using evaluation metrics such as the area under the receiver operating curve (AUC), accuracy, precision, recall, and F1 score. The importance of features was explained using Shapley additive explanations (SHAP). RESULTS: A total of 2561 eyes of 1479 TAO patients were included in this study. The original dataset was randomly divided into a training set (80%, n = 2048) and a test set (20%, n = 513). In the performance evaluation of the test set, the LightGBM model had the best diagnostic performance (AUC 0.9260). According to the SHAP results, features such as conjunctival congestion, swollen caruncles, oedema of the upper eyelid, course of TAO, and intraocular pressure had the most significant impact on the LightGBM model. CONCLUSION: This study used contrast-enhanced MRI as an objective evaluation criterion and constructed a LightGBM model based on readily accessible clinical data. The model had good classification performance, making it a promising artificial intelligence (AI)-assisted tool to help community hospitals evaluate the inflammatory activity of extraocular muscles in TAO patients in a timely manner.

Photosynthesis of 3-Alkylated Coumarins from Carboxylic Acids Catalyzed by a Na2S-Based Electron Donor-Acceptor Complex.

A simple and practical electron donor-acceptor (EDA) strategy to synthesize various 3-alkylated coumarins from easily available coumarins and naturally abundant carboxylic acids under photocatalyst-, oxidant-, and additive-free and mild conditions is reported. Using Na2S as the catalytic electron donor, a series of primary, secondary, and tertiary carbon radicals can be efficiently generated, and the EDA complex can be regenerated without an alkaline additive.

Visible-Light-Induced Annulation of Iodonium Ylides and 2-Isocyanobiaryls to Access 6-Arylated Phenanthridines.

A 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4-CzIPN)-photocatalyzed cascade arylation/cyclization reaction of 2-isocyanobiaryls and iodonium ylides was established for the synthesis of 6-arylated phenanthridines. This is the first example of employing iodonium ylides as aryl radical sources in a visible-light-induced radical cascade cyclization reaction.

Selectfluor-Mediated Electrophilic Annulation of 2-Alkynyl Biaryls with Diorganyl Diselenides.

A general and efficient method for the synthesis of various selanyl phenanthrenes/polycyclic heteroaromatics through the electrophilic annulation of 2-alkynyl biaryls with diorganyl diselenides under metal-free and mild conditions was established. The sulfanyl phenanthrene was also obtained in moderate yields.

Visible-light-initiated external photocatalyst-free synthesis of α,α-difluoro-ß-ketoamides from 4-aminocoumarins.

A concise and efficient ring-opening difluorination strategy was developed for the synthesis of highly functionalized hydroxy-containing α,α-difluoro-ß-ketoamides from the one-pot multicomponent reaction of 4-aminocoumarins, NFSI, and water in dimethyl carbonate (DMC) as a green solvent. The reactions were smoothly achieved under visible light irradiation in air at room temperature without the addition of any other external photocatalysts. With this protocol, various α,α-difluoro-ß-ketoamides were successfully synthesized under mild conditions (25 examples, 73-91% yields). This transition-metal-free synthetic procedure shows good functional group compatibility and attractive practical potential for large-scale synthesis.

Clinical features and factors affecting prognosis and partial deterioration of ocular papilloma: a retrospective study of 298 cases.

PURPOSE: This study aimed to analyze the clinicopathological features of ocular papilloma, a common benign tumor, and the risk factors related to its recurrence and partial deterioration. METHODS: We collected and analyzed the clinical information of 298 patients (51.68% males) with mean age of 41.54 ± 21.95 years, in the ophthalmology department of the West China Hospital. Clinical and pathological factors that might be related to papilloma recurrence and partial deterioration were studied. RESULTS: The top three papilloma sites were bulbar conjunctiva, eyelid skin and palpebral conjunctiva. Moreover, 3.59% of lesions presented a malignant transformation, and 16.28% of patients had one or more recurrences after an average follow-up of 4.47 years. The multivariate logistic regression model showed that multiple lesions were a risk factor for recurrence (p = 0.022, OR = 3.088, 95% CI: 1.180-8.079), while cryotherapy decreased the recurrence risk (p = 0.044, OR = 0.364, 95% CI: 0.136-0.972). Additionally, elderly patients and lesions on the corneal limbus or cornea had a higher risk of malignant transformation (p = 0.004 and 0.01, OR = 1.086 and 7.827, 95% CI: 1.027-1.150 and 1.629-37.596, respectively). CONCLUSION: Ocular papilloma usually occurs in middle-aged and young patients, with no significant gender differences. Older patients and lesions on the corneal limbus or cornea are risk factors for partial malignant transformation. Finally, multiple lesions were a risk factor for recurrence, and cryotherapy reduced the recurrence rate.

Clinical phenotypes of euthyroid, hyperthyroid, and hypothyroid thyroid-associated ophthalmopathy.

OBJECTIVE: To compare the demographic and clinical phenotypes of thyroid-associated ophthalmopathy (TAO) with euthyroidism (Eu-TAO), hyperthyroidism (Hr-TAO), and hypothyroidism (Ho-TAO). METHODS: We enrolled 2158 TAO patients in this retrospective study and assessed their demographics, clinical manifestations, activity, and severity. RESULTS: Among the enrolled patients, 526 (24.37%) had Eu-TAO, 1544 (71.55%) had Hr-TAO, and 88 (4.08%) had Ho-TAO. Compared to Hr-TAO (2.02) and Ho-TAO (2.52) patients, Eu-TAO (1.57) patients had the lowest female-to-male ratio (p = 0.026). The mean ages of Eu-TAO, Hr-TAO, and Ho-TAO patients were 43.11 ± 12.05, 42.23 ± 13.63, and 47.39 ± 13.28 years, respectively (p = 0.001). Patients with Eu-TAO had more unilateral involvement (50% vs. 14.38% vs. 21.59%, p < 0.001) than Hr-TAO or Ho-TAO patients. Clinically active TAO patients presented 8.56% in euthyroid vs. 13.86% in hyperthyroid vs. 11.36% in hypothyroid (p = 0.006). Regarding the severity of the European Group on Graves' Orbitopathy (EUGOGO) classification among euthyroid, hyperthyroid, and hypothyroid patients, mild TAO was present in 67.68, 54.27, and 72.72% of participants, moderate-to-severe TAO in 31.18, 42.49, and 26.14%, and sight-threatening TAO in 1.14, 3.24, and 1.14%, respectively. Eu-TAO was positively correlated with unilateral involvement (OR = 5.671, p < 0.001) and age (OR = 1.013, p = 0.003) and negatively correlated with the female-to-male ratio (OR = 0.656, p < 0.001) and TAO severity (OR = 0.742, p < 0.01). CONCLUSIONS: Eu-TAO patients are older and less likely to be female, and show more unilateral and milder clinical phenotypes than hyper/hypothyroid TAO patients.

Orbital solitary fibrous tumours: clinicopathological characteristics and recurrence prediction.

BACKGROUND: SFTs are thought to have an unpredictable clinical course and currently have no recognized prognostic criterion. Our study aimed to determine the relationship between clinicopathological characteristics and the prognosis of patients with orbital SFTs. METHODS: The clinicopathological features of these patients were extracted from clinical records. The relationships between these features and prognosis were analysed. RESULTS: The positive rates of CD34, CD99, Blc2, and STAT6 expression were 90.3%, 90.3%, 83.9%, and 100%, respectively. The tumour recurrence rate was 38.7%. A higher recurrence rate was observed in patients with Ki67 index ≥ 5 (56.25% vs. 20%, P = 0.038). CONCLUSION: A Ki67 index ≥ 5 was an effective parameter for predicting tumour recurrence of orbital SFTs. Close follow-up is needed for these patients.

Occult intraocular aluminium foreign body causing rhegmatogenous retinal detachment: a case report.

BACKGROUND: Ocular trauma is complex and varied, and some occult intraocular foreign bodies (IOFBs) can lead to uncommon symptoms and signs. We report a case of rhegmatogenous retinal detachment (no obvious wound, no pain, no intraocular infection or other symptoms) caused by an occult intraocular aluminium foreign body, which could have been easily missed. CASE PRESENTATION: A 42-year-old male presented to the outpatient department of our hospital complaining of fluttering black dots and decreased vision in his left eye that began 3 months earlier. He was diagnosed with "floaters" at a community hospital. He denied a history of ocular trauma or previous surgery. The cornea and lens of the left eye were clear. A small patch of pigmentation was noted in the temporal sclera. Fundoscopy revealed macula-off retinal detachment. After mydriasis, elliptical holes were seen in the peripheral retina at 2:30, and a suspicious hyperreflective strip was found under the anterior lip of the retina by Goldmann three-mirror contact lens examination; the strip was confirmed to be an IOFB by orbital CT. The IOFB was removed through pars plana vitrectomy without any complications. CONCLUSION: Unlike iron and copper IOFBs, aluminium IOFBs are more inert and more likely to be missed. For people with special occupations (construction workers, mechanics, etc.), when abnormal pigmentation of the sclera is found, the possibility of foreign bodies in the eye should be considered. In the process of disease diagnosis and treatment, it is necessary to ask for a detailed history, including occupation history and practice, and perform careful physical and targeted examinations. Such comprehensive analysis regarding the above information will minimize the chance of missed diagnosis.Awareness of occult IOFB in high risk occupations and prompt referral to a retinal surgeon is of outmost importance.

Erdheim-Chester disease with bilateral orbital masses and multi-systemic symptoms: two case reports.

BACKGROUND: Erdheim-Chester disease (ECD) is a rare histiocytic disorder characterized by multisystem xanthogranulomatous infiltration by lipid-laden histiocytes. We report two cases of ECD involving the orbit and describe their clinicopathologic factors, treatments, and prognosis. One was a rare case of ECD complicated with primary thrombocytosis. CASE PRESENTATION: This study describes two patients with bilateral orbital ECD. Both presented with proptosis and visual loss; imaging findings showed bilateral intraorbital masses. Both had different degrees of systemic symptoms (pleural effusion, pericardial effusion, ascites, and heart failure) before the ocular symptoms and did not find the cause before ophthalmic tumor resection and pathological biopsy. The diagnosis of ECD was confirmed after pathological biopsy and detection of BRAFV600E mutation. Patient 2 also with primary thrombocytosis and had a CALR mutation as well as the BRAFV600E mutation. Both patients were recommended to receive targeted therapy. Patient 1 refused targeted therapy for financial reasons and was discharged after local radiotherapy only. The patient had no light perception in either eye and no improvement in systemic symptoms. Patient 2 began targeted treatment after diagnosis and reached the discharge criteria 2 weeks later. He is in good condition at present, but unfortunately, his eyesight has not improved because of the irreversible damage to his visual function. CONCLUSION: ECD is easily misdiagnosed and missed because of its rarity and diverse clinical manifestations. Orbital involvement is common in ECD, and surgery is the most frequently employed approach. Despite the surgical resection is not curative, its significance lies in biopsy to establish diagnosis and/or surgical debulking to relieve mass effect, minimizing further impairment of visual function. Targeted therapy is the most effective treatment for patients with a positive BRAF mutation gene. Evaluation of a concomitant myeloid neoplasm is also critical before initiating targeted therapies for refractory ECD.

Clinical characteristics and treatment outcomes of secondary ocular adnexal lymphoma.

BACKGROUND: To describe the clinical characteristics and treatment outcomes of secondary ocular adnexal lymphoma (OAL), and emphasise the impact of timely biopsy and systemic evaluation on the diagnosis and treatment. METHODS: The data of patients with secondary OAL in our hospital from January 2010 to June 2021 were retrospectively reviewed. RESULTS: A total of 54 patients (30 men and 24 women) were included in the study. The mean age at presentation was 60 years (median 62 years; range 37-83 years). The main symptoms included ocular mass (74%), periorbital swelling (43%), and proptosis (39%). The main histopathological types were mucosa-associated lymphoid tissue lymphoma (30%), diffuse large B-cell lymphoma (28%), and natural killer/T-cell lymphoma (18%). In particular, three patients exhibited different pathological types of ocular lymphoma compared to previously diagnosed systemic lymphoma. The most common site of ocular and systemic involvement was the orbit (85%) and lymph nodes (56%), respectively, and 25 (46%) patients had occult extraocular lesions. Additionally, the 5-year overall survival rate of the entire cohort was 56%, and significant differences were observed between the three main pathological types and stages of the disease (all p < 0.001). CONCLUSIONS: Secondary OAL is a rare disease with a poor prognosis. That the disease is associated with a more aggressive pathological type is well established, indolent lymphoma is not uncommon. Furthermore, OAL and previously diagnosed systemic lymphoma may be pathologically distinct in some patients. Therefore, we recommend a prompt excision biopsy and a thorough systemic evaluation of patients with suspected OAL.

Paired Electrolysis Enabled Cyanation of Diaryl Diselenides with KSCN Leading to Aryl Selenocyanates.

The first example of paired electrolysis-enabled cyanation of diaryl diselenides, with KSCN as the green cyanating agent, has been developed. A broad range of aryl selenocyanates can be efficiently synthesized under chemical-oxidant- and additive-free, energy-saving and mild conditions.

Electrocatalytic three-component synthesis of 4-halopyrazoles with sodium halide as the halogen source.

The first example of the electrocatalytic multicomponent synthesis of 4-chloro/bromo/iodopyrazoles from hydrazines, acetylacetones and sodium halides under chemical oxidant- and external electrolyte-free conditions has been developed. Sodium halides played a dual role as a halogenation reagent and a supporting electrolyte. Mechanism studies revealed that the bromination reaction proceeded via an ionic pathway, whereas both chlorination and iodination proceeded via a radical pathway.

A Rare Case of Orbitocranial Penetrating Injury with Intracranial Wooden Foreign Body Residue.

Orbitocranial penetrating injuries (OPIs) caused by wooden foreign bodies (WFBs) are very rare and life threatening. Their diagnosis and treatment could be challenging for an ophthalmologist, requiring us to remain alert for possible intracranial extension. We present a case of a 52-year-old man with a residual wooden foreign body in the left frontal lobe. He had a notable history of trauma from a fall on a tree stump and surgical removal of a wooden foreign body from his left orbit 6 years ago. He was referred to us due to recurrent discharge from the eyelid wound. Wooden foreign body residue was successfully removed with a carefully planned craniotomy without complications. This case describes the clinical manifestation, radiographic features, and treatment of this rare trauma, with an emphasis on imaging diagnosis and multi-disciplinary management.

Altered peripapillary vessel density and nerve fiber layer thickness in thyroid-associated ophthalmopathy using optical coherence tomography angiography.

OBJECTIVE: To measure the peripapillary vessel density (VD) and retinal nerve fiber layer thickness (RNFLT) in thyroid-associated ophthalmopathy (TAO) and dysthyroid optic neuropathy (DON) patients using optical coherence tomography angiography (OCTA), and determine their prognostic relevance. METHODS: Forty-three TAO patients with or without DON (82 eyes in total) and 26 healthy subjects (52 eyes) were enrolled. All participants underwent ophthalmology and endocrinology tests. The peripapillary VD in retinal peripapillary capillary layer and RNFLT were analyzed using OCTA images. Multiple linear regression analysis was used to assess the relationship between peripapillary VD /RNFLT and the relevant factors. RESULTS: The total peripapillary VD and RNFLT were significantly lower in the DON patients compared to the other groups (P < 0.001, 95% confidence intervals), and each quadrant of VD and RNFLT showed similar results except temporal RNFLT. No significant difference was seen between the RNFLT and VD of active non-DON (ANDON), inactive non-DON (NDON) patients and normal control (NC) group. Multivariable linear regression model showed that high IOP is an independent risk factor for lower peripapillary VD and RNFLT (ß = -0.465, P < 0.001 and ß = -0.343, P = 0.002 respectively). CONCLUSION: OCTA parameters are suitable indicators for diagnosing DON. TAO patients with high IOP should be considered at high risk of retinal vessel and nerve fiber layer deterioration. In addition, patients with TAO should be advised to quit smoking since it could affect peripapillary VD and RNFLT.

[Clinical Analysis of 2 170 Cases of Thyroid-Associated Ophthalmopathy Involving Extraocular Muscles].

OBJECTIVE: To explore the clinical features of thyroid-associated ophthalmopathy (TAO) with extraocular muscle involvement. METHODS: The data of 2170 TAO patients who were seen at the Orbital Disease Clinic, West China Hospital, Sichuan University from September, 2009 to January, 2020 were collected retrospectively. The extraocular muscle involvement of these patients was confirmed by CT or MRI. Their general condition, medical history, clinical manifestations and imaging features were analyzed retrospectively. RESULTS: Among the 2170 TAO patients, 932 were male and 1238 were female. The mean (± SD) age of all the patients was (46.95±13.06) years, ranging between 6 and 85. 1684 patients (77.60%) suffered from hyperthyroidism, 13 patients (0.59%) had thyroid cancer, 80 patients (3.69%) had hypothyroidism, and 393 patients (18.11%) had normal thyroid function. Proptosis (55.25%) and diplopia (33.09%) were the main reasons for their visits to the clinic, and restricted eye movements (83.46%) was the most common sign. 122 patients with a mean age of (53.24±13.07) years did not show any eyelid sign and had only extraocular muscle involvement. The 2170 TAO patients had a total of 3799 eyes of extrocular muscle involvement, with 541 patients experiencing monocular involvement and 1629 patients, binocular involvement; 1204 eyes (31.69%) had a single extrocular muscle involved and 2595 eyes (68.31%) had multiple extrocular muscles involved. Inferior rectus was the most commonly involved muscle, followed by superior rectus, medial rectus, and lateral rectus in descending order of involvement frequency. Of the 1014 patients who underwent enhanced MRI, 71.99% were shown to be in the active phase. 69.03% of the 775 patients identified as being in inactive phase according to their clinical activity score (CAS) were shown to be in the active phase according to their MRI results. CONCLUSION: TAO patients with extraocular muscle involvement have their own specific clinical manifestations. CT and MRI can both be used to assist in the diagnosis of extraocular muscle involvement. MRI can be used to assess the pathological stage of extraocular muscles and is more sensitive than CAS.