Photoelectrocatalysis for Hydrogen Evolution Ventures into the World of Organic Synthesis.

The use of light as a catalytic prompt for the synthesis of industrial relevant compounds is widely explored in the past years, with a special consideration over the hydrogen evolution reaction (HER). However, semiconductors for heterogeneous photocatalysis suffer from fast charge recombination and, consequently, low solar-to-hydrogen efficiency. These drawbacks can be mitigated by coupling photocatalysts with an external circuit that can physically separate the photogenerated charge carriers (electrons and holes). For this reason, photoelectrochemical (PEC) production of hydrogen is under the spotlight as promising green and sustainable technique and widely investigated in numerous publications. However, considering that a significant fraction of the hydrogen produced is used for reduction processes, the development of PEC devices for direct in situ hydrogenation can address the challenges associated with hydrogen storage and distribution. This Perspective aims at highlighting the fundamental aspects of HER from PEC systems, and how these can be harnessed toward the implementation of suitable settings for the hydrogenation of organic compounds of industrial value.

Comparative Study of the Efficacy of Anti-CGRP mAbs on Migraineurs: Analysis of the First Year of Therapy, 1-Month Suspension Period, and Reprisal.

Background: Few studies compare the clinical effectiveness of the three anti-CGRP mAbs. Moreover, no studies compare their efficacy during suspension and reprisal. Our study aimed to compare the efficacy of migraine frequency, intensity, and symptomatic medication intake during the first year of therapy, a 1-month suspension period, and a 3-month drug reprisal. Methods: A total of 160 migraineurs (chronic and high-frequency episodic) were treated with anti-CGRP mAbs (49 with fremanezumab, 55 with erenumab, and 55 with galcanezumab) for 12 months. They discontinued the therapy for 1 month and then reprised the therapy. In the three groups, we analyzed and compared the migraine days per month, migraine intensity, and symptomatic medication intake per month at baseline, 3-month, 6-month, and 12-month follow-up. We also compared these variables during the 1-month suspension and 3 months after the reprisal of the therapy. We compared the data and evaluated the response rate (>50% reduction in migraine days per month) at different follow-ups. This comparison was also performed separately for chronic and high-frequency episodic migraineurs. Results: There was no statistical difference in monthly migraine days, intensity, or symptomatic medication intake per month at the different follow-ups. Moreover, there was no difference in the response rate overall. However, in chronic migraineurs treated with galcanezumab, the response rate was higher during the 1-month suspension when compared to fremanezumab and erenumab. In high-frequency episodic migraineurs, fremanezumab had a higher response rate at 12-month follow-up when compared to galcanezumab and erenumab. Conclusions: In our study, the three anti-CGRP mAbs presented a similar response, with no significant differences, during the first year of therapy, the suspension period, and 3 months after the drug reprisal. The response rate during the 1-month suspension period in chronic migraineurs may be higher with galcanezumab.

The use of alteplase, although safe, does not offer clear clinical advantages when mild stroke is non-disabling.

Introduction: It is unknown whether alteplase is effective and safe in patients with mild acute ischemic stroke (AIS). Determining whether symptoms are "disabling" or not is a crucial factor in the management of these patients. This study aimed to investigate the efficacy and safety of alteplase in patients with mild, non-disabling AIS. Methods: We included all consecutive patients admitted for AIS at our institution from January 2015 to May 2022 who presented a baseline NIHSS score of 0-5 and fit the criteria to receive intravenous thrombolysis. In order to select only subjects with non-disabling AIS, we excluded patients who scored more than 1 point in the following NIHSS single items: vision, language, neglect, and single limb. Patients who scored at least 1 point in the NIHSS consciousness item were excluded as well. This study is a retrospective analysis of a prospectively collected database. Results: After the application of the exclusion criteria, we included 319 patients, stratified into patients receiving and not receiving alteplase based on non-disabling symptoms. The two groups were comparable regarding demographic and clinical data. Rates of a 3-month favorable outcome, defined as a 3-month mRS score of 0-1, were similar, being 82.3% and 86.1% in the treated and untreated patients, respectively. Hemorrhagic complications and mortality occurred infrequently and were not affected by alteplase treatment. Discussion: This observational study suggests that the use of alteplase, although safe, is not associated with a better outcome in highly selected patients with non-disabling AIS.

Graphitic Carbon Nitride as Photocatalyst for the Direct Formylation of Anilines.

The use of graphitic carbon nitride (g-CN) for the photocatalytic radical formylation of anilines, which represents a more sustainable and attractive alternative to the currently used approaches, is reported herein. Our operationally simple method occurs under mild conditions, employing air as an oxidant. In particular, the chemistry is driven by the ability of g-CN to reach an electronically excited state upon visible-light absorption, which has a suitable potential energy to trigger the formation of reactive α-amino radical species from anilines. Mechanistic investigations also proved the key role of the g-CN to form reactive superoxide radicals from O2 via single electron transfer. Importantly, this photocatalytic transformation provides a variety of functionalized formamides (15 examples, up to 89 % yield).

Improvement in the fertility rate after placement of microsurgical shunts in men with recurrent varicocele.

OBJECTIVE: To evaluate the effectiveness of microsurgical shunts for secondary varicocele repair after ligation-like procedures, focusing on long-term functional outcomes. DESIGN: Long-term survey (mean follow-up, 8.5 years) of infertile men after secondary microsurgical reconstructive varicocelectomy. SETTING: University-based medical center. PATIENT(S): Thirty-four infertile men (group A, <30 years of age; and group B, >30 years) with recurrent palpable varicocele after varicocelectomy, according to Ivanissevich (n = 28), or after angiographic vein occlusion (n = 6). Ten patients presented bilateral recurrence. INTERVENTION(S): Microsurgical shunts between spermatic vein and inferior epigastric vein. MAIN OUTCOME MEASURE(S): Sperm count, pregnancy rate, and ultrasound evaluation of varicosity. RESULT(S): Complete disappearance of varicosity was achieved in 97.06% of patients, while in 2.94%, a consistent reduction in size was observed. In patients with severe infertility, a significant postoperative increase in seminal parameters was observed. Pregnancy rates were 43.75% in group A and 22.22% in group B. CONCLUSION(S): Microsurgical drainage in patients with recurrent varicocele after ligation-like procedures was shown to be an effective minimally invasive treatment, with immediate hemodynamic recovery of testicular venous outflow and excellent long-term results in patients with left or bilateral recurrences.