Electrochemical Synthesis of Itaconic Acid Derivatives via Chemodivergent Single and Double Carboxylation of Allenes with CO2.

Leveraging electrochemistry, a new synthesis of non-natural derivatives of itaconic acid is proposed by utilizing carbon dioxide (CO2) as a valuable C1 synthon. An electrochemical cross-electrophile coupling between allenoates and CO2 was targeted, allowing for the synthesis of both mono- and di-carboxylation products in a catalyst- and additive-free environment (yields up to 87%, 30 examples). Elaboration of the model mono-carboxylation product, and detailed cyclovoltammetric, as well as mechanistic analyses complete the present investigation.

Reductive cyclodimerization of chalcones: exploring the "self-adaptability" of galvanostatic electrosynthesis.

The "self-adaptability" of galvanostatic electrolysis was shown to assist a multistage unprecedented chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. The process, all involving the reductive events, delivered densely functionalized cyclopentanes featuring five contiguous stereocenters (25 examples, yields of up to 95%, dr values up to >20 : 1). Dedicated and combined experimental as well as electrochemical investigation revealed the key role of a dynamic kinetic resolution of the aldol intermediate for the reaction mechanism.

Major liver resections, perioperative issues and posthepatectomy liver failure: A comprehensive update for the anesthesiologist.

Significant advances in surgical techniques and relevant medium- and long-term outcomes over the past two decades have led to a substantial expansion in the indications for major liver resections. To support these outstanding results and to reduce perioperative complications, anesthesiologists must address and master key perioperative issues (preoperative assessment, proactive intraoperative anesthesia strategies, and implementation of the Enhanced Recovery After Surgery approach). Intensive care unit monitoring immediately following liver surgery remains a subject of active and often unresolved debate. Among postoperative complications, posthepatectomy liver failure (PHLF) occurs in different grades of severity (A-C) and frequency (9%-30%), and it is the main cause of 90-d postoperative mortality. PHLF, recently redefined with pragmatic clinical criteria and perioperative scores, can be predicted, prevented, or anticipated. This review highlights: (1) The systemic consequences of surgical manipulations anesthesiologists must respond to or prevent, to positively impact PHLF (a proactive approach); and (2) the maximal intensive treatment of PHLF, including artificial options, mainly based, so far, on Acute Liver Failure treatment(s), to buy time waiting for the recovery of the native liver or, when appropriate and in very selected cases, toward liver transplant. Such a clinical context requires a strong commitment to surgeons, anesthesiologists, and intensivists to work together, for a fruitful collaboration in a mandatory clinical continuum.

Heat shock protein 70 kDa (HSP70) increase in sea bass (Dicentrarchus labrax, L 1758) thymus after vaccination against Listonella anguillarum.

Heat shock proteins 70 kDa (HSP70) and apoptosis were investigated in thymus of sea bass juveniles (Dicentrarchus labrax) subsequently to a vaccination against Listonella (syn. Vibrio) anguillarum. HSP70 expression was measured by immunohistochemistry and immunoenzymatic methods, resulting in increase in HSP70 after bath immunization and persistent in fish exposed to an intraperitoneal (i.p.) booster. The HSP70 increase in thymus was suggested as induction in lymphocytic cells, to be related to immune system stimulation after vaccination. However, a thymic recruitment of lymphocyte subpopulations, characterized by higher expression of HSP70, was also hypothesized after vaccination. No apparent relationships were found between HSP70 and apoptosis. In fact, the vaccination did not modulate the apoptosis response, as measured by TUNEL assay and by immunohistochemistry for active caspase-3 expression. The lack of apoptosis effects could be ascribed to the use of inactivated bacteria that appeared not able to interfere with programmed cell death mechanisms. This manuscript aims to contribute to the knowledge of some biochemical features underlying the immunization, with a particular emphasis on the modulation of HSP70. However, further parameters involved in innate/adaptative immunity and apoptosis pathways have to be taken into account to well establish the functional role of HSP70 in fish vaccination.

Innovative vaccination protocol against vibriosis in Dicentrarchus labrax (L.) juveniles: improvement of immune parameters and protection to challenge.

The effect of vaccination on immune parameters of European sea bass, Dicentrarchus labrax, is not fully established, as well as surveyed throughout rearing till the commercial size. Furthermore, available information on the possible role of booster treatments is scarce. Sea bass juveniles were vaccinated against Listonella anguillarum using a commercial bivalent formulation administered by immersion (priming: 95 dph; booster: 165 dph) or by immersion (priming: 95 dph; booster: 165 dph) and subsequent i.p. injection (booster: 233 dph). Serum specific IgM and numbers of IgM(+) cells in head kidney and spleen evidenced B-cell responses mainly after the immersion booster, accompanied by increased TcR-ß transcripts and leucocyte respiratory burst. Immune enhancement was confirmed by the protection towards i.p. challenges with a virulent strain. RPS accounted for >70% in fish immersion-boosted and near 100% in fish further boosted i.p. Differently from usual farm practices, this innovative vaccination protocol proved to be highly effective. Booster treatments are therefore strongly recommended.