Eating through time: Understanding dietary practices across late prehistory in the northeastern Iberian Peninsula.

OBJECTIVE: This study seeks to contribute to the current understanding of dietary variation in the late Prehistory of the northeastern Iberian Peninsula by examining buccal dental microwear patterns alongside archeological data from the same populations. MATERIALS AND METHODS: Teeth from 84 adult individuals from eight distinct samples spanning the Middle-Late Neolithic to the Middle Bronze Age (Cova de l'Avi, Cova de Can Sadurní, Cova de la Guineu, Cova Foradada, Cova del Trader, Roc de les Orenetes, Cova del Gegant, Cova dels Galls Carboners) were analyzed using optical microscopy to examine buccal dental microwear patterns. RESULTS: The analysis did not reveal clear chronological contrasts in the dietary habits of these samples. Nevertheless, significant differences emerged among the samples, leading to their classification into two distinct sets based on the abrasiveness of the diet informed by the microwear patterns. These findings offer similarities and differences among samples in the Iberian Peninsula, shedding light on the diverse lifestyles of these individuals. DISCUSSION: Integrating our new results with other available proxies points to a multifaceted specialization in dietary patterns among these samples, influenced by factors such as habitat, resource selection, and available technology. By contextualizing the results within the broader context of the Iberian Peninsula, this research discerns shared characteristics and distinctive adaptations in the dietary practices and subsistence strategies of these groups. Ultimately, this study contributes to a deeper understanding of the intricate interplay between culture and environment in shaping human diets throughout late Prehistory.

Non-Directed C-H Arylation of Anisole Derivatives via Pd/S,O-Ligand Catalysis.

Non-directed C-H arylation is one of the most efficient methods to synthesize biaryl compounds without the need of the prefuctionalization of starting materials, or the installment and removal of directing groups on the substrate. A direct C-H arylation of simple arenes as limiting reactants remains a challenge. Here we disclose a non-directed C-H arylation of anisole derivatives as limiting reagents with aryl iodides under mild reaction conditions. The arylated products are obtained in synthetically useful yields and the arylation of bioactive molecules is also demonstrated. Key to the success of this methodology is the use of a one-step synthesized S,O-ligand.

meta-C-H Arylation of Aniline Derivatives via Palladium/ S,O-Ligand/Norbornene Cooperative Catalysis.

Aromatic amines are ubiquitous moieties in organic molecules and their direct functionalization is of great interest in many research areas due to their prevalence in pharmaceuticals and organic electronics. While several synthetic tools exist for the ortho- and para-functionalization of anilines, the functionalization of the less reactive meta-position is not easy to achieve with current methods. To date, the meta-C-H arylation of aniline derivatives has been restricted to either the use of directing groups & templates, or their transformation into anilides & quaternary anilinium salts. Herein, we report the first general and efficient meta-C-H-arylation of non-directed aniline derivatives via cooperative catalysis with a palladium-S,O-ligand-norbornene system. The reaction proceeds under mild conditions with a wide range of aniline derivatives and aryl iodides, while being operationally simple and scalable. Our preliminary mechanistic investigation-including the isolation of several palladium complexes and deuterium experiments-reveal useful insights into the substituent-effects of both the aniline-substrate and the norbornene-mediator during the meta-C-H activation step.

Mechanistic studies of the palladium-catalyzed S,O-ligand promoted C-H olefination of aromatic compounds.

Pd-catalyzed C-H functionalization reactions of non-directed substrates have recently emerged as an attractive alternative to the use of directing groups. Key to the success of these transformations has been the discovery of new ligands capable of increasing both the reactivity of the inert C-H bond and the selectivity of the process. Among them, a new type of S,O-ligand has been shown to be highly efficient in promoting a variety of Pd-catalyzed C-H olefination reactions of non-directed arenes. Despite the success of this type of S,O-ligand, its role in the C-H functionalization processes is unknown. Herein, we describe a detailed mechanistic study focused on elucidating the role of the S,O-ligand in the Pd-catalyzed C-H olefination of non-directed arenes. For this purpose, several mechanistic tools, including isolation and characterization of reactive intermediates, NMR and kinetic studies, isotope effects and DFT calculations have been employed. The data from these experiments suggest that the C-H activation is the rate-determining step in both cases with and without the S,O-ligand. Furthermore, the results indicate that the S,O-ligand triggers the formation of more reactive Pd cationic species, which explains the observed acceleration of the reaction. Together, these studies shed light on the role of the S,O-ligand in promoting Pd-catalyzed C-H functionalization reactions.

Modification of the inverted flap technique compared to conventional internal limiting membrane peeling in complete macular hole surgery.

AIM: To describe the efficacy of a modification of the superior inverted flap technique, with maculorrhexis, in vitrectomy for full-thickness macular hole (MH) surgery compared to internal limiting membrane peeling (ILM). METHODS: Retrospective and comparative study of patients with MH. In group A, a superior ILM flap is created to cover the macular hole, and in group B conventional ILM peeling was performed. RESULTS: A total of 80 eyes were included (44 group A and 36 group B). MH closure occurred in 100% in group A and 91.67% in group B (p = 0.0869). There were more U-type closures in group A(90.91%) than in group B(58.33%), p = 0.0017. Both groups showed Best corrected visual acuity (BCVA) improvement at 3 and 6 months. At 3 months BCVA in group A was significantly better but at 6 months results were similar. Ellipsoid layer (EZ) recovery at 6 months was achieved in 81.82% patients in group A and 52.78% in B (p = 0.005), and external limiting membrane in 81.82% in group A and 69.44% in B (p = 0.1957). CONCLUSIONS: The superior inverted flap maculorrhexis technique is suitable for idiopathic MH treatment, with better anatomical and non-inferior functional results than the classic ILM peeling. It achieves functional recoveries earlier, better BCVA and greater gains at 3 months compared to the classic ILM peeling. It also obtains a higher number of U-shaped closures and higher EZ restorations.

Percutaneous Achilles tendon repair with absorbable suture: Outcomes and complications.

BACKGROUND AND OBJECTIVE: The purpose of this study is to evaluate the clinical outcomes and complications of percutaneous Achilles tendon repair with absorbable sutures. MATERIAL AND METHODS: Prospective cohort study including 52 patients treated for Achilles tendon ruptures (January 2016 to March 2019). INCLUSION CRITERIA: ≥18 years of age, non-insertional Achilles tendon ruptures. Diagnosis based on clinical criteria, confirmed by ultrasonography. Assessment using Visual Analogue Scale (VAS), Achilles Tendon Rupture Score (ATRS) and ultrasound. Re-rupture rate and postoperative complications were collected. RESULTS: VAS scoring (SD) at 1, 3, 6 and 12 months follow-up (FU) were 2.63 (0.83), 1.79 (1.25), 0.69 (1.09) and 0.08 (0.39), respectively. Mean (SD) ATRS score was 92.45 points at 6 months (6.27) and 94.04 points at 12 months FU (4.59). Three re-ruptures (5.77%) occurred with a mean time between surgery and re-rupture of 108.75 days (SD 28.4), all of them within 4-month FU. No ruptures at the time to return to sports activity. Thirteen complications (25%) (3 re-ruptures, 1 superficial wound infection and 9 transitory sural nerve injuries). CONCLUSIONS: Percutaneous Achilles tendon repair with absorbable sutures in patients with acute Achilles tendon ruptures has shown good functional results but with a high incidence of complications. Although most complications were transitory sural nerve symptoms, these would be avoided with conservative treatment. Conservative treatment associated with an early weight-bearing rehabilitation protocol should be considered a viable option for patients with Achilles tendon ruptures, specially in cooperative young patients.

Percutaneous achilles tendon repair with absorbable suture: Outcomes and complications. / Reparación percutánea del tendón de Aquiles con sutura reabsorbible: resultados y complicaciones.

OBJECTIVE: The purpose of this study is to evaluate the clinical outcomes and complications of percutaneous achilles tendon repair with absorbable sutures. MATERIAL AND METHODS: A prospective cohort study including patients treated for an achilles tendon rupture from January 2016 to March 2019 was conducted. INCLUSION CRITERIA: ≥18 years of age, non-insertional (2-8cm proximal to insertion) achilles tendon ruptures. Open or partial ruptures were excluded. The diagnosis was based on clinical criteria and confirmed by ultrasonography in all patients. Epidemiological data, rupture and healing risk factors, previous diagnosis of tendinopathy, pre-rupture sport activity, job information, mechanism of rupture and the time in days between lesion and surgery were collected. Patients were assessed using visual analogue scale at the 1, 3, 6 and 12-month follow-up. The achilles tendon rupture score were assessed at the 6 and 12 month follow-up. Ultrasound was performed at the 6-month follow-up. The re-rupture rate and postoperative complications were also collected. CONCLUSIONS: In our experience, percutaneous achilles tendon repair with absorbable sutures in patients with an acute achilles tendon rupture has shown good functional results but with a high incidence of complications. Although most complications were transitory sural nerve symptoms, this complication would be avoided in patients treated conservatively. For this reason, conservative treatment associated with an early weightbearing rehabilitation protocol should be considered a viable option for patients with achilles tendon ruptures, mainly in cooperative young patients.

Percutaneous Achilles tendon repair with absorbable suture: Outcomes and complications. / [Artículo traducido] Reparación percutánea del tendón de Aquiles con sutura reabsorbible: resultados y complicaciones.

BACKGROUND AND OBJECTIVE: The purpose of this study is to evaluate the clinical outcomes and complications of percutaneous Achilles tendon repair with absorbable sutures. MATERIAL AND METHODS: Prospective cohort study including 52 patients treated for Achilles tendon ruptures (January 2016 to March 2019). INCLUSION CRITERIA: ≥18 years of age, non-insertional Achilles tendon ruptures. Diagnosis based on clinical criteria, confirmed by ultrasonography. Assessment using Visual Analogue Scale (VAS), Achilles Tendon Rupture Score (ATRS) and ultrasound. Re-rupture rate and postoperative complications were collected. RESULTS: VAS scoring (SD) at 1, 3, 6 and 12 months follow-up (FU) were 2.63 (0.83), 1.79 (1.25), 0.69 (1.09) and 0.08 (0.39), respectively. Mean (SD) ATRS score was 92.45 points at 6 months (6.27) and 94.04 points at 12 months FU (4.59). Three re-ruptures (5.77%) occurred with a mean time between surgery and re-rupture of 108.75 days (SD 28.4), all of them within 4-month FU. No ruptures at the time to return to sports activity. Thirteen complications (25%) (3 re-ruptures, 1 superficial wound infection and 9 transitory sural nerve injuries). CONCLUSIONS: Percutaneous Achilles tendon repair with absorbable sutures in patients with acute Achilles tendon ruptures has shown good functional results but with a high incidence of complications. Although most complications were transitory sural nerve symptoms, these would be avoided with conservative treatment. Conservative treatment associated with an early weight-bearing rehabilitation protocol should be considered a viable option for patients with Achilles tendon ruptures, specially in cooperative young patients.

Percutaneous achilles tendon repair with absorbable suture: Outcomes and complications.

OBJECTIVE: The purpose of this study is to evaluate the clinical outcomes and complications of percutaneous achilles tendon repair with absorbable sutures. MATERIAL AND METHODS: A prospective cohort study including patients treated for an achilles tendon rupture from January 2016 to March 2019 was conducted. INCLUSION CRITERIA: ≥18 years of age, non-insertional (2-8cm proximal to insertion) achilles tendon ruptures. Open or partial ruptures were excluded. The diagnosis was based on clinical criteria and confirmed by ultrasonography in all patients. Epidemiological data, rupture and healing risk factors, previous diagnosis of tendinopathy, pre-rupture sport activity, job information, mechanism of rupture and the time in days between lesion and surgery were collected. Patients were assessed using visual analogue scale (VAS) at the 1, 3, 6 and 12-month follow-up. The achilles tendon rupture score (ATRS) were assessed at the 6 and 12 month follow-up. Ultrasound was performed at the 6-month follow-up. The re-rupture rate and postoperative complications were also collected. CONCLUSIONS: In our experience, percutaneous achilles tendon repair with absorbable sutures in patients with an acute achilles tendon rupture has shown good functional results but with a high incidence of complications. Although most complications were transitory sural nerve symptoms, this complication would be avoided in patients treated conservatively. For this reason, conservative treatment associated with an early weightbearing rehabilitation protocol should be considered a viable option for patients with achilles tendon ruptures, mainly in cooperative young patients.

Modified superior inverted internal limiting membrane flap technique with vitrectomy versus vitrectomy with internal limiting membrane peeling for retinal detachment with myopic macular hole.

PURPOSE: To evaluate the efficacy of the modified superior inverted internal limiting (ILM) membrane flap technique in retinal reattachment, macular hole closure and external retinal layers restoration in macular hole associated retinal detachment compared to ILM peeling. METHODS: Retrospective case series of 10 patients that required pars plana vitrectomy for retinal detachment with macular hole followed for more than 12 months. Data from medical records were retrospectively collected and patients were divided into the superior inverted flap (5 patients) and ILM peeling group (5 patients). We compared best corrected visual acuity (BCVA) before and after surgery, retinal attachment, macular hole closure rate and external retinal layer restoration between groups. RESULTS: There were significant improvements in BCVA in both groups before and after surgery, with no differences between the two groups at 12 months after surgery (p=0.9). The macular hole closed in 100% of cases in the inverted flap group and 80% of the ILM peeling group with no significant differences between groups. The retina was reattached in 100% of cases in both groups. Only 2 patients in the inverted flap group (40%) had external retinal layer restoration and none in ILM peeling group (p=0.62). CONCLUSIONS: ILM peeling and superior inverted flap techniques are useful for treating retinal detachment with macular hole in myopic eyes.

S,O-Ligand Promoted meta-C-H Arylation of Anisole Derivatives via Palladium/Norbornene Catalysis.

Reversing the conventional site-selectivity of C-H activation processes provides new retrosynthetic disconnections to otherwise unreactive bonds. Here, we report a new catalytic system based on palladium/norbornene and an S,O-ligand for the meta-C-H arylation of aryl ethers that significantly outperforms previously reported systems. We demonstrate the unique ability of this system to employ alkoxyarene substrates bearing electron donating and withdrawing substituents. Additionally, ortho-substituted aryl ethers are well tolerated, overcoming the "ortho constraint", which is the necessity to have a meta-substituent on the alkoxyarene to achieve high reaction efficiency, by enlisting novel norbornene mediators. Remarkably, for the first time the monoarylation of alkoxyarenes is achieved efficiently enabling the subsequent introduction of a second, different aryl coupling partner to rapidly furnish unsymmetrical terphenyls. Further insight into the reaction mechanism was achieved by isolation and characterization of some Pd-complexes-before and after meta C-H activation-prior to evaluation of their respective catalytic activities.

Selective Para-C-H Alkynylation of Aniline Derivatives by Pd/S,O-Ligand Catalysis.

Herein, we report a nondirected para-selective C-H alkynylation of aniline derivatives by a Pd/S,O-ligand-based catalyst. The reaction proceeds under mild conditions and is compatible with a variety of substituted anilines. The scalability and further derivatizations of the alkynylated products have been also demonstrated.

Removal efficiency for emerging contaminants in a WWTP from Madrid (Spain) after secondary and tertiary treatment and environmental impact on the Manzanares River.

The effluents from wastewater treatment plants (WWTPs) can be an important contamination source for receiving waters. In this work, a comprehensive study on the impact of a WWTP from Madrid on the aquatic environment has been performed, including a wide number of pharmaceuticals and pesticides, among them those included in the European Watch List. 24-h composite samples of influent (IWW) and effluent wastewater after secondary (EWW2) and after secondary + tertiary treatment (EWW3) were monitored along two campaigns. Average weekly concentrations in IWW and EWW2 and EWW3 allowed estimating the removal efficiency of the WWTP for pharmaceutical active substances (PhACs). In addition, the impact of EWW3 on the water quality of the Manzanares River was assessed, in terms of PhAC and pesticide concentrations, through analysis of the river water collected upstream and downstream of the discharge point. After a preliminary risk assessment, a detailed evaluation of the impact on the aquatic environment, including a toxicological study and screening of pharmaceutical metabolites, was made for the seven most relevant PhACs: sulfamethoxazole, azithromycin and clarithromycin (antibiotics), metoprolol (antihypertensive), diclofenac (anti-inflammatory/analgesic), irbesartan (antihypertensive), and the antidepressant venlafaxine. Among selected PhACs, irbesartan, clarithromycin and venlafaxine presented moderate or high risk in the river water downstream of the discharge. Albeit no acute toxicity was detected, more detailed studies should be carried out for these substances, including additional toxicological studies, to set up potential sublethal and chronic effects on aquatic organisms.

Divergent Total Syntheses of Yaequinolone-Related Natural Products by Late-Stage C-H Olefination.

Divergent total syntheses of 10 yaequinolone-related natural products have been achieved for the first time by late-stage C-H olefination of 3,4-dioxygenated 4-aryl-5-hydroxyquinolin-2(1H)-ones, core structures of this family of natural products. A robust synthetic methodology to construct the core structures has been established, and the C-H olefination reaction has been carried out with synthetically useful yields and high levels of site-selectivity under mild reaction conditions in the presence of a Pd/S,O-ligand catalyst.

[Influence of the covid-19 pandemic period of alert on perceived quality of hospital emergencies]. / Influencia del periodo de alarma por la pandemia covid-19 en la calidad percibida de la atención en urgencias hospitalarias.

OBJECTIVE: To assess changes in perceived quality in patients who required A&E hospital care before and during the COVID-19 period of alert. METHODS: Retrospective descriptive observational study using the «Net Promoter Score¼ (NPS), which classifies patients as promoters or detractors. Three perceived quality dimensions (accessibility, professionals, and information) were measured in 160 patients discharged home before alert, and in a further 160 in the first 2 months during alert. A standard of ≥90% promoters and ≤10% detractors was verified by lot acceptance (LQAS) in different access routes and times. Factors related to the probability that a patient was a promoter, or a detractor were analysed using logistic regression. RESULTS: The mean score was lower in accessibility than in the other dimensions (8.6 vs. 9.1 and 9.0, P<.0001). During alert, accessibility obtained better results (NPS 70 vs. 32, P<.001). Per access route, Paediatrics and Ophthalmology improved and Maternity did not experience changes. LQAS showed more lots accepted during alert (85 vs. 72%). The likelihood for a patient to be a promoter was higher during alert (OR 1.85, P<.0001), especially in accessibility (OR 3.08, P<0.0001). The likelihood to be a detractor was reduced (OR .54, P<.05), and also greater in accessibility (OR .39, P<.05). CONCLUSIONS: Perceived quality improved during the period of alert, its declaration being the most influential factor. This improvement is evident in paediatric and ophthalmological patients, but imperceptible in Maternity or Traumatology, perhaps because the pandemic acted as an adequacy corrector.

Efficacy of dual carbapenem treatment in a murine sepsis model of infection due to carbapenemase-producing Acinetobacter baumannii.

OBJECTIVES: To evaluate the in vivo efficacy of a dual carbapenem combination containing imipenem plus meropenem against carbapenem-resistant Acinetobacter baumannii producing carbapenemases OXA-23 or OXA-58. METHODS: An experimental model of peritonitis using C57BL/6J female mice was developed and the minimum lethal doses were calculated for infections due to OXA-23 or OXA-58 producers of A. baumannii clinical isolates. The efficacies of the carbapenems in monotherapy and in combination were tested. RESULTS: Meropenem was better than imipenem in mice infected with either of the carbapenem-resistant A. baumannii (CRAb) strains. The combination of meropenem plus imipenem significantly improved the clearance of CRAbs from spleen compared with non-treated groups. The carbapenem-containing combination was better than imipenem for treating mice infected with both carbapenemase producers. In blood, the carbapenem combination significantly decreased the bacterial load of the OXA-23 producers compared with imipenem or meropenem used in monotherapy. CONCLUSIONS: These results suggest that dual carbapenem combination could be an option for the treatment of infections due to carbapenemase-producing A. baumannii such as OXA-23 and OXA-58 producers.

Predictors of good visual outcomes in patients with neovascular age-related macular degeneration in daily practice.

PURPOSE: To report predictive factors for therapeutic response to anti-VEGF in patients with neovascular age-related macular degeneration (nAMD) in daily clinical practice in our patient population. METHODS: Retrospective cohort study including 56 patients (69 eyes) with nAMD treated with anti-VEGF, followed for at least two years between February 2012 and April 2018. Patients received three intravitreal anti-VEGF (bevacizumab) injections (loading dose) and were monitored and treated according to a PRN regimen. We analysed whether a gain in visual acuity of 15 or more ETDRS letters at the final visit was associated with demographic characteristics, presence of systemic comorbidities, fundus lesions or measurable improvement on Cirrus optical coherence tomography (OCT) between the first and last visit. RESULTS: After a mean follow-up of 15.5 months (4.7-27.8 interquartile range), central retinal thickness (CRT) (RR: 1.004; IC 95%: 1.001-1.007; P=0.011) and macular hemorrhage (RR: 0.30; IC 95%: 0.10-0.90, P=0.032) at baseline were found to be useful predictive factors for visual acuity improvement (≥15 letters) in patients treated for nAMD by anti-VEGF in a real world clinical setting. CONCLUSION: In the present series of patients with nAMD receiving a loading dose of bevacizumab and followed according to a PRN regimen for 24 months, the only predictable factors for a ≥15 letter gain in visual acuity were anatomical response as measured by OCT and macular hemorrhage at baseline.

The effect of the AKT1 gene and cannabis use on cognitive performance in healthy subjects.

BACKGROUND: Evidence suggests that the AKT1 gene may modulate the degree to which cannabis use induces cognitive alterations in patients with a psychotic disorder. AIM: To examine the interplay between AKT1 and cannabis use in terms of the cognitive performance of the general population. METHODS: Our sample consisted of 389 Spanish university students. Sustained attention was measured via the Continuous Performance Test-Identical Pairs, immediate and delayed verbal memory with the Logical Memory subtest of the Wechsler Memory Scale, and working memory with the Wisconsin Card Sorting Test. Lifetime cannabis use frequency was assessed and individuals were classified as cannabis users or non-users. Two single nucleotide polymorphisms of the AKT1 gene were genotyped and, according to previous studies, each subject was defined as a carrier of two, one or no copies of the haplotype (rs2494732(C)-rs1130233(A)). Multiple linear regressions were conducted to test the effect of the genetic variability and cannabis use (and their interaction) on cognitive performance. RESULTS: An effect of the AKT1 haplotype was found on attention scores: individuals with two copies of the haplotype performed better (ß=0.18, p<0.001 (adjusted for false discovery rate)), while neither cannabis nor the AKT1-cannabis interaction was associated with attention. No effect of AKT1, cannabis or the AKT1-cannabis interaction was found on verbal memory or working memory. CONCLUSIONS: Our study provides additional evidence that AKT1 modulates cognitive performance. However, in our non-clinical sample, the previously reported interaction between cannabis use and the AKT1 gene was not replicated.