Laparoscopic versus open rectal resection: a 1:2 propensity score-matched analysis of oncological adequateness, short- and long-term outcomes.

BACKGROUND: Laparoscopic resections for rectal cancer are routinely performed in high-volume centres. Despite short-term advantages have been demonstrated, the oncological outcomes are still debated. The aim of this study was to compare the oncological adequateness of the surgical specimen and the long-term outcomes between open (ORR) and laparoscopic (LRR) rectal resections. METHODS: Patients undergoing laparoscopic or open rectal resections from January 1, 2013, to December 31, 2019, were enrolled. A 1:2 propensity score matching was performed according to age, sex, BMI, ASA score, comorbidities, distance from the anal verge, and clinical T and N stage. RESULTS: Ninety-eight ORR were matched to 50 LRR. No differences were observed in terms of operative time (224.9 min. vs. 230.7; p = 0.567) and postoperative morbidity (18.6% vs. 20.8%; p = 0.744). LRR group had a significantly earlier soft oral intake (p < 0.001), first bowel movement (p < 0.001), and shorter hospital stay (p < 0.001). Oncological adequateness was achieved in 85 (86.7%) open and 44 (88.0%) laparoscopic resections (p = 0.772). Clearance of the distal (99.0% vs. 100%; p = 0.474) and radial margins (91.8 vs. 90.0%, p = 0.709), and mesorectal integrity (94.9% vs. 98.0%, p = 0.365) were comparable between groups. No differences in local recurrence (6.1% vs.4.0%, p = 0.589), 3-year overall survival (82.9% vs. 91.4%, p = 0.276), and disease-free survival (73.1% vs. 74.3%, p = 0.817) were observed. CONCLUSIONS: LRR is associated with good postoperative results, safe oncological adequateness of the surgical specimen, and comparable survivals to open surgery.

The burden of depressive disorders in musculoskeletal diseases: is there an association between mood and inflammation?

IMPORTANCE: Evidence emerged concerning how inflammatory arthritis and mood disorders can often occur in the same patient and show a similar clinical pattern. An overview of the rheumatological and psychiatric aspects of these diseases can certainly be useful for the improvement of patients' clinical and therapeutic management. OBJECTIVE: The aim of this narrative review was to summarize existing literature about common pathogenetic and clinical aspects as a means of improving management and therapeutic approach in patients affected by rheumatoid arthritis, psoriatic arthritis and spondyloarthritis. Outcomes such as disease activity indexes and patient reported outcomes (PROs) were considered. FINDINGS: Common pathogenetic pathways emerged between inflammatory arthritis and mood disorders. Pro-inflammatory mechanisms, such as TNFα, IL-6, IL-17 and oxidative stress factors as well as neurotransmitter alterations at the level of CNS and blood-brain barrier (BBB) cells are involved. The activation of these common pathogenetic pathways is, also, affected by the same triggers, such as smoking, stress, lifestyle, and evidence has emerged concerning the possibility of the clinical efficacy of using the same therapeutic approaches. CONCLUSIONS: The main causes of the variability in clinical studies outcomes are the rheumatological diseases considered, the prevalence of depression in the general population and in patients with rheumatological diseases and the type of depressive symptom examined. Patients affected by inflammatory arthritis can present symptoms and signs in common with mood disorders, leading to possible clinical overlap. There are still few studies analyzing this concept: they are extremely heterogeneous, both in the characteristics of the population taken into consideration and in the methods used for the definition of depressive disorder, but the suggestions of the data obtained so far are promising and deserve to be pursued.

A Semisynthetic Approach to New Immunoadjuvant Candidates: Site-Selective Chemical Manipulation of Escherichia coli Monophosphoryl Lipid†A.

A semisynthetic approach to novel lipid A derivatives from Escherichia coli (E. coli) lipid A is reported. This methodology stands as an alternative to common approaches based exclusively on either total synthesis or extraction from bacterial sources. It relies upon the purification of the lipid A fraction from fed-batch fermentation of E. coli, followed by its structural modification through tailored, site-selective chemical reactions. In particular, modification of the lipid pattern and functionalization of the phosphate group as well as of the sole primary hydroxyl group were accomplished, highlighting the unusual reactivity of the molecule. Preliminary investigations of the immunostimulating activity of the new semisynthetic lipid A derivatives show that some of them stand out as promising, new immunoadjuvant candidates.

Is EUS-FNA of solid-pseudopapillary neoplasms of the pancreas as a preoperative procedure really necessary and free of acceptable risks?

BACKGROUND: Solid-pseudopapillary neoplasms (SPNs) of the pancreas are infrequent tumors since, as of 2014, only 2744 patients have been described. Its rarity, unclear histogenesis, pleomorphic aspect on radiology (cystic, solid or mixed) and unpredictable biological behavior with an insidious high-grade malignant potential make SPN difficult to recognize preoperatively even in its target patient population which is predominantly composed of young women (about 87% of cases). METHODS: Endoscopic ultrasound-guided fine needle aspiration (EUS-FNA) showed to improve the preoperative diagnostic yield for this tumor and obviate the risks formerly given by percutaneous biopsy. RESULTS: In light of our experience, such a procedure could not be so innocuous as generally acknowledged. CONCLUSION: We report the first case of rupture of pancreatic SPN following EUS-FNA and entertain both the actual and potential complications ensuing from this type of mishap.

Profiling the prognosis of gastric cancer patients: is it worth correlating the survival with the clinical/pathological and molecular features of gastric cancers?

BACKGROUND: The prognosis of gastric cancer patients still remains poor. The aim of this study was investigating the prognostic value of several clinical/pathological/molecular features in a consecutive series of gastric cancers. METHODS: 150 R0 gastrectomies plus 77 gastric cancer patients evaluated for the HER2 overexpression were selected. Survival was calculated and patients stratified according to the stage, the T-stage, the LNRs, the LNH, and the HER2 scoring system. ROC curves were calculated in order to compare the performance of the LRN and LNH systems. RESULTS: Prognosis correlated with the stage and with the T-stage. We documented a statistical correlation between the LNRs and the survival. Conversely, a LNH > 15 did not correlate with the outcomes. The ROC curves documented a significant performance of the LRN system, whereas a statistical correlation was documented for the LNH exclusively with the endpoint of disease-free survival. We documented a trend of worse prognosis for patients with an HER2 overexpression, even though it was not of statistical value. CONCLUSION: The LNR and the evaluation of the HER2 overexpression might be useful since they correlate with survival, might identify patients with a higher risk of recurrence, and might select patients for a tailored medical treatment.

Computational Study of the Solid-State Incorporation of Sn(II) Acetate into Zeolite ß.

Sn-doped zeolites are potent Lewis acid catalysts for important reactions in the context of green and sustainable chemistry; however, their synthesis can have long reaction times and harsh chemical requirements, presenting an obstacle to scale-up and industrial application. To incorporate Sn into the ß zeolite framework, solid-state incorporation (SSI) has recently been demonstrated as a fast and solvent-free synthetic method, with no impairment to the high activity and selectivity associated with Sn-ß for its catalytic applications. Here, we report an ab initio computational study that combines periodic density functional theory with high-level embedded-cluster quantum/molecular mechanical (QM/MM) to elucidate the mechanistic steps in the synthetic process. Initially, once the Sn(II) acetate precursor coordinates to the ß framework, acetic acid forms via a facile hydrogen transfer from the ß framework onto the monodentate acetate ligand, with low kinetic barriers for subsequent dissociation of the ligand from the framework-bound Sn. Ketonization of the dissociated acetic acid can occur over the Lewis acidic Sn(II) site to produce CO2 and acetone with a low kinetic barrier (1.03 eV) compared to a gas-phase process (3.84 eV), helping to explain product distributions in good accordance with experimental analysis. Furthermore, we consider the oxidation of the Sn(II) species to form the Sn(IV) active site in the material by O2- and H2O-mediated mechanisms. The kinetic barrier for oxidation via H2 release is 3.26 eV, while the H2O-mediated dehydrogenation process has a minimum barrier of 1.38 eV, which indicates the possible role of residual H2O in the experimental observations of SSI synthesis. However, we find that dehydrogenation is facilitated more significantly by the presence of dioxygen (O2), introduced in the compressed air gas feed, via a two-step process oxidation process that forms H2O2 as an intermediate and has greatly reduced kinetic barriers of 0.25 and 0.26 eV. The results provide insight into how Sn insertion into ß occurs during SSI and demonstrate the possible mechanism of top-down synthetic procedures for metal insertion into zeolites.

Radiomic Cancer Hallmarks to Identify High-Risk Patients in Non-Metastatic Colon Cancer.

The study was aimed to develop a radiomic model able to identify high-risk colon cancer by analyzing pre-operative CT scans. The study population comprised 148 patients: 108 with non-metastatic colon cancer were retrospectively enrolled from January 2015 to June 2020, and 40 patients were used as the external validation cohort. The population was divided into two groups­High-risk and No-risk­following the presence of at least one high-risk clinical factor. All patients had baseline CT scans, and 3D cancer segmentation was performed on the portal phase by two expert radiologists using open-source software (3DSlicer v4.10.2). Among the 107 radiomic features extracted, stable features were selected to evaluate the inter-class correlation (ICC) (cut-off ICC > 0.8). Stable features were compared between the two groups (T-test or Mann−Whitney), and the significant features were selected for univariate and multivariate logistic regression to build a predictive radiomic model. The radiomic model was then validated with an external cohort. In total, 58/108 were classified as High-risk and 50/108 as No-risk. A total of 35 radiomic features were stable (0.81 ≤ ICC < 0.92). Among these, 28 features were significantly different between the two groups (p < 0.05), and only 9 features were selected to build the radiomic model. The radiomic model yielded an AUC of 0.73 in the internal cohort and 0.75 in the external cohort. In conclusion, the radiomic model could be seen as a performant, non-invasive imaging tool to properly stratify colon cancers with high-risk disease.

Acceptorless Alcohol Dehydrogenation Catalysed by Pd/C.

Although the selective oxidation of alcohols to carbonyl compounds is a critical reaction, it is often plagued by several challenges related to sustainability. Here, the continuous, acceptorless dehydrogenation of alcohols to carbonyl compounds over heterogeneous catalysts was demonstrated, in the absence of oxidants, bases or acceptor molecules. In addition to improving selectivity and atom efficiency, the absence of an acceptor resulted in the co-production of molecular H2 , a clean energy source, and permitted dehydrogenation to proceed at >98 % selectivity at turnover frequency values amongst the highest in the literature. Moreover, excellent durability was observed during continuous operation over 48 h, reaching space-time yields of 0.683 g(product) mL-1 h-1 , better than the state of the art by over two orders of magnitude. Alongside these breakthroughs, the basic kinetic parameters of the reaction were also determined, allowing some of the elementary reaction steps to be identified.

Porous metallosilicates for heterogeneous, liquid-phase catalysis: perspectives and pertaining challenges.

Porous silicates containing dilute amounts of tri-, tetra- and penta-valent metal sites, such as TS-1, Sn-ß and Fe-ZSM-5, have recently emerged as state of the art catalysts for a variety of sustainable chemical transformations. In contrast with their aluminosilicate cousins, which are widely employed throughout the refinery industry for gas-phase catalytic transformations, such metallosilicates have exhibited unprecedented levels of performance for a variety of liquid-phase catalytic processes, including the conversion of biomass to chemicals, and sustainable oxidation technologies with H2O2. However, despite their unique levels of performance for these new types of chemical transformations, increased utilization of these promising materials is complicated by several factors. For example, their utilization in a liquid, and often polar, medium hinders process intensification (scale-up, catalyst deactivation). Moreover, such materials do not generally exhibit the active-site homogeneity of conventional aluminosilicates, and they typically possess a wide variety of active-site ensembles, only some of which may be directly involved in the catalytic chemistry of interest. Consequently, mechanistic understanding of these catalysts remains relatively low, and competitive reactions are commonly observed. Accordingly, unified approaches towards developing more active, selective and stable porous metallosilicates have not yet been achieved. Drawing on some of the most recent literature in the field, the purpose of this mini review is both to highlight the breakthroughs made with regard to the use of porous metallosilicates as heterogeneous catalysts for liquid-phase processing, and to highlight the pertaining challenges that we, and others, aim to overcome during the forthcoming years.