Unusual Reaction of Isocyanides with Aromatic Aldehydes Catalyzed by a Supramolecular Capsule.

The supramolecular resorcinarene hexameric capsule efficiently promotes the unprecedented reaction between isocyanides and electron-deficient aromatic aldehydes leading to the formation of imines and carbon monoxide. The mechanism of the reaction was investigated via isotope labelling, kinetic analysis of the reaction, computational studies and the independent synthesis of a proposed intermediate. Control experiments indicate that the formation of the key aziridinone intermediate is limited to the cavity of the capsule.

Symmetric Aromatic Amidoalkylations of Triphenylenes.

Triphenylene derivatives are highly investigated for their electronic, supramolecular and photophysical properties, but the direct modification of the central aromatic core is particularly challenging especially in the internal positions 1, 4, 5, 8, 9, and 12. Herein we present an efficient alkylation method of 2,3,6,7,10,11-hexasubstituted triphenylene derivatives leading to tris-alkylated C-symmetric derivatives in good yields using N-(hydroxymethyl)carboxamide or N-(alkoxylmethyl)carboxamide alkylating agents.

A β-Glucosyl Sterol Probe for in situ Fluorescent Labelling in Neuronal Cells to Investigate Neurodegenerative Diseases.

A β-glucosyl sterol probe bearing a terminal alkyne moiety for fluorescent tagging enables the investigation of the neuronal and intracellular localization of this class of compounds involved in neurodegenerative diseases. The compound showed localization in the neuronal cells, with marked differences in the uptake and metabolism leading to enhanced persistence with respect to the un-glycosylated sterol analogue. In addition, a different impact was observed towards lysosomes, with the simple sterol probe showing the enlargement of the lysosome structures, while the β-glucosyl sterol was less capable to alter the morphology of this specific organelle.

Substrate Selectivity Imparted by Self-Assembled Molecular Containers and Catalysts.

Recent trends in catalysis are devoted to mimicking some peculiar features of enzymes like site selectivity, through functional group recognition, and substrate selectivity, through recognition of the entire surface of the substrate. The latter is a specific feature of enzymes that is seldomly present in homogeneous catalysis. Supramolecular catalysis, thanks to the self-assembly of simple subunits, enables the creation of cavities and surfaces whose confinement effects drive the preferential binding of a substrate among others with consequent substrate selectivity.

Is Micellar Catalysis Green Chemistry?

Many years ago, twelve principles were defined for carrying out chemical reactions and processes from a green chemistry perspective. It is everyone's endeavor to take these points into account as far as possible when developing new processes or improving existing ones. Especially in the field of organic synthesis, a new area of research has thus been established: micellar catalysis.

A resorcin[4]arene hexameric capsule as a supramolecular catalyst in elimination and isomerization reactions.

The hexameric resorcin[4]arene capsule as a self-assembled organocatalyst promotes a series of reactions like the carbonyl-ene cyclization of citronellal preferentially to isopulegol, the water elimination from 1,1-diphenylethanol, the isomerization of α-pinene and β-pinene preferentially to limonene and minor amounts of camphene. The role of the supramolecular catalyst consists in promoting the protonation of the substrates leading to the formation of cationic intermediates that are stabilized within the cavity with consequent peculiar features in terms of acceleration and product selectivity. In all cases the catalytic activity displayed by the hexameric capsule is remarkable if compared to many other strong Brønsted or Lewis acids.

Focus on Key Issues in Immune Thrombotic Thrombocytopenic Purpura: Italian Experience of Six Centers.

Immune-mediated thrombotic thrombocytopenic purpura is a rare and challenging hematological disease caused by the antibody anti-ADAMTS13. Though the mortality rate has decreased considerably in recent years, fatalities still remain unacceptable. This study aimed at further adding to the existing knowledge of this medical challenge.

Emergency Medicine Cases in Underwater and Hyperbaric Environments: The Use of Simulation as a Learning Technique.

Introduction: Hyperbaric chambers and underwater environments are challenging and at risk of serious accidents. Personnel aiming to assist patients and subjects should be appropriately trained, and several courses have been established all over the world. In healthcare, simulation is an effective learning technique.

Extremely Old Patients Hospitalized in Internal Medicine: What about Their Anemia?

In western countries, about half of the hospitalized patients are anemic. Generally, these patients are old, often with multiple diseases, and anemia worsens the prognosis, finally increasing the risk of death. We describe a monocentric observational study that evaluates 249 consecutive adult patients (160 women and 89 men) with anemia admitted in the internal medicine department over five months.

PAR-4/Ca-calpain pathway activation stimulates platelet-derived microparticles in hyperglycemic type 2 diabetes.

Background: Patients with type 2 diabetes (T2DM) have a prothrombotic state that needs to be fully clarified; microparticles (MPs) have emerged as mediators and markers of this condition. Thus, we investigate, in vivo, in T2DM either with good (HbA1c ≤ 7.0%; GGC) or poor (HbA1c > 7.

Admission criteria for a cardiovascular short stay unit: a retrospective analysis on a pilot unit.

Rapid intensive observation (RIO) units have been created to guarantee high standards of care in a sustainable health-care system. Within short stay units (SSUs), which are a subgroup of RIOs, only rapidly manageable patients should be admitted. Physicians are unable to predict the length of stay (LOS) as objective criteria to make such a prediction are missing.

Effectiveness of In-Hospital Cholecalciferol Use on Clinical Outcomes in Comorbid COVID-19 Patients: A Hypothesis-Generating Study.

Little information is available on the beneficial effects of cholecalciferol treatment in comorbid patients hospitalized for COVID-19. The aim of this study was to retrospectively examine the clinical outcome of patients receiving in-hospital high-dose bolus cholecalciferol. Patients with a positive diagnosis of SARS-CoV-2 and overt COVID-19, hospitalized from 15 March to 20 April 2020, were considered.

Life-Saving Procedures Performed While Wearing CBRNe Personal Protective Equipment: A Mannequin Randomized Trial.

Introduction: Chemical-biological-radiological-nuclear-explosive (CBRNe) are complex events. Decontamination is mandatory to avoid harm and contain hazardous materials, but can delay care. Therefore, the stabilization of patients in the warm zone seems reasonable, but research is limited.

Histology of the spleen in immune thrombocytopenia: clinical-pathological characterization and prognostic implications.

Objective: Immune thrombocytopenia (ITP) is an acquired disorder, characterized by immune-mediated platelet destruction. The spleen plays a key pathogenic role in ITP and splenectomy is a valuable second-line therapy for this disease. Little is known on ITP spleen histology and response to splenectomy is unpredictable.

A novel RUNX1 mutation with ANKRD26 dysregulation is related to thrombocytopenia in a sporadic form of myelodysplastic syndrome.

Aging is associated with a higher risk of developing malignant diseases, including myelodysplastic syndromes, clonal disorders characterised by chronic cytopenias (anaemia, neutropenia and thrombocytopenia) and abnormal cellular maturation. Myelodysplastic syndromes arising in older subjects are influenced by combinations of acquired somatic genetic lesions driving evolution from clonal haematopoiesis to myelodysplastic syndromes and from myelodysplastic syndromes to acute leukaemia. A different pattern of mutations has been identified in a small subset of myelodysplastic syndromes arising in young patients with familial syndromes.

Platelet-Derived Microparticles Bearing PF4 and Anti-GAGS Immunoglobulins in Patients with Sepsis.

PF4 is a megakaryocyte-derived cationic chemokine that plays a part in innate immunity through its activity on the macrophages. In bacterial sepsis, PF4 binds to glycosaminoglycans (GAGs) on the surface of aerobic bacteria, giving rise to an antigenic complex that induces the early formation of anti-PF4 IgG-IgA-IgM. This triggers the immune response in patients receiving heparin therapy who develop heparin-induced thrombocytopenia (HIT).

Testing the vibrational exciton and the local mode models on the instructive cases of dicarvone, dipinocarvone, and dimenthol vibrational circular dichroism spectra.

The vibrational circular dichroism (VCD) spectra of dicarvone (1), dipinocarvone (2), and dimenthol (3) have been recorded in the range 900-3200 cm , encompassing the mid-infrared (mid-IR), the CO stretching, and the CH-stretching regions. For compound 3 also, the fundamental and the first overtone OH stretching regions have been investigated by IR/NIR absorption and VCD. Density functional theory (DFT) calculations allow one to interpret the IR and VCD spectra and to confirm the configuration/conformational studies previously conducted by X-ray diffraction.

Prevalence and Causes of Anemia in Hospitalized Patients: Impact on Diseases Outcome.

Anemia is extremely common in hospitalized patients who are old and often with multiple diseases. We evaluated 435 consecutive patients admitted in the internal medicine department of a hub hospital and 191 (43.9%) of them were anemic.

Antithrombotic prophylaxis for surgery-associated venous thromboembolism risk in patients with inherited platelet disorders. The SPATA-DVT Study.

Major surgery is associated with an increased risk of venous thromboembolism (VTE), thus the application of mechanical or pharmacologic prophylaxis is recommended. The incidence of VTE in patients with inherited platelet disorders (IPD) undergoing surgical procedures is unknown and no information on the current use and safety of thromboprophylaxis, particularly of low-molecular-weight-heparin in these patients is available. Here we explored the approach to thromboprophylaxis and thrombotic outcomes in IPD patients undergoing surgery at VTE-risk participating in the multicenter SPATA study.

Systemic Mastocytosis and Essential Thrombocythemia: Case Report and Literature Overview.

Mastocytosis is a rare disease in which heightened amounts of mast cells accumulate in the skin, bone marrow, and other visceral organs. Upon activation, mast cells release a wide variety of preformed or newly synthesized mediators which can induce allergic symptoms and inflammatory reactions. Mastocytosis is diagnosed by biopsy and can be divided into cutaneous and systemic mastocytosis (SM).

Increased Risk of Bone Fractures in Hemodialysis Patients Treated with Proton Pump Inhibitors in Real World: Results from the Dialysis Outcomes and Practice Patterns Study (DOPPS).

Long-term treatment with proton pump inhibitors (PPIs) is associated with an increased risk of fractures in the general population. PPIs are widely prescribed to dialysis patients but to date no study has specifically tested, by state-of-art statistical methods, the relationship between use of PPIs and fractures in this patient population. This study aimed to assess whether use of PPIs is associated with bone fractures (ie, hip fractures and fractures other than hip fractures) in a large international cohort of hemodialysis patients.

Eltrombopag for the treatment of inherited thrombocytopenias: a phase II clinical trial.

Patients with inherited thrombocytopenias often require platelet transfusions to raise their platelet count before surgery or other invasive procedures; moreover, subjects with clinically significant spontaneous bleeding may benefit from an enduring improvement of thrombocytopenia. The hypothesis that thrombopoietin-mimetics can increase platelet count in inherited thrombocytopenias is appealing, but evidence is scarce. We conducted a prospective, phase II clinical trial to investigate the efficacy of the oral thrombopoietin-mimetic eltrombopag in different forms of inherited thrombocytopenia.

Relapsing thrombotic thrombocytopenic purpura with low ADAMTS13 antigen levels: An indication for splenectomy?

With more recent modalities of immunosuppression, splenectomy is now rarely considered in refractory/relapsed thrombotic thrombocytopenic purpura (TTP). However, the surgical approach had shown convincing evidences of high efficacy in the pre-rituximab era and therefore may still represent a lifesaving option in selected challenging cases. To define the characteristics of subjects who may benefit from splenectomy may ease clinical decision making.