Green synthesis of gold nanoparticles from pomegranate juice ascertained by a combined approach based on MALDI FT-ICR MS and LC-ESI-MS/MS.

This research employs advanced analytical techniques to explore the specific roles of Pomegranate Juice (PJ) phytochemicals in both the reduction and stabilization of gold nanoparticles (AuNPs) obtained by means of juice from wasted fruits. A level 3 for classes annotation, used for MALDI FT ICR-MS data, was useful to provide an immediate visualization of the main involved metabolites in AuNPs synthesis, through van Krevelen diagrams. More than 25 elemental formulae containing at least one Au atom were assigned to AuNPs sample, confirming the formation of organogold complexes.

Deep-Cavity Calix[4]naphth[4]arene Macrocycles: Synthesis, Conformational Features, and Solid-State Structures.

We recently introduced calix[]naphth[]arenes as a novel class of deep-cavity hybrid macrocycles constituted by phenol (n) and naphthalene (m) units. In this study, we report the synthesis, conformational analysis, spectroscopic properties, and solid-state structures of calix[4]naphth[4]arene () and its permethylated analog (), thereby expanding the calix[]naphth[]arene family. was synthesized through a 2 + 2 fragment coupling macrocyclization under acidic conditions, where the solvent played a crucial role in selectively forming the derivative.

L. Pod Valves: A By-Product with High Potential as an Adjuvant in the Treatment of Parkinson's Disease.

L. is a leguminous plant with seeds rich in nutritional compounds, such as polyphenols and L-dopa, a dopamine precursor and first-line treatment for Parkinson's symptoms. Recently, its by-products have been revalued as a sustainable source of bioactive compounds.

Thermodynamically Templated Macrocyclizations: Enhancing the Synthesis of Prism[5]arenes with Tailor-Made Guests.

The macrocyclization of 2,6-dialkoxynaphthalene monomers to prism[5]arenes is thermodynamically templated by DABCO cations. In this study, we demonstrate that a greater template affinity for prism[5]arene improves the macrocyclization yield. By using novel templating cations, the yield of alkoxy-prism[5]arenes increases significantly compared with those of previously reported procedures, while the purification process becomes easier and faster.

Under the Influence of Water: Molecular Recognition of Organic Hydrophilic Molecules in Water with a Prismarene Host Driven by Hydration Effects.

A water-soluble prism[5]arene host can form endo-cavity complexes with hydrophilic organic substances in water by displacing frustrated water molecules from its deep cavity. Water molecules structured at both rims of the prismarene host can mediate hydrogen bonding interactions with the guest. Water-mediated hydrogen bonding interactions were invoked here to elucidate the elevated binding affinities and selectivity of the prismarene host toward hydrophilic organic guests.

Chirality Sensing of Cryptochiral Guests with Prism[n]arenes.

Optical chirality sensing has gained significant attention in recent years. Within this field, the quest for stereodynamic chiroptical probes capable of detecting cryptochiral guests presents a formidable challenge. Macrocycles exhibiting planar chirality have emerged as promising candidates for amplifying the chirality of cryptochiral guests.

The Resorcinarene Hexameric Capsule as a Supramolecular Photoacid to Trigger Olefin Hydroarylation in Confined Space.

The self-assembled resorcinarene capsule C shows remarkable photoacidity upon light irradiation, which is here exploited to catalyze olefin hydroarylation reactions in confined space. An experimental pKa* value range of -3.3--2.

Hexahexyloxycalix[6]arene, a Conformationally Adaptive Host for the Complexation of Linear and Branched Alkylammonium Guests.

Hexahexyloxycalix[6]arene leads to the -cavity complexation of linear and branched alkylammonium guests showing a conformational adaptive behavior in CDCl solution. Linear -pentylammonium guest induces the cone conformation of at the expense of the 1,2,3-alternate, which is the most abundant conformer of in the absence of a guest. In a different way, branched alkylammonium guests, such as -butylammonium and isopropylammonium , select the 1,2,3-alternate as the favored conformation (/⊂), but other complexes in which adopts different conformations, namely, /⊂, /⊂, and /⊂, have also been revealed.

Size-age population structure of an endangered and anthropogenically introgressed northern Adriatic population of marble trout ( Cuv.): insights for its conservation and sustainable exploitation.

Salmonid species are main actors in the Italian socio-ecological landscape of inland fisheries. We present novel data on the size-age structure of one of the remnant Italian populations of the critically endangered marble trout , which co-occurs with other stocked non-native salmonids in a large glacial river of the Lake Maggiore basin (Northern Italy-Southern Switzerland). Like other Italian native trout populations, the Toce River marble trout population is affected by anthropogenic introgression with the non-native brown trout .

Confused-Prism[5]arene: a Conformationally Adaptive Host by Stereoselective Opening of the 1,4-Bridged Naphthalene Flap.

The confused-prism[5]arene macrocycle (c-PrS[5] ) shows conformational adaptive behavior in the presence of ammonium guests. Upon guest inclusion, the 1,4-bridged naphthalene flap reverses its planar chirality from pS to pR (with reference to the pS(pR) enantiomer). Stereoselective directional threading is also observed in the presence of directional axles, in which up/down stereoisomers of homochiral (pR) -c-PrS[5] pseudorotaxanes are formed.

Carbocation catalysis in confined space: activation of trityl chloride inside the hexameric resorcinarene capsule.

Carbocation catalysis can be performed inside the confined space of the hexameric resorcinarene capsule. The inner cavity of the capsule can host the trityl carbocation, which catalyses the Diels-Alder reaction between dienes and unsaturated aldehydes. Experimental results and calculations show that the hexameric resorcinarene capsule C can promote the formation of the trityl carbocation from trityl chloride through the cleavage of the carbon-halogen bond promoted by OH⋯X hydrogen bonding.

Molecular Recognition in an Aqueous Medium Using Water-Soluble Prismarene Hosts.

The synthesis of water-soluble prism[]arenes ( = 5 and 6) bearing anionic carboxylato groups on the rims is described. The binding properties of this novel class of water-soluble hosts are studied by nuclear magnetic resonance and calorimetry. The complexation of singly and doubly charged ammonium guests with the more rigid pentamer is enthalpically driven by secondary interactions, while the thermodynamic fingerprint for the larger hexamer reveals driving forces that strongly depend on the guest charge and/or size.

Unusual Calixarenes Incorporating Chromene and Benzofuran Moieties Obtained via Propargyl Claisen Rearrangement.

Monopropargyloxy-tripropoxy-calix[4]arene was subjected to a propargyl Claisen rearrangement to give unusual calix[3]arene[1]chromene and homocalix[3]arene[1]benzofuran macrocycles. Quantum mechanical density functional theory calculations indicated that an initial [3,3] sigmatropic reaction affords a highly reactive allene intermediate, stabilized by two main diradical pathways leading to six- and five-membered oxygenated rings. In the presence of a -butylammonium guest, calix[3]arene[1]chromane forms two stereoisomeric complexes stabilized by N-H···O and cation···π interactions.

-Hydroxylated Prism[]arenes: Supramolecularly Assisted Demethylation of Methoxy-Prism[5]arene.

Methoxy-prism[5]arene is demethylated by a supramolecularly assisted reaction. In the presence of a tetramethylammonium cation, is demethylated by BBr in high yield, while in its absence a 55/40 mixture of / is formed. The dealkylation of prismarenes, such as (R = Et, Pr) and , can be easily obtained in high yields in the presence of BBr.

Efficacy and safety of prolonged-release hyaluronic acid derivative vaginal application in the postpartum period: a prospective randomised clinical trial.

Introduction: In puerperium, the hypoestrogenic state induced by delivery and subsequently sustained by lactation may lead to vaginal dryness, burning, and itching sensation, contributing to the onset of sexual dysfunction.

Material And Methods: This was a prospective, randomized, controlled, open-label study (NCT04560283) for evaluating the effects of application of a prolonged-release hyaluronic acid derivative vaginal gel in restoring sexual function during the postpartum period. Eighty-five patients were randomized to apply prolonged-release Hydeal-D 0.

Chromogenic Properties of -Pyridinium- and -Viologen-Calixarenes and Their Cation-Sensing Abilities.

The synthesis of calix[4]- and -[6]arene derivatives (H)·(Cl), (H)·(Cl)·(I), and (H)·(Cl)·(I) bearing -linked pyridinium () and viologen () units at the upper rim is described here. A rare example of an anionic conformational template is reported for -pyridiniumcalix[6]arene (H), which adopts a 1,3,5-alternate conformation in the presence of chloride anions. Derivatives (H)·(Cl), (H)·(Cl)·(I), and (H)·(Cl)·(I) show a negative solvatochromism, while their UV-vis acid-base titration evidenced that upon addition of a base, new bands appear at 487, 583, and 686 nm, respectively, due to the formation of betainic monodeprotonated species (H), (H), and (H).

An intramolecularly self-templated synthesis of macrocycles: self-filling effects on the formation of prismarenes.

Ethyl- and propyl-prism[6]arenes are obtained in high yields and in short reaction times, independent of the nature and size of the solvent, in the cyclization of 2,6-dialkoxynaphthalene with paraformaldehyde. or adopt, both in solution and in the solid state, a folded cuboid-shaped conformation, in which four inward oriented alkyl chains fill the cavity of the macrocycle. On these bases, we proposed that the cyclization of or occurs through an intramolecular thermodynamic self-templating effect.

Poly(Ethylene Glycol)/β-Cyclodextrin Pseudorotaxane Complexes as Sustainable Dispersing and Retarding Materials in a Cement-Based Mortar.

Pseudorotaxane complexes between β-CD and mPEG derivatives bearing a carboxylic acid function (mPEG-COOH) were synthesized and investigated for their dispersing properties in a cement-based mortar. The formation of mPEG-COOH derivatives and their pseudorotaxanes was investigated by 1D nuclear magnetic resonance, diffusion ordered spectroscopy, and thermogravimetric analysis experiments. Mortar tests clearly indicate that mPEG-COOH@β-CD-interpenetrated supramolecules show excellent dispersing abilities.

Neoadjuvant Chemotherapy Followed by Radical Surgery versus Concurrent Chemo-Radiotherapy in the Treatment of Locally Advanced Cervical Cancer: A Multicenter Retrospective Analysis.

Objectives: This study aims to evaluate oncological outcomes in women affected by locally advanced cervical cancer (LACC) treated by neoadjuvant chemotherapy before radical surgery (NACT + RS) or concurrent chemo-radiotherapy (CCRT).

Methods: This was a multicenter retrospective analysis of data related to women with LACC (FIGO stage IB2-IVA), who were treated by NACT + RS or CCRT between November 2006 and January 2018. The first endpoints were the evaluation of disease-free survival (DFS) and overall survival (OS); univariate and multivariate analyses were performed for identifying the prognostic factors independently associated with these oncological outcomes.

Study on the Influence of Chirality in the Threading of Calix[6]arene Hosts with Dialkylammonium Axles.

The influence of chirality in calixarene threading has been studied by exploiting the "superweak anion approach". In particular, the formation of chiral pseudo[2]rotaxanes bearing a classical stereogenic center in their axle and/or wheel components has been considered. Two kind of pseudo[2]rotaxane stereoadducts, the "-chiral" and "-chiral" ones, having the stereogenic center of a cationic axle inside or outside, respectively, the calix-cavity of a chiral calixarene were preferentially formed with specifically designed chiral axles by a fine exploitation of the so-called "-alkyl rule" and a newly defined "endo-α-methyl-benzyl rule" ( endo).

Synthesis and Glycosidase Inhibition Properties of Calix[8]arene-Based Iminosugar Click Clusters.

A set of 6- to 24-valent clusters was constructed with terminal deoxynojirimycin (DNJ) inhibitory heads through C6 or C9 linkers by way of Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reactions between mono- or trivalent azido-armed iminosugars and calix[8]arene scaffolds differing in their valency and their rigidity but not in their size. The power of multivalency to upgrade the inhibition potency of the weak DNJ inhibitor (monovalent DNJ being at 322 and 188 µM for C6 or C9 linkers, respectively) was evaluated on the model glycosidase Jack Bean α-mannosidase (JBα-man). Although for the clusters with the shorter C6 linker the rigidity of the scaffold was essential, these parameters had no influence for clusters with C9 chains: all of them showed rather good relative affinity enhancements per inhibitory epitopes between 70 and 160 highlighting the sound combination of the calix[8]arene core and the long alkyl arms.

Kinetic and Thermodynamic Modulation of Dynamic Imine Libraries Driven by the Hexameric Resorcinarene Capsule.

The composition of dynamic covalent imine libraries (DCL) adapts to the presence of the hexameric resorcinarene capsule. In the presence of the self-assembled capsule, a kinetic and thermodynamic modulation of the imine constituents of the DCLs was observed, which was induced by an unusual predatory action of the capsule on specific imine constituents. More complex 2 × 2 DCLs also adapt to the presence of the hexameric capsule, showing a thermodynamic and kinetic modulation of the constituents induced by the predatory action of the capsule.

Dispersing and Retarding Properties of Water-Soluble Tetrasulfonate Resorcin[4]arene and Pyrogallol[4]arene Macrocycles in Cement-Based Mortar.

Water-soluble tetrasulfonate resorcin[4]arene ( and ) and pyrogallol[4]arene () macrocycles were synthesized and investigated for their dispersing properties in cement-based mortars. Mortar tests clearly show that these polyhydroxylated macrocycles (nonpolymeric) work as cement dispersants. Setting time determinations indicate that the macrocycles and show a retarding effect that is reminiscent of the behavior of superplasticizers (SPs) functionalized with polyhydroxylated β-CDs.

Calix[2]naphth[2]arene: A Class of Naphthalene-Phenol Hybrid Macrocyclic Hosts.

Calix[2]naphth[2]arenes make up a new class of phenol-naphthalene hybrid macrocycles. X-ray studies show that calix[2]naphth[2]arene adopts a 1,2-alternate conformation. Alkali metal cations are complexed by the calixnaphtharenes in a 1,2-alternate conformation, by cation···π interactions with the naphthalene walls, and by RO···M ion-dipole interactions.

Prexasertib: an investigational checkpoint kinase inhibitor for the treatment of high-grade serous ovarian cancer.

Introduction Patients with high-grade serous ovarian cancer (HGSOC) have a poor prognosis, and current chemotherapy regimens for treating advanced disease are far from satisfactory. Prexasertib (LY2606368) is a novel checkpoint kinase inhibitor (CHK) under investigation for the treatment of HGSOC. Data from a recent phase II trial showed promising efficacy and safety results for treating wild-type BRCA HGSOC.