Parsimonious and Efficient Likelihood Composition by Gibbs Sampling

The traditional maximum likelihood estimator (MLE) is often of limited use in complex high-dimensional data due to the intractability of the underlying likelihood function. Maximum composite likelihood estimation (McLE) avoids full likelihood specification by combining a number of partial likelihood objects depending on small data subsets, thus enabling inference for complex data. A fundamental difficulty in making the McLE approach practicable is the selection from numerous candidate likelihood objects for constructing the composite likelihood function. In this article, we propose a flexible Gibbs sampling scheme for optimal selection of sub-likelihood components. The sampled composite likelihood functions are shown to converge to the one maximally informative on the unknown parameters in equilibrium, since sub-likelihood objects are chosen with probability depending on the variance of the corresponding McLE. A penalized version of our method generates sparse likelihoods with a relatively small number of components when the data complexity is intense. Our algorithms are illustrated through numerical examples on simulated data as well as real genotype single nucleotide polymorphism (SNP) data from a case–control study.     

Argyres-Seiberg Duality and the Higgs Branch

We demonstrate the agreement between the Higgs branches of two ${\mathcal{N}=2}We demonstrate the agreement between the Higgs branches of two N=2{\mathcal{N}=2} theories proposed by Argyres and Seiberg to be S-dual, namely the SU(3) gauge theory with six quarks, and the SU(2) gauge theory with one pair of quarks coupled to the superconformal theory with E ₆ flavor symmetry. In mathematical terms, we demonstrate the equivalence between a hyperk?hler quotient of a linear space and another hyperk?hler quotient involving the minimal nilpotent orbit of E ₆, modulo the identification of the twistor lines.     

Characterization and Structural Insights of the Reaction Products by Direct Leaching of the Noble Metals Au,Pd and Cu with N,N′-Dimethyl-piperazine-2,3-dithione/I2 Mixtures

In the context of new efficient and safe leaching agents for noble metals, this paper describes the capability of the Me₂pipdt/I₂ mixture (where Me₂pipdt = N,N′-dimethyl-piperazine-2,3-dithione) in organic solutions to quantitatively dissolve Au, Pd, and Cu metal powders in mild conditions (room temperature and pressure) and short times (within 1 h in the reported conditions). A focus on the structural insights of the obtained coordination compounds is shown, namely [AuI₂(Me₂pipdt)]I₃ (1), [Pd(Me₂pipdt)₂]I₂ (2a) and [Cu(Me₂pipdt)₂]I₃ (3), where the metals are found, respectively, in 3+, 2+ and 1+ oxidation states, and of [Cu(Me₂pipdt)₂]BF₄ (4) and [Cu(Me₂dazdt)₂]I₃ (5) (Me₂dazdt = N,N′-dimethyl-perhydrodizepine-2,3-dithione) compared with 3. Au(III) and Pd(II) (d⁸ configuration) form square–planar complexes, whereas Cu(I) (d¹⁰) forms tetrahedral complexes. Density functional theory calculations performed on the cationic species of 1–5 help to highlight the nature of the bonding in the different complexes. Finally, the valorization of the noble metals-rich leachates is assessed. Specifically, gold metal is quantitatively recovered from the solution besides the ligands, showing the potential of these systems to promote metal recycling processes.     

How Computations Can Assist the Rational Design of Drugs for Photodynamic Therapy: Photosensitizing Activity Assessment of a Ru(II)-BODIPY Assembly

Ruthenium-based complexes represent a new frontier in light-mediated therapeutic strategies against cancer. Here, a density functional-theory-based computational investigation, of the photophysical properties of a conjugate BODIPY-Ru(II) complex, is presented. Such a complex was reported to be a good photosensitizer for photodynamic therapy (PDT), successfully integrating the qualities of a NIR-absorbing distyryl-BODIPY dye and a PDT-active [Ru(bpy)₃]²⁺ moiety. Therefore, the behaviour of the conjugate BODIPY-Ru(II) complex was compared with those of the metal-free BODIPY chromophore and the Ru(II) complex. Absorptions spectra, excitation energies of both singlet and triplet states as well as spin–orbit-matrix elements (SOCs) were used to rationalise the experimentally observed different activities of the three potential chromophores. The outcomes evidence a limited participation of the Ru moiety in the ISC processes that justifies the small SOCs obtained for the conjugate. A plausible explanation was provided combining the computational results with the experimental evidences.     

In Vitro Bioaccessibility and Antioxidant Activity of Phenolic Compounds in Coffee-Fortified Yogurt

Yogurt is considered one of the most popular and healthy dairy products, and has been exploited as a delivery matrix for phenolic compounds. In this study, coffee powder was added to yogurt as a functional ingredient to produce coffee-fortified yogurt. Total phenolic compounds, antioxidant activity and individual hydroxycinnamic acids have been identified and quantified through mass spectrometry. The results from coffee-fortified yogurt were compared with fermented coffee and plain yogurt. Coffee-fortified yogurt had higher total phenolic content and antioxidant activity compared to plain yogurt. However, the total phenolic compounds found in coffee-fortified yogurt represented only 38.9% of the original content in coffee. Caffeoylquinic acids were the most abundant phenolic compounds in coffee. Fermented coffee and coffee-fortified yogurt displayed lower amounts of individual phenolic compounds with respect to coffee (69.8% and 52.4% of recovery, respectively). A protective effect of the yogurt matrix on total and individual coffee phenolic compounds has been observed after in vitro digestion, resulting in a higher bioaccessibility in comparison with digested fermented coffee. Moreover, coffee-fortified yogurt showed the highest antioxidant values after digestion. These findings clearly demonstrate that coffee-fortified yogurt can be considered a significant source of bioaccessible hydroxycinnamic acids, besides its health benefits as a fermented dairy product.     

From the Streets to the Judicial Evidence: Determination of Traditional Illicit Substances in Drug Seizures by a Rapid and Sensitive UHPLC-MS/MS-Based Platform

According to the 2021 World Drug Report, around 275 million people use drugs of abuse, and 36 million people suffer from addiction, fostering a thriving market for illicit substances. In Italy, 30,083 people were reported to the Judicial Authority for offenses in violation of the Italian Law D.P.R. 309/1990. These offences are sentenced after a qualitative–quantitative analysis of seized materials. Given the large quantity of seized drugs and the need to perform accurate analytical determinations, Italian forensic laboratories struggle to complete analyses in a short time, delaying the entire reporting process needed to achieve sentencing. For this purpose, an UHPLC-MS/MS-based platform was developed at the University of Milano-Bicocca to support law-enforcement authorities. Software was designed to easily manage street seizure acquisition, documentation registration, and sampling. A sensitive UHPLC-MS/MS method was fully validated for the quantification of the traditional illicit substances (cocaine, heroin, 6-MAM, morphine, amphetamine, methamphetamine, MDMA, ketamine, GHB, GBL, LSD, trans-∆9-THC, and THCA) at the ppb level. The final report is relayed to the Prefecture in 3–4 days, even within 24 h for urgent requests. The platform allows for semi-automatic data handling to minimize erroneous results for an accurate report generation by standardized procedures.     

Correction: An exchange coupled meso–meso linked vanadyl porphyrin dimer for quantum information processing

Correction for ‘An exchange coupled meso–meso linked vanadyl porphyrin dimer for quantum information processing’ by Davide Ranieri et al., Chem. Sci., 2022, https://doi.org/10.1039/d2sc04969d.

During the editorial production of the finished article, the graphics associated with Fig. 3(a) and (b) were inadvertently switched.Open in a separate windowFig. 3Room temperature angular-dependent CW EPR X-band spectra of (a) m-[VO(TrPP)]₂ and (b) o-[VO(TrPP)]₂ for crystal rotations around three orthogonal axes. For both panels, the upper row shows the 2D experimental EPR contour plots for the three rotations, acquired with a 3° step; the lower row shows representative EPR spectra (black lines) for the three rotations – from 0° to 180° every 15° – together with the best spectral simulations (red lines) obtained by using |J| = 0.01 (0.005) cm⁻¹ and |J| = 0.05 (0.01) cm⁻¹ for (a) and (b), respectively. Experimental frequency: 9.40 GHz for (a), 9.87 GHz for (b).The intended version of Fig. 3 is shown below, and replaces that of the original article:The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.     

Controlled Decoration of [60]Fullerene with Polymannan Analogues and Amino Acid Derivatives through Malondiamide-Based Linkers

In the last few years, nanomaterials based on fullerene have begun to be considered promising tools in the development of efficient adjuvant/delivery systems for vaccination, thanks to their several advantages such as biocompatibility, size, and easy preparation and modification. In this work we reported the chemoenzymatic synthesis of natural polymannan analogues (di- and tri-mannan oligosaccharides characterized by α1,6man and/or α1,2man motifs) endowed with an anomeric propargyl group. These sugar derivatives were submitted to 1,3 Huisgen dipolar cycloaddition with a malondiamide-based chain equipped with two azido terminal groups. The obtained sugar-modified malondiamide derivatives were used to functionalize the surface of Buckminster fullerene (C₆₀) in a highly controlled fashion, and yields (11–41%) higher than those so far reported by employing analogue linkers. The same strategy has been exploited to obtain C₆₀ endowed with natural and unnatural amino acid derivatives. Finally, the first double functionalization of fullerene with both sugar- and amino acid-modified malondiamide chains was successfully performed, paving the way to the possible derivatization of fullerenes with immunogenic sugars and more complex antigenic peptides.     

Three novel interpenetrating diamondoid networks from self-assembly of 1,12-dodecanedinitrile with silver(I) salts

The self-assembly of 1,12-dodecanedinitrile (ddn) with various silver salts (NO(3)(-), PF(6)(-), AsF(6)(-), ClO(4)(-)) afforded new polymeric coordination networks with the general formula [Ag(ddn)(2)]X. All these species contain interpenetrating diamondoid nets showing interesting features: with X=NO(3)(-) the cationic [Ag(ddn)(2)](+) network exhibits the highest interpenetration (tenfold) ever found within diamondoid nets exclusively based on coordinative bonds. When X=PF(6)(-) or AsF(6)(-) an eightfold diamondoid network is obtained that shows an unusual [4+4] mode of interpenetration, instead of the "normal" set of eight nets equally translated along a principal axis of the adamantanoid cages. The polymeric species that forms with X=ClO(4)(-) is a fourfold interpenetrating diamondoid network; the lower degree of interpenetration in this case is related to the conformation assumed by the flexible ddn ligands.