Preparation,crystal structures and spectroscopic characterization of oxalate copper(II) complexes containing the nitrogen ligands 4,4′-dimethyl-2,2′-bipyridine and di(2-pyridyl)sulfide

The preparation, crystal structures and spectroscopic characterization of four oxalate copper(II) complexes containing the 4,4′-dimethyl-2,2′-bipyridine (Mebpy) or di(2-pyridyl)sulfide (DPS) nitrogen ligands namely [μ-(ox){Cu(Mebpy)(NO₃)(H₂O)}₂] (1), [μ-(ox){Cu(Mebpy)(ClO₄)(H₂O)}₂] (2), [μ-(ox){Cu(DPS)(H₂O)}₂](ClO₄)₂ (3) and [Cu(DPS)(ox)(H₂O)] · 2H₂O (4) are described. X-ray diffraction measurements have shown that complexes 1–3 are binuclear, in which the oxalate anion bridges two Cu(II) centers, while the complex (4) is mononuclear and the oxalate anion adopts the terminal bidentate chelating coordination mode. In 1 and 2 the Cu(II) sites display a distorted octahedral geometry (4+2 environment) and in compounds 3 and 4 the Cu(II) centers exhibit a slightly distorted square pyramidal geometry. In addition, complexes 1 and 2 present a 2D supramolecular arrangement through hydrogen bonds between coordination water molecules and nitrate or perchlorate anions and π-stacking interaction between the pyridyl rings of Mebpy nitrogen ligands.     

A new, efficient and stereoselective synthesis of tricyclic and tetracyclic compounds by samarium diiodide induced cyclisations of naphthyl-substituted arylketones--an easy access to steroid-like skeletons

In this report, we present the application of samarium diiodide induced cyclisations of naphthyl-substituted ketones towards an easy and stereoselective access to tri- and tetracyclic-functionalised compounds. Typical naphthalene derivatives were studied to investigate the scope and limitations of this novel cyclisation process. The model substrates studied demonstrate that the samarium ketyl cyclisations are essentially restricted to the formation of six-membered rings. The diastereoselectivity of these reactions is strongly influenced by the connection of the alkyl side chain to the naphthalene core. Gamma-naphth-1-yl-substituted ketones furnished cyclisation products, such as 17 or 22-26, as single diastereomers, whereas gamma-naphth-2-yl-substituted precursors gave mixtures of diastereomers--as demonstrated by the conversion of model compound 10 into tricyclic products 18 a/18 b, or that of cyclohexanone derivative 33 into tetracyclic diastereomers 34 a/34 b. Cyclic ketones as ketyl precursors furnished steroid-like tetracyclic skeletons; however, due to the cis/cis fusion of rings B/C and C/D these products have an "unnatural" bowl-like shape. Several of the cyclisation products have been identified by X-ray analyses, which not only proved the constitutions, but also the relative configurations and the preferred conformations. Steroid analogue 23 was subjected to subsequent transformations, which demonstrate that the styrene-like double bond of such compounds can be used for further structural diversification. First attempts to synthesise related azasteroids by incorporating nitrogen atoms into the ketone moiety are also reported. Thus, pyrrolidine derivatives 44 and 47 as well as piperidine derivatives 50 and 52 were subjected to samarium diiodide induced cyclisations. The expected tetracyclic products 48, 49 a/49 b, 51 and 53 a/53 b were obtained in moderate to good yields. The stereoselectivities observed follow the rules already established for the all-carbon precursors. The resulting products, bearing a nitrogen atom in ring D, are interesting azasteroid analogues with "unnatural" configuration.     

Enzymatic removal of carboxyl protecting groups. III. Fast removal of allyl and chloroethyl esters by Bacillus subtilis esterase (BS2)

An esterase from Bacillus subtilis (BS2) allows the fast and selective removal of allyl, 2-chloroethyl, and 2,2,2-chloroethyl esters under mild conditions in high yields. In addition, BS2 easily hydrolyzes phenacyl esters, while the hydrolysis of sterically hindered diphenylmethyl esters is slow, requiring longer reaction time and higher enzyme/substrate ratio.     

Identification, synthesis, and conformation of tri- and tetrathiacycloalkanes from marine bacteria

Seven new cyclic natural polysulfides 1-7 were identified in extracts of two bacterial Cytophaga strains (CFB-phylum) isolated from biofilms from the North Sea. Their structures are based on mono- and dimeric-cyclization products of 2-methylpropane-1,2-dithiol 8, which was also present in the extract in trace amounts. The structures were deduced by analysis of their mass spectra and confirmed by synthesis. The 1H NMR spectra of some these compounds suggested a high flexibility of the trithiepane and tetrathiocane systems. Therefore, their conformation was further analyzed by DFT calculations and dynamic NMR spectroscopy. While thiepane 4 possesses a twist-chair lowest energy conformation, its isomers 2 and 3 adopt a chairlike conformation, as does the tetrathiocane 5. In contrast, tetrathiocane 6 favors again a twisted chair conformation.     

Dynamical Renormalization Group for Mode-Coupling Field Theories with Solenoidal Constraint

Journal of Statistical Physics - A correction to this paper has been published: https://doi.org/10.1007/s10955-021-02770-w     

Relaxation of bulk and interfacial energies

In this paper we obtain an integral representation for the relaxation inBV(Ω; ? ^p ) of the functional $$u \mapsto \int\limits_\Omega {f(x.\nabla u(x))dx + \int\limits_{\sum _{(u)} } {\varphi (x,[u](x),v(x))dH_{N - 1} (x)} }$$ with respect to theBV weak * convergence.     

Direct Catalytic Enantio‐ and Diastereoselective Mannich Reaction of Isocyanoacetates and Ketimines

A catalytic asymmetric synthesis of imidazolines with a fully substituted β‐carbon atom by a Mannich‐type addition/cyclization reaction of isocyanoacetate pronucleophiles and N‐diphenylphosphinoyl ketimines has been developed. When a combination of a cinchona‐derived aminophosphine precatalyst and silver oxide was employed as a binary catalyst system, good reactivity, high diastereoselectivities (up to 99:1 d.r.), and excellent enantioselectivities (up to 99 % ee) were obtained for a range of substrates.     

High‐resolution high‐performance liquid chromatography with electrospray ionization mass spectrometry and tandem mass spectrometry characterization of a new isoform of human salivary acidic proline‐rich proteins named Roma‐Boston Ser22(Phos) → Phe variant

During a survey of human saliva by a top‐down reversed‐phase high‐performance liquid chromatography with electrospray ionization mass spectrometry approach, two proteins eluting at 27.4 and 28.4 min, with average masses of 15 494 ± 1 and 11 142 ± 1 Da, were detected in a subject from Boston. The Δmass value (4352 Da) of the two proteins was similar to the difference in mass values between intact (150 amino acids, [a.a.]) and truncated acidic proline‐rich proteins (aPRPs; 106 a.a.) suggesting an a.a. substitution in the first 106 residues resulting in a strong reduction in polarity, since under the same experimental conditions aPRPs eluted at ～22.5 min (intact) and 23.5 min (truncated forms). Manual inspection of the high‐resolution high‐performance liquid chromatography with electrospray ionization tandem mass spectra of the truncated isoform showed the replacement of the phosphorylated Ser‐22 in PRP‐3 with a Phe residue. Inspection of the tandem mass spectra of the intact isoform confirmed the substitution, which is allowed by the code transition TCT→TTT and is in agreement with the dramatic increase in elution time. The isoform was also detected in two other subjects, one from Boston (unrelated to the previous) and one from Rome. For this reason we propose to name this variant PRP‐1 (PRP‐3) RB (Roma‐Boston) Ser₂₂(phos)→Phe.     

Glycosaminoglycan profiling in different cell types using infrared spectroscopy and imaging

We recently identified vibrational spectroscopic markers characteristic of standard glycosaminoglycan (GAG) molecules. The aims of the present work were to further this investigation to more complex biological systems and to characterize, via their spectral profiles, cell types with different capacities for GAG synthesis. After recording spectral information from individual GAG standards (hyaluronic acid, chondroitin sulfate, dermatan sulfate, heparan sulfate) and GAG-GAG mixtures, GAG-defective mutant Chinese hamster ovary (CHO)-745 cells, wild-type CHO cells, and chondrocytes were analyzed as suspensions by high-throughput infrared spectroscopy and as single isolated cells by infrared imaging. Spectral data were processed and interpreted by exploratory unsupervised chemometric methods based on hierarchical cluster analysis and principal component analysis. Our results showed that the spectral information obtained was discriminant enough to clearly delineate between the different cell types both at the cell suspension and single-cell levels. The abilities of the technique are to perform spectral profiling and to identify single cells with different potentials to synthesize GAGs. Infrared microspectroscopy/imaging could therefore be developed for cell screening purposes and further for identifying GAG molecules in normal tissues during physiological conditions (aging, healing process) and numerous pathological states (arthritis, cancer). Figure

FTIR imaging for profiling GAG-synthesizing cells     

Urine 2DE proteome analysis in healthy condition and kidney disease

Urine is a source of potential markers of disease. In the context of renal disease, urine is particularly important as it may directly reflect kidney injury. Current markers of renal dysfunction lack both optimal specificity and sensitivity, and improved technologies and approaches are needed. There is no clear consensus about the best sample pretreatment procedure for 2DE analysis of the urine proteome. Sample pretreatment conditions spots resolution and detection sensitivity, critically. As a first goal, we exhaustively compared eight different sample cleaning and protein purification methodologies for 2DE analysis of urine from healthy individuals. Oasis® HLB cartridges allowed the detection of the highest number of low molecular weight proteins; while PD10 desalting columns resulted in the highest number of detected spots in the high molecular weight area. Sample pretreatment strategies were also explored in the context of proteinuria, a clinical condition often associated to renal damage. Testing of urine samples from 13 patients with hypertension or kidney disease and different levels of proteinuria identified Oasis® HLB cartridge purification in combination with albumin depletion by ProteoPrep kit as the best option for urine proteome profiling from patients with proteinuric (> 30 mg/L albumin in urine) renal disease.