Theoretical descriptions of novel triplet germylenes M<Subscript>1</Subscript>-Ge-M<Subscript>2</Subscript>-M<Subscript>3</Subscript> (M<Subscript>1</Subscript> = H,Li, Na,K; M<Subscript>2</Subscript> = Be,Mg, Ca; M<Subscript>3</Subscript> = H,F, Cl,Br)

In a quest to identify new ground-state triplet germylenes, the stabilities (singlet–triplet energy differences, ΔE_S–T) of 96 singlet (s) and triplet (t) M₁-Ge-M₂-M₃ species were compared and contrasted at the B3LYP/6–311++G**, QCISD(T)/6–311++G**, and CCSD(T)/6–311++G** levels of theory (M₁?=?H, Li, Na, K; M₂?=?Be, Mg, Ca; M₃?=?H, F, Cl, Br). Interestingly, F-substituent triplet germylenes (M₃?=?F) appear to be more stable and linear than the corresponding Cl- or Br-substituent triplet germylenes (M₃?=?Cl or Br). Triplets with M₁?=?K (i.e., the K-Ge-M₂-M₃ series) seem to be more stable than the corresponding triplets with M₁?=?H, Li, or Na. This can be attributed to the higher electropositivity of potassium. Triplet species with M₃?=?Cl behave similarly to those with M₃?=?Br. Conversely, triplets with M₃?=?H show similar stabilities and linearities to those with M₃?=?F. Singlet species of formulae K-Ge-Ca-Cl and K-Ge-Ca-Br form unexpected cyclic structures. Finally, the triplet germylenes M₁-Ge-M₂-M₃ become more stable as the electropositivities of the α-substituents (M₁ and M₂) and the electronegativity of the β-substituent (M₃) increase.     

Au Gravettien, dans la grotte Cosquer (Marseille, Bouches-du-Rhône), l'Homme a-t-il compté sur ses doigts ?

Negative hands, occasionally with incomplete fingers, are often found in Paleolithic caves but so far have received no definitive explanation. Nowadays they are more commonly seen as the expression of a gestural language. In this paper, we suggest that the negative hands visible in the Cosquer cave and dating from around 27?000 BP could represent counting on fingers. Several arguments are developed to support this hypothesis. Furthermore we also suggest that the dots and dashes often associated with negative hands in numerous caves, might be another, more advanced way of representing numbers.     

Backbone and Ile-δ1, Leu,Val methyl <Superscript>1</Superscript>H, <Superscript>15</Superscript>N,and <Superscript>13</Superscript>C,chemical shift assignments for <Emphasis Type="Italic">Rhizopus chinensis</Emphasis> lipase

Lipase r27RCL is a 296-residue, 33 kDa monomeric enzyme with high ester hydrolysis activity, which has significant applications in the baking, paper and leather industries. The lipase gene proRCL from Rhizopus microsporus var. chinensis (also Rhizopus chinensis) CCTCC M201021 was cloned as a fusion construct C-terminal to a maltose-binding protein (MBP) tag, and expressed as MBP-proRCL in an Escherichia coli BL21 trxB (DE3) expression system with uniform ²H,¹³C,¹⁵N-enrichment and Ile-δ1, Leu, and Val ¹³CH₃ methyl labeling. The fusion protein was hydrolyzed by Kex2 protease at the recognition site Lys-Arg between residues ?29 and ?28 of the prosequence, producing the enzyme form called r27RCL. Here we report extensive backbone ¹H, ¹⁵N, and ¹³C, as well as Ile-δ1, Leu, and Val side chain methyl, NMR resonance assignments for r27RCL.     

Études stratigraphique,sédimentologique et paléomagnétique des travertins de Kocabaş, Bassin de Denizli,Anatolie, Turquie,contenant des restes fossiles quaternaires

Stratigraphic, sedimentological and paleomagnetic studies were conducted on the travertine from Denizli Basin, near Kocabas village, in the Denizli region in Turkey, following the paleontological discovery in 2002. The stratigraphic and sedimentological studies show at least two main cycles of mass travertine, separated by a fluvial deposit and overlain by a fluvio-lacustrine deposit. These travertines must have formed in environments with strong hydrodynamics (streams or waterfalls) and are preferentially located at breaks of slopes. The paleomagnetic study shows that all the quarry travertine presents reverse magnetic polarity. On the other hand, the detrital fluvio-lacustrine deposit above the travertine presents normal geomagnetic polarity, except at the top, where it is reversed. Given the presence of an archaic Homo erectus skull and Villafranchian paleontological remains in the upper travertine unit, the whole travertine dates from the upper Matuyama, and is more recent than the Olduvai event (1.78 Ma). The normal polarity recorded in the upper fluvio-lacustrine deposit could correspond to the Cobb Mountain excursion, dated to 1.22 Ma.     

Electric-field-induced spin switch of endohedral dodecahedrane heterodimers H@C<Subscript>20</Subscript>H<Subscript>n</Subscript>–C<Subscript>20</Subscript>H<Subscript>n</Subscript>@M (M= Cu,Ag and Au,n = 15, 18, and 19): a theoretical study

We designed nine endohedral dodecahedrane heterodimers H@C₂₀H_n-C₂₀H_n@M (M = Cu, Ag, and Au, n = 15, 18, and 19) that may act as single-molecule spin switches, and we predicted theoretically that the ground states of the dimmers shift from low-spin states (S = 0) to the high-spin states (S = 1) under an external electric field applied parallel or perpendicular to the molecular symmetry axes, consisting well with the analyses of Stark effect. Molecular orbitals analyses provide an intuitive insight into the spin crossover behavior. This study expands the application of endohedral chemistry and provides new molecules for designing single-molecule spin switch.     

Effects of activation of μ-, κ<Subscript>1</Subscript>-, δ<Subscript>1</Subscript>-, δ<Subscript>2</Subscript>-, and ORL<Subscript>1</Subscript>-receptors on heart resistance to the pathogenic action of delayed ischemia and reperfusion

Different subtypes of opioid receptors (OR) were activated in rats in vivo to study the activation effect on the heart’s resistance to ischemia and reperfusion. It has been established that administration of deltorphin II, a selective δ₂-OR agonist, lowered the infarct size/area at risk index (IS/AAR) by 23%. Naltrexone, naloxone methiodide (an OR inhibitor not penetrating the blood-brain barrier (BBB)), and naltriben (δ₂-antagonist) eliminated the cardioprotective effect of deltorphin II, while BNTX (a δ₁-antagonist) produced no effect on the cardioprotective action of the δ₂-agonist. The infarct-reducing effect of deltorphin II was eliminated by administration of chelerythrine (a protein kinase C (PKC) inhibitor), glibenclamide (a K_ATP-channels inhibitor), and 5-hydroxydecanoate (a mitochondrial K_ATP-channel blocker). Administration of other opioids did not reduce the IS/AAR index. It has been established that all the deltorphins manifest antiarrhythmic potency. Other opioids do not produce any effect on the incidence of arrhythmia occurrences. The antiarrhythmic effect of deltorphin II was eliminated by preliminary administration of naltrexone, naloxone methiodide, and naltriben, but BNTX did not affect the δ₂-agonist’s anti-arrhythmic effect. The preliminary administration of chelerythrine, a PKC inhibitor, eliminated the δ₂ agonist’s antiarrhythmic action. However, glibenclamide and 5-hydroxydecanoate did not alter the antiarrhythmic effect by deltorphin II. Therefore, activation of the peripheral δ₂-ORs reduces the infarct size and prevents the onset of arrhythmias. The antiarrhythmic effect of the δ₂-OR stimulation is mediated by activating PKC and opening the mitochondrial K_ATP-channels. PKC participates in the antiarrhythmic effect of the δ₂-OR activation, but this effect does not depend on the condition of K_ATP-channels.     

Metal–metal bonding and aromaticity in [M<Subscript>2</Subscript>(NHCHNH)<Subscript>3</Subscript>]<Subscript>2</Subscript> (μ-E)<Subscript>2</Subscript> (E = O,S; M = Nb,Mo, Tc,Ru, Rh)

The nature of M–M bonding and aromaticity of [M₂(NHCHNH)₃]₂(μ-E)₂ (E?=?O, S; M?=?Nb, Mo, Tc, Ru, Rh) was investigated using atoms in molecules (AIM) theory, electron localization function (ELF), natural bond orbital (NBO) and molecular orbital analysis. These analyses led to the following main conclusions: in [M₂(NHCHNH)₃]₂(μ-E)₂ (E?=?O, S; M?=?Nb, Mo, Tc, Ru, Rh), the Nb–Nb, Ru–Ru, and Rh–Rh bonds belong to “metallic” bonds, whereas Mo–Mo and Tc–Tc drifted toward the “dative” side; all these bonds are partially covalent in character. The Nb–Nb, Mo–Mo, and Tc–Tc bonds are stronger than Ru–Ru and Rh–Rh bonds. The M–M bonds in [M₂(NHCHNH)₃]₂(μ-S)₂ are stronger than those in [M₂(NHCHNH)₃]₂(μ-O)₂ for M?=?Nb, Mo, Tc, and Ru. The NICS(1)_ZZ values show that all of the studied molecules, except [Ru₂(NHCHNH)₃]₂(μ-O)₂, are aromaticity molecules. O-bridged compounds have more aromaticity than S-bridged compounds.

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Graphical Abstract Left Molecular graph, and right electron localization function (ELF) isosurface of [M₂(NHCHNH)₃]₂(μ-E)₂(E?=?O, S; M?=?Nb, Mo, Tc, Ru, Rh)

     

Development,optimization, and biovalidation of <Superscript>99m</Superscript>Tc–insulin complex

Human biosynthetic insulin is a polypeptide hormone that plays an important and essential role in control of the level of carbohydrate, protein, and fat metabolism in the blood. Human pancreatic insulin was labeled with ^99mTc to form a new radiopharmaceutical with a labeling yield of 99 ± 1% under optimum conditions: 0.1 mL insulin, pH 7, 25 μg stannous chloride, 1 mL (19 mCi) of pertechnetate, room temperature, and 10 min reaction time. The ^99mTc–insulin complex was examined using paper chromatography, ITLC, electrophoresis, and HPLC. In addition, in vitro and in vivo study of ^99mTc–insulin complex was performed at different time intervals.     

<Superscript>1</Superscript>H, <Superscript>13</Superscript>C,and <Superscript>15</Superscript>N resonance assignments for the pro-inflammatory cytokine interleukin-36α

Interleukin-36α (IL-36α) is a recently characterised member of the interleukin-1 superfamily. It is involved in the pathogenesis of inflammatory arthritis in one third of psoriasis patients. By binding of IL-36α to its receptor IL-36R via the NF-κB pathway other cytokines involved in inflammatory and apoptotic cascade are activated. The efficacy of complex formation is controlled by N-terminal processing. To obtain a more detailed view on the structure function relationship we performed a heteronuclear multidimensional NMR investigation and here report the ¹H, ¹³C, and ¹⁵N resonance assignments for the backbone and side chain nuclei of the pro-inflammatory cytokine interleukin-36α.     

Valbro : un nouveau site à vertébrés de l’Oligocène inférieur (MP22) de France (Quercy). I – Contexte géologique ; Mammalia : Rodentia,Hyaenodontida, Carnivora

The locality Valbro (Quercy, France) has yielded a rich fossil vertebrate fauna. Here are presented the geological context, a preliminary faunal list and the systematics of the Rodentia and carnivores, the most abundant taxa of the fauna. The Rodentia are known from 11 taxa: the Theridomyidae Blainvillimys gregarius Schlosser, 1884, Blainvillimys ?gemellus Vianey-Liaud, 1989, Issiodoromys medius (Vianey-Liaud, 1976) and S. cayluxi Schlosser, 1884, the Aplodontidae Plesispermophilus angustidens Filhol, 1882, the Gliridae Butseloglis tenuis (Bahlo, 1975), Butseloglis micio (Misonne, 1957) and Bransatoglis planus (Bahlo, 1975), the Sciuridae Palaeosciurus goti Vianey-Liaud, 1974 and cf. Oligopetes sp., and the Cricetidae Atavocricetodon sp. aff. A. nanus (Pelaez-Campomanes, 1995). Thirteen taxa of carnivores are present at Valbro; among the Hyaenodontida: Hyaenodon leptorhynchus Laizer et Parieu, 1838 and cf. Apterodon sp.; among the Carnivora: a Feliformia gen. et sp. indet., the Nimravidae Nimravus intermedius (Filhol, 1872), Dinailurictis bonali Helbing, 1922 and Nimravidae gen. et sp. indet. (Certainly belonging to one the two already identified species), the Ursida Pachycynodon crassirostris Schlosser, 1888, Pachycynodon sp., Amphicynodon sp. 1 cf. A. typicus (Schlosser, 1888), Amphicynodon ? sp. 2 and Ursida gen. et sp. indet. cf. Pachycynodon boriei (Filhol, 1876), the Mustelida M. olivieri Bonis, 1997, the Carnivora incertae sedis Palaeogale sectoria (Gervais, 1848–1852), the Arctoidea gen. et sp. indet. and Carnivora gen. et sp. indet. (probably representing taxa already identified at lower taxonomic levels). The evolutionary grade of B. gregarius of Valbro compares to that of the species from Mas de Got, La Plante 2 and Cavalé, which supports an MP22 age for Valbro. This datation is further supported by the association of Theridomyinae yielded by the locality (B. gregarius, B. gemellus, I. medius and S. cayluxi), and by the presence of a N. intermedius that well compares the material of the species from Villebramar, La Plante et Mas de Got, of D. bonali, P. sectoria, M. olivieri (species known only from Mas de Got), and by additional evidence from the remaining vertebrates from Valbro, especially the squamates. Despite a limited amount of specimens (341 specimens have been studied), the faunas of rodents and carnivores from Valbro are the most speciose and diverse known for the MP22 level and, for the Carnivora fauna in particular, for the Oligocene of the Old World.     

Correction to: Plastome phylogenomics of Allaeanthus,Broussonetia and Malaisia (Dorstenieae,Moraceae) and the origin of B. × kazinoki

Journal of Plant Research -     

Revision,cladistic analysis and biogeography of Typhochlaena C. L. Koch, 1850, Pachistopelma Pocock, 1901 and Iridopelma Pocock, 1901 (Araneae,?Theraphosidae,Aviculariinae)

Three aviculariine genera endemic to Brazil are revised. Typhochlaena C. L. Koch, 1850 is resurrected, including five species; Pachistopelma Pocock, 1901 includes two species; and Iridopelma Pocock, 1901, six species. Nine species are newly described: Typhochlaena amma sp. n., Typhochlaena costae sp. n., Typhochlaena curumim sp. n., Typhochlaena paschoali sp. n., Pachistopelma bromelicola sp. n., Iridopelma katiae sp. n., Iridopelma marcoi sp. n., Iridopelma oliveirai sp. n. and Iridopelma vanini sp. n. Three new synonymies are established: Avicularia pulchra Mello-Leitão, 1933 and Avicularia recifiensis Struchen & Brändle, 1996 are junior synonyms of Pachistopelma rufonigrum Pocock, 1901 syn. n., and Avicularia palmicola Mello-Leitão, 1945 is a junior synonym of Iridopelma hirsutum Pocock, 1901 syn. n. Pachistopelma concolor Caporiacco, 1947 is transferred to Tapinauchenius Ausserer, 1871, making the new combination Tapinauchenius concolor (Caporiacco, 1947) comb. n. Lectotypes are newly designed for Pachistopelma rufonigrum Pocock, 1901 , Iridopelma hirsutum Pocock, 1901 and Pachistopelma concolor Caporiacco, 1947. Cladistic analyses using both equal and implied weights were carried out with a matrix comprising 62 characters and 38 terminal taxa. The chosen cladogram found with X-Pee-Wee and concavity 6 suggests they are monophyletic. All species are keyed and mapped and information on species habitat and area cladograms are presented. Discussion on biogeography and conservation is provided.     

<Emphasis Type="Italic">N</Emphasis>-Methylation of <Emphasis Type="Italic">N</Emphasis><Superscript>α</Superscript>-Acetylated,Fully C<Superscript>α</Superscript>-Ethylated,Linear Peptides

“Mono-N-methyl scan” is a rational approach for the optimization of the peptide biological properties. N-Methylation of the –CONH– functionality is also a useful tool for discriminating solvent exposed from intramolecularly H-bonded secondary amide groups in peptides. We are currently extending this reaction to linear peptides based on C^α-tetrasubstituted α-amino acids. Following our study on the synthesis and conformation of the mono-N-methylated peptides from C^α-methylated residues, in this work we investigated the N-methylation reaction on homo-peptides to the pentamer level from the C^α-ethylated residue C^α,α-diethylglycine. Under the classical experimental conditions used, exclusively mono-N-methylation (on the N-terminal, acetylated residue) takes place, as unambiguously shown by mass spectrometry, 2D-NMR, and X-ray diffraction techniques. This backbone modification does not seem to involve any significant change in the peptide conformation in the crystalline state. Dedicated to the memory of Prof. Miroslav T. Leplawy (Technical University of Łodz, Poland), who performed the first synthesis of the extremely sterically demanding C^α,α-diethylglycine peptides.     

Synthesis,characterization, and studies on DNA binding of the complex Fe(Sal<Subscript>2</Subscript>dienNO<Subscript>3</Subscript>·H<Subscript>2</Subscript>O)

A new metal complex, Fe(Sal₂dienNO₃·H₂O) (where Sal is salicylaldehyde and dien is diethylenetriamine), has been synthesized and characterized. The interactions between the Fe(III) complex and calf thymus DNA has been investigated using UV and fluorescence spectra, viscosity, thermal denaturation, and molecular modeling. The cleavage reaction on plasmid DNA has been monitored by agarose gel electrophoresis. The experimental results show that the mode of binding of the complex to DNA is classical intercalation and the complex can cleave pBR322 DNA.     

The interaction of CCl<Subscript>4</Subscript> with Ng (Ng = He,Ne, Ar), O<Subscript>2</Subscript>, D<Subscript>2</Subscript>O and ND<Subscript>3</Subscript>: rovibrational energies,spectroscopic constants and theoretical calculations

This investigation generated rovibrational energies and spectroscopic constants for systems of CCl₄ with Ng (Ng?=?He, Ne, Ar), O₂, D₂O and ND₃ from scattering experimental data, and the results presented are of interest for microwave spectroscopy studies of small halogenated molecules. The rovibrational spectra were obtained through two different approaches (Dunham and DVR) within the improved Lennard Jones (ILJ) model. Spectra were also generated within ordinary Lennard Jones and deviations suggest that the ILJ model should be preferred due to interactions beyond dispersion forces presented in these systems. Data from the literature and additional high level quantum mechanical calculations presented in this work show that these systems should not be considered as van der Waals complexes due to halogen bonding (HB) interactions, and this is especially true for the CCl₄–D₂O and CCl₄–ND₃ complexes. The charge displacement from the latter systems are one order of magnitude higher than the values from literature for CCl₄ and He, Ne, Ar and O₂ systems, and show significant deviations between DFT and Hartree-Fock values not previously reported in the literature.     

Recombination initiation: Easy as A, B, C, D… χ?

The octameric Chi (χ) sequence is a recombination hotspot in Escherichia coli. Recent studies suggest a singular mechanism by which χ regulates not only the nuclease activity of RecBCD enzyme, but also the ability of RecBCD to promote loading of the strand exchange protein, RecA, onto χ-containing DNA.     

Theoretical study of noncovalent interactions in XCN···YO<Subscript>2</Subscript>H (X = F,Cl, Br,I; Y = P,As, Sb) complexes

Noncovalent interactions in XCN···YO₂H (X = F, Cl, Br, I; Y = P, As, Sb) complexes were investigated using ab initio calculations at the MP2/aug-cc-pVDZ level of theory. There are four different configurations of these complexes, and the complexes are formed via hydrogen bonds, halogen bonds, π-hole interactions, or dual interactions. An examination of binding distances and interaction energies suggested that π-hole bonds are more stable than the other interactions. Molecular electrostatic potentials, electron densities, second-order stabilization energies, and electron density differences were computed to study the character of these interactions.     

A DFT study of the catalytic pyrolysis of benzaldehyde on ZnO, γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, and CaO models

The catalytic pyrolysis pathways of carbonyl compounds in coal were systematically studied using density functional theory (DFT), with benzaldehyde (C₆H₅CHO) employed as a coal-based model compound and ZnO, γ-Al₂O₃, and CaO as catalysts. The results show that the products of both pyrolysis and catalytic pyrolysis are C₆H₆ and CO. However, the presence of any of the catalysts changes the reaction pathway and reduces the energy barrier, indicating that these catalysts promote C₆H₅CHO decomposition.

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Graphical abstract The presence of catalysts changes the reaction pathway and the energy barrier decreases in the order Ea (no catalyst)> Ea (CaO)> Ea (γ-Al₂O₃)> Ea (ZnO), indicating that these catalysts promote C₆H₅CHO decomposition.