Aortic Dissection: Spectacular Survival or Nightmare?

We describe the case of a male patient who remarkably survived two severe cardiovascular events: ascending aortic dissection and descending aortic dissection two years later. Later, the third occurrence of aortic dissection, this time involving the abdominal aorta, became an absolute nightmare for the patient, progressively being complicated by periaortic hematoma and severe anemia - events that ultimately led to his death.

The Effect of the Organizational Climate on the Integrative-Qualitative Intentional Behavior in Romanian Preschool Education-A Top-Down Perspective.

The concept of educational organizational climate relates to the relational, social, psychological, affective, intellectual, cultural and moral environment that characterizes educational/teaching and managerial activity at the level of a school organization. This study is based on the theory of planned behavior framework in measuring preschool teachers' intentional integrative-qualitative behaviors and Marzano's Model of Teaching Effectiveness. The Marzano Model outlines educational strategies and gives teachers and administrators tools to help teachers become more effective. A sample of 200 valid responses was gathered in an online investigation that targeted preschool educators from Romania. Marzano's Model of Teaching Effectiveness is an evaluation tool used to measure the success of highly effective teachers, which is further utilized in this study to measure preschool teachers' effectiveness in relation to intentional integrative-qualitative behaviors. The integrative-qualitative intentional behaviors are measured with the IQIB scale. This research assumes collegiality and professionalism as independent variables and interrogates preschool teachers' behavioral intention toward adopting integrative-qualitative behaviors through the sequential mediators of Planning and Preparing, Reflecting on Teaching and Classroom Strategies and Behaviors from a top-down perspective. The results revealed a significant indirect effect of Collegiality and Professionalism on preschool teachers' behavioral intention toward adopting intentional integrative-qualitative behaviors through the sequential mediators Planning and Preparing, Reflecting on Teaching and Classroom Strategies and Behaviors, confirming our hypothesis. Discussion and implications are offered from a top-down sustainable educational management perspective.

Synthesis of 2- and 2,3-substituted pyrazolo[1,5-a]pyridines: scope and mechanistic considerations of a domino direct alkynylation and cyclization of N-iminopyridinium ylides using alkenyl bromides, alkenyl iodides, and alkynes.

Direct functionalization and tandem processes have both received considerable recent interest due to their cost and time efficiency. Herein we report the synthesis of difficult to obtain 2-substituted pyrazolo[1,5-a]pyridines through a tandem palladium-catalyzed/silver-mediated elimination/direct functionalization/cyclization reaction involving N-benzoyliminopyridinium ylides. As such, these biologically important molecules are prepared in an efficient, high-yielding manner, only requiring a two-step sequence from pyridine. Aryl-substituted alkenyl bromides and iodides are effective ylide coupling partners. Mechanistic studies led to the use of terminal alkynes, which extended the scope of the reaction to include alkyl substitution on the unsaturated reactive site. The optimization, scope, and mechanistic considerations of the process are discussed.

Ligand-controlled selectivity in the desymmetrization of meso cyclopenten-1,4-diols via rhodium(I)-catalyzed addition of arylboronic acids.

A highly enantioselective desymmetrization of meso cyclopent-2-ene-1,4-diethyl dicarbonates has been developed using a Rh-catalyzed asymmetric allylic substitution. Depending on the type of ligand used, each of two regioisomeric products can be obtained in good yield and excellent enantioselectivity. Under rhodium(I) catalysis, bisphosphine P-Phos ligands form trans-1,2-arylcyclopentenols as the major product, whereas Segphos ligands lead predominantly to trans-1,4-arylcyclopentenols.

Pseudomonas Species Diversity Along the Danube River Assessed by rpoD Gene Sequence and MALDI-TOF MS Analyses of Cultivated Strains.

A collection of 611 Pseudomonas isolated from 14 sampling sites along the Danube River were identified previously by MALDI-TOF MS with the VITEK MS system and were grouped in 53 clusters by their main protein profiles. The strains were identified in the present study at the phylospecies level by rpoD gene sequencing. Partial sequences of the rpoD gene of 190 isolates representatives of all clusters were analyzed. Strains in the same MALDI-TOF cluster were grouped in the same phylospecies when they shared a minimum 95% similarity in their rpoD sequences. The sequenced strains were assigned to 34 known species (108 strains) and to 32 possible new species (82 strains). The 611 strains were identified at the phylospecies level combining both methods. Most strains were assigned to phylospecies in the Pseudomonas putida phylogenetic group of species. Special attention was given to 14 multidrug resistant strains that could not be assigned to any known Pseudomonas species and were considered environmental reservoir of antibiotic resistance genes. Coverage indices and rarefaction curves demonstrated that at least 50% of the Pseudomonas species in the Danube River able to grow in the isolation conditions have been identified at the species level. Main objectives were the confirmation of the correlation between the protein profile clusters detected by MALDI-TOF MS and the phylogeny of Pseudomonas strains based on the rpoD gene sequence, the assessment of the higher species discriminative power of the rpoD gene sequence, as well as the estimation of the high diversity of Pseudomonas ssp. along the Danube river. This study highlights the Pseudomonas species diversity in freshwater ecosystems and the usefulness of the combination of MALDI-TOF mass spectrometry for the dereplication of large sets of strains and the rpoD gene sequences for rapid and accurate identifications at the species level.

Transition-Metal-Free Amination of Pyridine-2-sulfonyl Chloride and Related N-Heterocycles Using Magnesium Amides.

A new transition-metal-free amination of pyridine-2-sulfonyl chloride and related N-heterocycles using magnesium amides of type R2NMgCl·LiCl is reported. Additionally, the directed ortho-magnesiation of pyridine-2-sulfonamides using TMPMgCl·LiCl was investigated. Reaction of the magnesium intermediates with various electrophiles and subsequent amination using magnesium amides led to a range of 2,3-functionalized pyridines. Also, cyclization reactions providing an aza-indole and an aza-carbazole were carried out.

Directed Zincation with TMPZnCl·LiCl and Further Functionalization of the Tropolone Scaffold.

The directed zincation of tropolone derivatives was achieved using TMPZnCl·LiCl. Various functionalizations of the zincated intermediates by halogenation, acylation, allylation, and Negishi cross-coupling were successfully performed. Additionally, 1,8-conjugate addition-elimination reactions with a variety of arylmagnesium and secondary alkylzinc reagents were carried out to further elaborate the tropolone core.

Transition-Metal-Free Cross-Coupling of Aryl and N-Heteroaryl Cyanides with Benzylic Zinc Reagents.

Functionalized 4-benzylated pyridines can be efficiently prepared by a transition-metal-free cross-coupling between various benzylic zinc chlorides and substituted 4-cyanopyridines in THF/DMPU under microwave irradiation (40 °C, 0.5-1.5 h). Selective benzylations on polycyano-aromatics have also been achieved under these mild conditions. We also report a novel oxidative nucleophilic substitution of a hydrogen on 1,3-dicyanobenzene using benzylic zinc reagents.

Spectroscopic studies of lanthanide complexes of varying nuclearity based on a compartmentalised ligand.

The synthesis, characterization and solid-state luminescence spectroscopy of mononuclear (f), heterodinuclear (d-f) and heterotrinuclear (d-f-d) coordination compounds with the compartmental ligand N,N'-bis(3-hydroxyl salicylidene)benzene-1,2-diamine (H2L) are reported. The trivalent lanthanide ions Nd(III), Sm(III), Eu(III), Gd(III), Tb(III) and Dy(III) as single metal centres or in combination with either Zn(II) or Ni(II) were coordinated. Compounds are characterised by elemental analyses, IR, 1D and 2D solution (1)H and (13)C NMR spectroscopy, measurements of magnetic moments and solid state UV-Vis-NIR reflectance, luminescence and Raman spectroscopy techniques. Crystal structures of the dinuclear compounds [SmZn(O2NO)3(L)(OH2)]·EtOH and [DyZn(O2NO)2(Cl)(L)(EtOH)]·3EtOH and the trinuclear compound [TbZn2(L)2(Cl)2(OH2)](NO3)·EtOH are presented, where samarium(iii) displays a coordination number of ten, with a bicapped cubic geometry, while for the dysprosium compound a nine-coordinated environment with a tricapped trigonal prismatic geometry is shown. Their crystals belong to the triclinic system and the P1[combining macron] space group. The coordination number for terbium(iii) in the trinuclear complex is nine, with a tricapped trigonal prismatic geometry, and its crystal belongs to the monoclinic system, space group C2/c. For these three compounds, the zinc ion stabilises a penta-coordinated environment with square pyramid geometry. All mononuclear and dinuclear compounds are neutral, whereas the trinuclear complexes are ionic. The results of DFT theoretical calculations for the ligand (H2L) are used to assign the ligand singlet and triplet excited state energy levels. Luminescence studies of the neodymium compounds indicate that the ligand is a sensitizer for NIR emitters.

TMP-magnesium and TMP-zinc bases for the regioselective metalation of the cinnoline scaffold.

A regioselective functionalization of cinnolines in positions 3 and 8 using metalations has been developed. This involves either the use of a frustrated Lewis pair consisting of BF3·Et2O and TMP2Mg·2LiCl or the in situ generated base TMP2Zn·2MgCl2·2LiCl. Successive metalations allow the preparation of 3,8-disubstituted cinnolines. Various functionalizations by acylation, allylation, and cross-coupling reactions with aryl halides or alkenyl iodides were carried out successfully.

C-H functionalization of cyclopropanes: a practical approach employing a picolinamide auxiliary.

A Pd-catalyzed, picolinamide-enabled, and efficient C-H arylation of cyclopropanes is described. The reaction can be promoted by either a silver additive or catalytic pivalic acid in the presence of a carbonate base. Various aryl iodides can be employed as coupling partners, providing exclusively cis-substituted cyclopropylpicolinamides.

Silver-promoted, palladium-catalyzed direct arylation of cyclopropanes: facile access to spiro 3,3'-cyclopropyl oxindoles.

The Pd-catalyzed, Ag(I)-mediated intramolecular direct arylation of cyclopropane C-H bonds is described. Various spiro 3,3'-cyclopropyl oxindoles can be obtained in good to excellent yields from easily accessible 2-bromoanilides. The kinetic isotope effect was determined and epimerization studies were conducted, suggesting that the formation of a putative Pd-enolate is not operative and that the reaction proceeds via a C-H arylation pathway.

Nickel(0)/NaHMDS adduct-mediated intramolecular alkylation of unactivated arenes via a homolytic aromatic substitution mechanism.

A variety of polycycles can be synthesized via an intramolecular alkylation cyclization promoted by Ni(PPh(3))(4) and NaHMDS. Mechanistic investigations support the catalytic nature of Ni(0) in the course of TEMPO scavenging experiments and its association with the substrate and NaHMDS to form an adduct by DOSY NMR.

Potassium tert-butoxide promoted intramolecular arylation via a radical pathway.

Potassium tert-butoxide mediated intramolecular cyclization of aryl ethers, amines, and amides was efficiently performed under microwave irradiation to provide the corresponding products in high regioisomeric ratios. The reaction proceeds via single-electron transfer to initiate the formation of an aryl radical, followed by a kinetically favored 5-exo-trig and subsequent ring expansion.