Acute pleurisy mimicking neck pain in a young volleyball player: a case report.

Introduction: Patients presenting to direct access physiotherapists may present with a serious pathology that mimics a musculoskeletal condition. Recognition of atypical clinical patterns allows for referral to an appropriate provider when a serious pathology is present. This case report details a patient with a pulmonary pathology who presented to a physiotherapist with a complaint of neck and chest pain following medical consultations.

as a Versatile and Predictable Chiral Stationary Phase for the Resolution of Racemic Mixtures.

Metal-organic frameworks (MOFs) have become promising materials for multiple applications due to their controlled dimensionality and tunable properties. The incorporation of chirality into their frameworks opens new strategies for chiral separation, a key technology in the pharmaceutical industry as each enantiomer of a racemic drug must be isolated. Here, we describe the use of a combination of computational modeling and experiments to demonstrate that high-performance liquid chromatography (HPLC) columns packed with as the chiral stationary phase are efficient, versatile, robust, and reusable with a wide array of mobile phases (polar and non-polar).

Differentiation of Epoxide Enantiomers in the Confined Spaces of an Homochiral Cu(II) Metal-Organic Framework by Kinetic Resolution.

TAMOF-1, a homochiral metal-organic framework (MOF) constructed from an amino acid derivative and Cu(II), was investigated as a heterogeneous catalyst in kinetic resolutions involving the ring opening of styrene oxide with a set of anilines. The branched products generated from the ring opening of styrene oxide with anilines and the unreacted epoxide were obtained with moderately high enantiomeric excesses. The linear product arising from the attack on the non-benzylic position of styrene oxide underwent a second kinetic resolution by reacting with the epoxide, resulting in an amplification of its final enantiomeric excess and a concomitant formation of an array of isomeric aminodiols.

Homochiral Metal-Organic Frameworks for Enantioselective Separations in Liquid Chromatography.

Selective separation of enantiomers is a substantial challenge for the pharmaceutical industry. Chromatography on chiral stationary phases is the standard method, but at a very high cost for industrial-scale purification due to the high cost of the chiral stationary phases. Typically, these materials are poorly robust, expensive to manufacture, and often too specific for a single desired substrate, lacking desirable versatility across different chiral analytes.

The role of proton shuttling mechanisms in solvent-free and catalyst-free acetalization reactions of imines.

Proton transfer is central to the understanding of chemical processes. More so in addition reactions of the type NuH + E → Nu-EH taking place under solvent-free and catalyst-free conditions. Herein we show that the addition of alcohols or amines (the NuH component) to imine derivatives (the E component), in 1 : 1 ratio, under solvent-free and catalyst-free conditions, are efficient methods to access N,O and N,N-acetal derivatives.

Towards Enzyme-like, Sustainable Catalysis: Switchable, Highly Efficient Asymmetric Synthesis of Enantiopure Biginelli Dihydropyrimidinones or Hexahydropyrimidinones.

Organocatalysts displaying a network of cooperative hydrogen bonds (NCHB) have been employed in an enzyme-like manner for a direct, switchable synthesis of enantiopure hexahydropyrimidinones (HHPMs) or dihydropyrimidinones (DHPMs), which starts at a common, easily accessible α-ureidosulfone stage. The NCHB organocatalyst exploits all its potential as a pure hydrogen-bond biomimetic catalyst even in the presence of organic bases. This one-pot, diastereo- and enantioselective synthetic procedure has been proven to be robust, scalable, highly efficient, and environmentally benign.

Organocatalysis by Networks of Cooperative Hydrogen Bonds: Enantioselective Direct Mannich Addition to Preformed Arylideneureas.

The concept of noncovalent organocatalysis by means of networks of cooperative hydrogen bonds (NCHB organocatalysis) has been explored. Arylideneureas were chosen as ideal substrates because of their powerful donor-acceptor properties. We have examined their uncatalyzed, direct Mannich reaction with acetoacetates in comparison with that catalyzed by a number of salan derivatives capable of providing a network of cooperative hydrogen bonds.

Phenylalanine hydroxylase deficiency in south Italy: Genotype-phenotype correlations, identification of a novel mutant PAH allele and prediction of BH4 responsiveness.

We investigated the mutation spectrum of the phenylalanine hydroxylase gene (PAH) in a cohort of patients from 33 Italian PKU families. Mutational screening of the known coding region, including conventional intron splice sites, was performed by direct sequencing of the patients' genomic DNA. Thirty-three different disease causing mutations were identified in our patient group, including 19 missense, 6 splicing, 3 nonsense, 5 deletions, with a detection rate of 100%.

Transition metal complexes with oligopeptides: single crystals and crystal structures.

The coordination chemistry of short chain peptides with transition metals is described in terms of the available crystal structures. Despite their high interest as synthetic models for metalloproteins and as building blocks for molecular materials based on the tuneable properties of oligopeptides, single crystal X-ray diffraction studies are scarce. A perusal of the most relevant results in this field allows us to define the main characteristics of oligopeptide-metal interactions, the fundamental problems for the crystallization of these complexes, and some hints to identify future promising approaches to advance the development of metallopeptide chemistry.

Intra-familiar discordant PKU phenotype explained by mutation analysis in three pedigrees.

Classical phenylketonuria (PKU) and mild hyperphenylalaninemia (MHP) are two phenotypes of phenylalanine hydroxylase (PAH) deficiency with different degrees of severity. We have analyzed three families in which classical PKU, MHP and a normal phenotype occurred within each family due to the different combinations of three mutations segregating within the family. Indeed, sequence PAH analysis revealed three different alleles segregating in each family.

Mutation analysis in hyperphenylalaninemia patients from South Italy.

Background: Mutations in the gene encoding phenylalanine hydroxylase (PAH, EC 1.14.16.

Aqueous synthesis of sulfonate-functionalized 1,2,4-triazole ligands and their 2D Cd2+ coordination networks: crystal structure and photoluminescent properties.

We have developed a water-based synthesis for the preparation of 4-substituted 1,2,4-triazole ligands with highly polar functional groups. This general synthetic approach has allowed us to prepare two sulfonate functionalized 4-substituted 1,2,4-triazole anions ( L1(-)= 4-(1,2,4-triazol-4-yl)benzenesulfonate; L2(-)= 4-(1,2,4-triazol-4-yl)ethanesulfonate). Reaction of these ligands with cadmium(II) salts leads to the formation of two novel two-dimensional coordination networks of formula [Cd(L)Cl]n (1, L1; and 2, L2), which were structurally characterized by X-ray diffraction.

[Predictors of long-term remission after transsphenoidal surgery in Cushing's disease].

There is no consensus on the remission criteria for Cushing's disease or on the definition of disease recurrence after transsphenoidal surgery, and comparison of the different published series is therefore difficult. A long-term recurrence rate of Cushing's disease ranging from 2%-25% has been reported. Predictors of long-term remission reported include: 1) adenoma-related factors (aggressiveness, size, preoperative identification in MRI), 2) surgery-related factors, mainly neurosurgeon experience, 3) clinical factors, of which dependence on and duration of glucocorticoid treatment are most important, and 4) biochemical factors.

Ni and Pd mediate asymmetric organoboron synthesis with ester functionality at the beta-position.

Catalytic systems based on Ni and Pd complexes modified with chiral P-P ligands can be used in a convenient strategy for enantioselectively adding a boron unit to the beta-position of alpha,beta-unsaturated esters.

Axially chiral P-N ligands for the copper catalyzed beta-borylation of alpha,beta-unsaturated esters.

The synthesis and resolution of a new axially chiral Quinazolinap ligand are reported. The application of this and other related P-N ligands to the copper catalyzed beta-borylation of alpha,beta-unsaturated esters resulted in conversions of up to 100% and ee values of up to 79%. A diastereomerically pure palladacycle of the new ligand was characterised by X-ray crystallography.

Asymmetric induction on beta-boration of alpha,beta-unsaturated compounds: an inexpensive approach.

Transition metal complexes mediate beta-boration of alpha,beta-unsaturated carbonyl compounds highlighting the advantages of using inexpensive catalytic systems, (Cu, Ni), both in the catalytic activity and selectivity. The new C(beta)-B bond can be accomplished in a stereoselective manner by modifying the metal complex with chiral ligands. Alternative mechanistic studies support the enantioselectivity observed, and large-scale applications of this reaction are currently being developed.

The selective catalytic formation of beta-boryl aldehydes through a base-free approach.

(NHC)Cu(I) complexes are key in a new strategy to selectively add a boron unit at the beta-position of alpha,beta-unsaturated aldehydes in the absence of a base.

Multifaceted palladium catalysts towards the tandem diboration-arylation reactions of alkenes.

Novel Pd(2) (6+) compounds have been synthesized in high yield. These compounds and their Pd(2) (4+) counterparts as synthetic precursors mediate the diboration of vinylarenes and aliphatic 1-alkenes, and under mild and basic reaction conditions they produce a variety of 1,2-diboronate esters with excellent conversions and chemoselectivities. The presence of bis(catecholato)diboron (B(2)cat(2)) favours the reduction of Pd(III) to Pd(II), while the catalytic precursor of Pd(II) is transformed into Pd(0)-nanoparticles.

Palladium-NHC complexes do catalyse the diboration of alkenes: mechanistic insights.

Novel catalytic activation of the B-B bond by palladium(II)-NHC complexes in presence of a mild base (NaOAc) and an excess of diboron reagent enables chemoselective 1,2-diboration of alkenes, suggesting the heterolytic cleavage of diboron rather than oxidative addition of a B-B bond to the metal.

Management and analysis of out-of-hospital health-related responses to simultaneous railway explosions in Madrid, Spain.

Objectives: On 11 March 2004, 10 simultaneous explosions at four different locations of the rail network in Madrid caused 198 deaths and 2312 persons were injured. The aim of this manuscript is to describe the prehospital health-related activities from the Emergency Medical Service of Madrid and to analyze the responses, the major conclusions, and the lessons learned.

Methods: Three meetings were held with professionals from the Emergency Medical Service of Madrid who were involved in the catastrophe.

The active role of NHC ligands in platinum-mediated tandem hydroboration-cross coupling reactions.

Stable N-heterocyclic platinum-carbene complexes are the first example of platinum-mediated regioselective H-B addition to vinylarenes and alkynes, allowing consecutive cross coupling reactions with the same catalytic system.

A valuable, inexpensive Cui/n-heterocyclic carbene catalyst for the selective diboration of styrene.

The complexes [Cu(NHC)(NCMe)]BF4 (NHC=N-heterocyclic ligand), with bis(catecholato)diboron (B2(cat)2) as the boron source, efficiently catalyze the diboration of styrene with very high degrees of conversion. With the appropriate NHC ligand, the reaction proceeds quantitatively toward the diborated derivative PhCH(Bcat)--CH2(Bcat). The [styrene]/[B2(cat)2] ratio also has a strong effect on the selectivity: the use of an excess of styrene allows modification of the selectivity toward the formation solely of the monoborated derivative, PhCH2--CH2(Bcat).

Pseudodiastrophic dysplasia type Burgio in a newborn.

Pseudodiastrophic dysplasia is a distinct disorder that differs from diastrophic dysplasia on the basis of elbow and proximal interphalangeal joint dislocations, platyspondyly, and scoliosis. We report on a new patient with this rare skeletal dysplasia and two previously undescribed major malformations: omphalocele and complex heart defect.