Advancement flap in the management of chronic anal fissure: A prospective study

Lateral internal sphincterotomy is the surgical treatment of choice of chronic anal fissure after failure of conservative measures. Several randomized trials identified an overall risk of incontinence of 10 % mostly for flatus. Fissurectomy is the most commonly used procedure to preserve the integrity of the anal sphincters. However, a possible complication is keyhole defect that may lead to faecal soiling. In this study, chronic anal fissure (CAF) was treated by fissurectomy and anal advancement flap to preserve the anatomo-functional integrity of sphincters and to reduce healing time and the risk of anal stenosis. In patients with hypertonia, surgical treatment was combined with chemical sphincterotomy by injection of botulinum toxin to enhance tissue perfusion. Forty eight patients with CAF underwent fissurectomy and anal advancement flap. In 22 subjects with hypertonia of the internal anal sphincter, intrasphincter injection of 30 UI of botulinum toxin at the completion of the surgical operation was used. All patients were followed up to 24 months. Since the first defecation, the intensity and duration of pain were significantly reduced. Two patients had urinary retention, five had infections and three had partial breakdowns. No anal stenosis, keyhole deformity or necrosis flap was recorded. At the 24 months follow-up visit, anal incontinence was similar to those detected preoperatively. Only four recurrences were detected at 18 and 20 months. After medical treatment failure, fissurectomy with advancement flap is a valid sphincter-conserving procedure for treatment of anterior or posterior CAF, regardless of hypertonia of the internal anal sphincter. © 2011 Springer-Verlag

MrkH, a Novel c-di-GMP-Dependent Transcriptional Activator, Controls Klebsiella pneumoniae Biofilm Formation by Regulating Type 3 Fimbriae Expression

Klebsiella pneumoniae causes significant morbidity and mortality worldwide, particularly amongst hospitalized individuals. The principle mechanism for pathogenesis in hospital environments involves the formation of biofilms, primarily on implanted medical devices. In this study, we constructed a transposon mutant library in a clinical isolate, K. pneumoniae AJ218, to identify the genes and pathways implicated in biofilm formation. Three mutants severely defective in biofilm formation contained insertions within the mrkABCDF genes encoding the main structural subunit and assembly machinery for type 3 fimbriae. Two other mutants carried insertions within the yfiN and mrkJ genes, which encode GGDEF domain- and EAL domain-containing c-di-GMP turnover enzymes, respectively. The remaining two isolates contained insertions that inactivated the mrkH and mrkI genes, which encode for novel proteins with a c-di-GMP-binding PilZ domain and a LuxR-type transcriptional regulator, respectively. Biochemical and functional assays indicated that the effects of these factors on biofilm formation accompany concomitant changes in type 3 fimbriae expression. We mapped the transcriptional start site of mrkA, demonstrated that MrkH directly activates transcription of the mrkA promoter and showed that MrkH binds strongly to the mrkA regulatory region only in the presence of c-di-GMP. Furthermore, a point mutation in the putative c-di-GMP-binding domain of MrkH completely abolished its function as a transcriptional activator. In vivo analysis of the yfiN and mrkJ genes strongly indicated their c-di-GMP-specific function as diguanylate cyclase and phosphodiesterase, respectively. In addition, in vitro assays showed that purified MrkJ protein has strong c-di-GMP phosphodiesterase activity. These results demonstrate for the first time that c-di-GMP can function as an effector to stimulate the activity of a transcriptional activator, and explain how type 3 fimbriae expression is coordinated with other gene expression programs in K. pneumoniae to promote biofilm formation to implanted medical devices

Prevalence, associated factors and outcomes of pressure injuries in adult intensive care unit patients: the DecubICUs study

Funder: European Society of Intensive Care Medicine; doi: http://dx.doi.org/10.13039/501100013347Funder: Flemish Society for Critical Care NursesAbstract: Purpose: Intensive care unit (ICU) patients are particularly susceptible to developing pressure injuries. Epidemiologic data is however unavailable. We aimed to provide an international picture of the extent of pressure injuries and factors associated with ICU-acquired pressure injuries in adult ICU patients. Methods: International 1-day point-prevalence study; follow-up for outcome assessment until hospital discharge (maximum 12 weeks). Factors associated with ICU-acquired pressure injury and hospital mortality were assessed by generalised linear mixed-effects regression analysis. Results: Data from 13,254 patients in 1117 ICUs (90 countries) revealed 6747 pressure injuries; 3997 (59.2%) were ICU-acquired. Overall prevalence was 26.6% (95% confidence interval [CI] 25.9–27.3). ICU-acquired prevalence was 16.2% (95% CI 15.6–16.8). Sacrum (37%) and heels (19.5%) were most affected. Factors independently associated with ICU-acquired pressure injuries were older age, male sex, being underweight, emergency surgery, higher Simplified Acute Physiology Score II, Braden score 3 days, comorbidities (chronic obstructive pulmonary disease, immunodeficiency), organ support (renal replacement, mechanical ventilation on ICU admission), and being in a low or lower-middle income-economy. Gradually increasing associations with mortality were identified for increasing severity of pressure injury: stage I (odds ratio [OR] 1.5; 95% CI 1.2–1.8), stage II (OR 1.6; 95% CI 1.4–1.9), and stage III or worse (OR 2.8; 95% CI 2.3–3.3). Conclusion: Pressure injuries are common in adult ICU patients. ICU-acquired pressure injuries are associated with mainly intrinsic factors and mortality. Optimal care standards, increased awareness, appropriate resource allocation, and further research into optimal prevention are pivotal to tackle this important patient safety threat

Correction to: Prevalence, associated factors and outcomes of pressure injuries in adult intensive care unit patients: the DecubICUs study

The original version of this article unfortunately contained a mistake

Prevalence, associated factors and outcomes of pressure injuries in adult intensive care unit patients: the DecubICUs study

Funder: European Society of Intensive Care Medicine; doi: http://dx.doi.org/10.13039/501100013347Funder: Flemish Society for Critical Care NursesAbstract: Purpose: Intensive care unit (ICU) patients are particularly susceptible to developing pressure injuries. Epidemiologic data is however unavailable. We aimed to provide an international picture of the extent of pressure injuries and factors associated with ICU-acquired pressure injuries in adult ICU patients. Methods: International 1-day point-prevalence study; follow-up for outcome assessment until hospital discharge (maximum 12 weeks). Factors associated with ICU-acquired pressure injury and hospital mortality were assessed by generalised linear mixed-effects regression analysis. Results: Data from 13,254 patients in 1117 ICUs (90 countries) revealed 6747 pressure injuries; 3997 (59.2%) were ICU-acquired. Overall prevalence was 26.6% (95% confidence interval [CI] 25.9–27.3). ICU-acquired prevalence was 16.2% (95% CI 15.6–16.8). Sacrum (37%) and heels (19.5%) were most affected. Factors independently associated with ICU-acquired pressure injuries were older age, male sex, being underweight, emergency surgery, higher Simplified Acute Physiology Score II, Braden score 3 days, comorbidities (chronic obstructive pulmonary disease, immunodeficiency), organ support (renal replacement, mechanical ventilation on ICU admission), and being in a low or lower-middle income-economy. Gradually increasing associations with mortality were identified for increasing severity of pressure injury: stage I (odds ratio [OR] 1.5; 95% CI 1.2–1.8), stage II (OR 1.6; 95% CI 1.4–1.9), and stage III or worse (OR 2.8; 95% CI 2.3–3.3). Conclusion: Pressure injuries are common in adult ICU patients. ICU-acquired pressure injuries are associated with mainly intrinsic factors and mortality. Optimal care standards, increased awareness, appropriate resource allocation, and further research into optimal prevention are pivotal to tackle this important patient safety threat

Hybrid Nanostructured Materials for Application in Catalysis and Molecular Recognition

This Ph.D. thesis describes the versatility of amine triphenolate complexes to be used either as self-assembling molecular scaffolds with applications in material sciences and molecular recognition, like titanium (IV) µ-oxo TPA complexes, or as active catalysts in homogeneous and heterogeneous catalysis, mainly vanadium (V) TPA complexes. In Chapter 1, the principles of self-assembly are listed, i.e. control on the electronic properties and size discrimination for the realization of supramolecular structures, error-checking, and efficiency, in the way of building up ordered and highly-structured entities under mild conditions. Different examples are proposed, but the analysis is mainly focused on the possibility of applying self-assembly in metal coordination chemistry in order to design highly ordered and functional systems, that may find applications in catalysis or material sciences. In this view, the coordination chemistry and the behaviour in solution of Ti(IV) TPA complexes are presented and in particular the possibility to switch between mononuclear and dinuclear µ-oxo species, depending on the steric nature of peripheral substituents, as well as the feasibility to build up highly functional Ti(IV) molecular scaffolds. A brief introduction on V(V) TPA complexes is reported as well, especially on their Lewis acid nature and structural characteristics that make them be considered as functional models of natural vanadium-dependent haloperoxidases and be used as active catalysts in oxygen transfer reactions. As the realization of new efficient and functional supramolecular systems supposes the design of the right building blocks, in Chapter 2, the modification of amine triphenolate skeleton is proposed. The functionalization strategy that has been adopted is based on a click-type oxime bond formation upon reaction of an aldehyde group, which can be effectively and selectively inserted on TPA ligands through the so-called Duff reaction, and a wide variety of alkoxyamines. In this way, the ligand skeleton has been efficiently decorated with polar and positively charged moieties, such as TEG arms and imidazolinium residues, and with pyrene groups. The functionalization has interested diverse positions of the ligand and even a double functionalization of two different positions on the same tri-phenolamine can be achieved. Chapter 3 deals with titanium (IV) amine triphenolate complexes and with the thermodynamic stability in solution of a Ti(IV) complex obtained by complexation with tris-(2-hydroxy-3-phenylbenzyl)amine. In more details, the reaction gives rise to a mononuclear complex, which upon reaction with water stereoselectively self-assembles into a highly stable, inert, dinuclear, heterochiral S6-symmetric µ-oxo TPA complex. Highly decorated Ti(IV) µ-oxo TPA complexes can be efficiently obtained by effecting the complexation reaction on functionalized ligands reported in Chapter 2, or by directly functionalizing Ti(IV) µ-oxo TPA complexes, which bear six aldehyde groups in para and/or meta positions, with the appropriate alkoxyamine. The functionalization strategy enables to construct stable and spatially ordered materials. In particular, two different Ti(IV) µ-oxo TPA complexes, bearing pyrene groups in para and meta positions, respectively, have been used as molecular receptors for fullerene. Fluorescence spectroscopies and DOSY-NMR analyses clearly indicate that pyrene groups on titanium complexes interact with fullerene through π-π interactions. Additionally, interactions between pyrene groups in para position on Ti(IV) µ-oxo TPA complex and SWCNTs (single walled carbon nanotubes) has been studied as well. Even in this case, fluorescence studies have been carried out and AFM images clearly show that CNTs are covered from Ti(IV) µ-oxo TPA complexes, highlighting the possibility to use such these systems for the design of ordered and functional supramolecular structures. Finally, in Chapter 4, the catalytic activity of V(V) TPA complexes is studied, both in sulfoxidation and aerobic oxidative C-C cleavage reactions. Firstly, the activity of an electron-poor V(V) TPA complex, bearing six chloro groups in ortho and para positions, is investigated in sulfoxidation reactions in presence of hydrogen peroxide as terminal oxidant. The reactions are performed with high yields and selectivities (catalyst loading down to 0.001% and TONs up to 89000). Both reaction rates and selectivities confirm the higher activity of the new catalyst with respect to the ones reported in literature. Moreover, modification of V(V) complexes through oxime bond formation has also led to the realization of organogelator-derived complexes, which have been found to form organogels in dioxane. Lastly, functionalization of V(V) complexes with positively charged moieties makes it possible to obtain water-soluble micelles, upon solubilisation with SDS (sodium dodecyl sulphate). The micellar like system has been tested in aerobic oxidative C-C cleavage of vicinal diols, with high selectivity and quite short reaction times. The compartmentalization of the catalytic system allowed its recycling and reuse for three times by extraction of products with organic solvents.Questa tesi di dottorato descrive la sintesi e la funzionalizzazione di complessi amminotrifenolati di titanio (IV) e vanadio (V) per applicazioni in reazioni di riconoscimento molecolare e in catalisi. Nel Capitolo 1, sono illustrati i principi che regolano il self-assembly, quali controllo, correzione degli errori ed efficienza. E’ mostrato come questi possano essere applicati per la realizzazione di entità ordinate e strutturate in chimica di coordinazione, per la costruzione di sistemi metallo-supramolecolari, con applicazione in catalisi o scienze dei materiali. In quest’ottica, sono studiati la chimica di coordinazione e il comportamento in soluzione di complessi TPA di titanio (IV) e in particolare la capacità di fornire specie mono- o dinucleari a seconda dell’ingombro sterico dei sostituenti periferici e la possibilità di costruire scaffolds molecolari di titanio (IV) altamente funzionalizzati. Inoltre, è riportata una breve introduzione sui complessi TPA di vanadio (V), in particolar modo sulla loro proprietà di acidi di Lewis e sulle loro caratteristiche strutturali, che fanno sì che vengano considerati dei modelli funzionali delle aloperossidasi naturali vanadio-dipendenti e quindi vengano utilizzati come catalizzatori in reazioni di trasferimento di ossigeno. Nel Capitolo 2, viene proposta una strategia sintetica per modificare lo scheletro trifenolamminico. La funzionalizzazione prevede la formazione di un legame ossimico, mediante una reazione click-simile tra un’aldeide, che può essere selettivamente introdotta sul legante mediante reazione di Duff, e una varietà di alcossiammine. In questo modo, lo scheletro del legante può essere efficientemente decorato con residui polari e carichi positivamente, come residui TEG o imidazolinio, e con gruppi pirene. La funzionalizzazione può coinvolgere diverse posizioni del legante, così come una doppia derivatizzazione di posizioni differenti sulla stessa trifenolammina. Nel Capitolo 3, è presentata la possibilità di ottenere dei complessi dinucleari µ-oxo amminotrifenolati di titanio (IV) per reazione di complessazione della tri-(2-idrossi-3-fenilbenzil)ammina con Ti(Oi-Pr)4. Più in dettaglio, il complesso mononucleare, che si forma dalla reazione, in presenze di tracce d’acqua è in grado di auto-assemblarsi in maniera stereoselettiva, dando origine a un complesso dinucleare, altamente stabile, inerte, eterochirale, con simmetria S6. La funzionalizzazione del complesso può essere ottenuta efficacemente mediante una duplice via: effettuando la reazione di complessazione sui leganti funzionalizzati riportati in Capitolo 2, oppure funzionalizzando direttamente complessi TPA µ-oxo di titanio (IV), che portano sei gruppi aldeidici in para e/o meta, con un’appropriata alcossiammina. La strategia di funzionalizzazione permette di costruire dei materiali stabili e spazialmente ordinati. In particolare, due complessi µ-oxo di titanio che portano gruppi pirene rispettivamente in para e meta sono stati utilizzati come recettori molecolari per il fullerene. Spettroscopie di fluorescenza ed esperimenti DOSY-NMR indicano chiaramente che i gruppi pirene sui complessi di titanio interagiscono con il fullerene mediante interazioni π-π. Come ulteriore applicazione, sono state studiate le interazioni tra gruppi pirene dei complessi TPA µ-oxo di titanio e nanotubi di carbonio (SWCNTs). Anche in questo caso, sono stati condotti studi di fluorescenza e analisi AFM mostrano chiaramente che i nanotubi sono rivestiti dai complessi di titanio, evidenziando la possibilità di usare questi sistemi per generare strutture supramolecolari ordinate e funzionali. Infine, nel Capitolo 4, è studiata l’attività catalitica di complessi TPA d vanadio (V), sia in reazioni di solfossidazione che in reazioni di cleavage aerobico ossidativo di legami C-C. Prima di tutto, viene analizzata l’attività catalitica di un complesso di vanadio (V) elettron-povero, portante sei atomi di cloro in posizioni orto e para, in reazioni di solfossidazione in presenza di perossido d’idrogeno come ossidante terminale. Le reazioni sono condotte con alte rese e selettività, anche in presenza dello 0.001% di catalizzatore, con TON fino a 89000. Le velocità di reazione e le selettività confermano una attività maggiore del catalizzatore rispetto ai catalizzatori riportati in letteratura. In più, la modificazione di complessi TPA di vanadio (V) mediante formazione di un’ossima ha portato anche alla realizzazione di complessi funzionalizzati con catene organogelator e alla formazione di organogel in diossano. In conclusione, la funzionalizzazione di complessi TPA di vanadio (V) con residui carichi positivamente permette di ottenere micelle solubili in acqua, in seguito a solubilizzazione con SDS (sodio dodecil solfato). Il sistema micellare è stato poi testato in reazioni di cleavage aerobico ossidativo di legami C-C di dioli vicinali, con elevate selettività e tempi di reazione relativamente bassi. Il sistema catalitico può essere inoltre riciclato e riutilizzato fino a tre volte in seguito a estrazione dei prodotti con solventi organic

Vanadium catalyzed aerobic carbon-carbon cleavage

In recent years, the use of vanadium complexes as catalysts and air or oxygen as oxidants has emerged as a new method for the effective oxidative carbon-carbon bond cleavage in a series of substrates, including 1,2-diols and α-hydroxy ethers. In addition to the advantageous use as a synthetic tool, vanadium catalyzed aerobic C. C bond cleavage becomes even more appealing if applied to the degradation of lignocellulosic biomass and in particular in the oxidative depolymerization/degradation of lignin or cellulose. In this review, this chemistry, the most recent advances and the role played by homogeneous vanadium complexes are presented and discussed.SCOPUS: re.jinfo:eu-repo/semantics/publishe

Stereoselective selenium catalyzed dihydroxylation and hydroxymethoxylation of alkenes

The selenium atom of the selenocysteine plays a crucial role in the reduction of peroxides. Herein we showed that, in the absence of a thiol cofactor, the same aminoacid efficiently catalyzed the dihydroxylation of carbon–carbon double bonds leading to the stereoselective formation of 1,2-diols at room temperature and in on water conditions. Alternatively, in the presence of methanol, the corresponding β-methoxyalcohol can be prepared. The stereoselectivity of the reaction will be discussed and NMR evidences of the actual catalyst are here reported

Viral nano-hybrids for innovative energy conversion and storage schemes

Typical rod-like viruses (the Tobacco Mosaic Virus (TMV) and the Bacteriophage M13) are biological nanostructures that couple a 1D mono-dispersed morphology with a precisely defined topology of surface spaced and orthogonal reactive domains. These biogenic scaffolds offer a unique alternative to synthetic nano-platforms for the assembly of functional molecules and materials. Spatially resolved 1D arrays of inorganic-organic hybrid domains can thus be obtained on viral nano-templates resulting in the functional arrangement of photo-triggers and catalytic sites with applications in light energy conversion and storage. Different synthetic strategies are herein highlighted depending on the building blocks and with a particular emphasis on the molecular design of viral-templated nano-interfaces holding great potential for the dream-goal of artificial photosynthesi