Light on the sustainable preparation of aryl-cored dibromides.

Both aryl and benzyl polybromides have gained significant importance as reactive building blocks in polymer and materials chemistry. Their preparation primarily relies on established synthetic methods using molecular bromine or N-bromosuccinimide, known for their reliability and effectiveness. However, from a sustainability perspective, these methods suffer from the generation of stoichiometric amounts of byproducts and often encounter selectivity troubles. To mitigate these issues, we extended the greener peroxide-bromide halogenation method, initially developed for monobromides, to afford aryl-cored polybromides in high yields. The same method can be employed in two variants modulated by light irradiation. This external switch can be used to selectively trigger side-chain or core halogenation.

Oligonuclear Metal Complexes with Schiff Base Ligands.

As stated by two of the seven papers [...].

Substituent-Guided Cluster Nuclearity for Tetranuclear Iron(III) Compounds with Flat {Fe4(µ3-O)2} Butterfly Core.

The tetranuclear iron(III) compounds [Fe4(µ3-O)2(µ-LZ)4] (1-3) were obtained by reaction of FeCl3 with the shortened salen-type N2O2 tetradentate Schiff bases N,N'-bis(salicylidene)-o-Z-phenylmethanediamine H2LZ (Z = NO2, Cl and OMe, respectively), where the one-carbon bridge between the two iminic nitrogen donor atoms guide preferentially to the formation of oligonuclear species, and the ortho position of the substituent Z on the central phenyl ring selectively drives towards Fe4 bis-oxido clusters. All compounds show a flat almost-symmetric butterfly-like conformation of the {Fe4(µ3-O)2} core, surrounded by the four Schiff base ligands, as depicted by both the X-ray molecular structures of 1 and 2 and the optimized geometries of all derivatives as obtained by UM06/6-311G(d) DFT calculations. The strength of the antiferromagnetic exchange coupling constants between the iron(III) ions varies among the three derivatives, despite their magnetic cores remain structurally almost unvaried, as well as the coordination of the metal ions, with a distorted octahedral environment for the two-body iron ions, Feb, and a pentacoordination with trigonal bipyramidal geometry for the two-wing iron ions, Few. The different magnetic behavior within the series of examined compounds may be ascribed to the influence of the electronic features of Z on the electron density distribution (EDD) of the central {Fe4(µ3-O)2} core, substantiated by a Quantum Theory of Atoms In Molecules (QTAIM) topological analysis of the EDD, as obtained by UM06 calculations 1-3.

Development of Stable Amino-Pyrimidine-Curcumin Analogs: Synthesis, Equilibria in Solution, and Potential Anti-Proliferative Activity.

With the clear need for better cancer treatment, naturally occurring molecules represent a powerful inspiration. Recently, curcumin has attracted attention for its pleiotropic anticancer activity in vitro, especially against colorectal and prostate cancer cells. Unfortunately, these encouraging results were disappointing in vivo due to curcumin's low stability and poor bioavailability. To overcome these issues, herein, the synthesis of eight new pyrimidine-curcumin derivatives is reported. The compounds were fully characterized (1H/13C NMR (Nuclear Magnetic Resonance), LC-MS (Liquid Chromatography-Mass Spectrometri), UV-Vis spectroscopy), particularly their acid/base behavior; overall protonation constants were estimated, and species distribution, as a function of pH, was predicted, suggesting that all the compounds are in their neutral form at pH 7.4. All the compounds were extremely stable in simulated physiological media (phosphate-buffered saline and simulated plasma). The compounds were tested in vitro (48 h incubation treatment) to assess their effect on cell viability in prostate cancer (LNCaP and PC3) and colorectal cancer (HT29 and HCT116) cell lines. Two compounds showed the same anti-proliferative activity as curcumin against HCT116 cells and improved cytotoxicity against PC3 cells.

Clinical outcomes and complications after anterior cruciate ligament reconstruction with bone-patellar tendon-bone in patient Tanner 3 and 4: a systematic review.

BACKGROUND: Clinical outcomes and potential complications associated with Bone-Patellar Tendon-Bone (BPTB) graft in skeletally immature ACL reconstruction (ACLR) are poorly defined. Considering that in Tanner 1-2 patients this kind of graft is not recommended, we focused our systematic review on the evaluation of all the studies in the literature that reported clinical outcomes and rate of complications of the ACLR using BPTB graft in Tanner 3-4 patients. METHODS: This review was conducted in accordance with the PRISMA statement. PubMed, Cochrane Library, EMBASE and Scopus were examined from 1965 to 2020 using different combinations of the following keywords: "ACL reconstruction", "skeletally immature", "young", "patellar tendon" and "BPTB". The database search yielded 742 studies, on which we performed a primary evaluation. After carrying out a full-text evaluation for the inclusion criteria, 4 studies were included in the final review and assessed using the Newcastle-Ottawa scale. Ninety-six cases with mean age of 14.2 years were reported. RESULTS: Good stability and functional outcomes were reported with a mean follow-up of 49.5 months. Return to sport rate ranged from 91.7% to 100%. A KT-1000 side-to-side difference higher than 5 mm was observed in five patients (5.2%). No lower limb length discrepancy and angulation were reported. Graft rupture rate was 5.2%. CONCLUSION: According to these results, BTPB graft could be a good choice in Tanner 3-4 patients who want to achieve their preinjury sport level with a low risk of growth disturbances and graft failure. Further investigations in a wider population are needed.

Structure illumination microscopy imaging of lipid vesicles in live bacteria with naphthalimide-appended organometallic complexes.

There is a lack of molecular probes for imaging bacteria, in comparison to the array of such tools available for the imaging of mammalian cells. Here, organometallic molecular probes have been developed and assessed for bacterial imaging, designed to have the potential to support multiple imaging modalities. The chemical structure of the probes is designed around a metal-naphthalimide structure. The 4-amino-1,8-naphthalimide moiety, covalently appended through a pyridine ancillary ligand, acts as a luminescent probe for super-resolution microscopy. On the other hand, the metal centre, rhenium(i) or platinum(ii) in the current study, enables techniques such as nanoSIMS. While the rhenium(i) complex was not sufficiently stable to be used as a probe, the platinum(ii) analogue showed good chemical and biological stability. Structured illumination microscopy (SIM) imaging on live Bacillus cereus confirmed the suitability of the probe for super-resolution microscopy. NanoSIMS analysis was used to monitor the uptake of the platinum(ii) complex within the bacteria and demonstrate the potential of this chemical architecture to enable multimodal imaging. The successful combination of these two moieties introduces a platform that could lead to a versatile range of multi-functional probes for bacteria.

An arthroscopic repair technique for proximal anterior cruciate tears in children to restore active function and avoid growth disturbances.

PURPOSE: The aim of this study was to assess midterm clinical outcomes in Tanner 1-2 patients with proximal anterior cruciate ligament (ACL) tears following arthroscopic-surgical repair using an absorbable or an all-suture anchor. METHODS: Fourteen (9.2 ± 2.9 years-old) of 19 skeletally immature patients reached the 2 years of clinical follow-up. Physical examinations included the Lachman test, Pivot-shift test, One-leg Hop test, Pedi-IKDC as well as Lysholm and Tegner activity scores; knee stability was measured with a KT-1000 arthrometer. Overall re-rupture rates were also evaluated in all operated patients. RESULTS: At 2 years post-surgery, the Lysholm score was 93.6 ± 4.3 points, and the Pedi-IKDC score was 95.7 ± 0.1. All patients returned to the same sport activity level as prior to ACL lesion within 8.5 ± 2.9 months, with one exception who reported a one-point reduction in their Tegner Activity score. No leg-length discrepancies or malalignments were observed. Four patients presented grade 1 Lachman scores, and of these, three presented grade 1 (glide) score at Pivot-shift; clinical stability tests were negative for all other patients. Anterior tibial shift showed a mean side-to-side difference of 2.2 mm (range 1-3 mm). The One-leg Hop test showed lower limb symmetry (99.9% ± 9.5) with the contralateral side. Overall, 4 out of 19 patients presented a re-rupture of the ACL with a median time between surgery and re-rupture of 3.9 years (range 1-7). CONCLUSION: This surgical technique efficiently repairs proximal ACL tears, leading to a restoration of knee stability and a quick return to an active lifestyle, avoiding growth plate disruption. LEVEL OF EVIDENCE: IV.

Bringing Homogeneous Iron Catalysts on the Heterogeneous Side: Solutions for Immobilization.

Noble metal catalysts currently dominate the landscape of chemical synthesis, but cheaper and less toxic derivatives are recently emerging as more sustainable solutions. Iron is among the possible alternative metals due to its biocompatibility and exceptional versatility. Nowadays, iron catalysts work essentially in homogeneous conditions, while heterogeneous catalysts would be better performing and more desirable systems for a broad industrial application. In this review, approaches for heterogenization of iron catalysts reported in the literature within the last two decades are summarized, and utility and critical points are discussed. The immobilization on silica of bis(arylimine)pyridyl iron complexes, good catalysts in the polymerization of olefins, is the first useful heterogeneous strategy described. Microporous molecular sieves also proved to be good iron catalyst carriers, able to provide confined geometries where olefin polymerization can occur. Same immobilizing supports (e.g., MCM-41 and MCM-48) are suitable for anchoring iron-based catalysts for styrene, cyclohexene and cyclohexane oxidation. Another excellent example is the anchoring to a Merrifield resin of an FeII-anthranilic acid complex, active in the catalytic reaction of urea with alcohols and amines for the synthesis of carbamates and N-substituted ureas, respectively. A SILP (Supported Ionic Liquid Phase) catalytic system has been successfully employed for the heterogenization of a chemoselective iron catalyst active in aldehyde hydrogenation. Finally, FeIII ions supported on polyvinylpyridine grafted chitosan made a useful heterogeneous catalytic system for C-H bond activation.

Selective Formation, Reactivity, Redox and Magnetic Properties of MnIII and FeIII Dinuclear Complexes with Shortened Salen-Type Schiff Base Ligands.

The reactivity of the shortened salen-type ligands H3salmp, H2salmen and H2sal(p-X)ben with variable para-substituent on the central aromatic ring (X = tBu, Me, H, F, Cl, CF3, NO2) towards the trivalent metal ions manganese(III) and iron(III) is presented. The selective formation of the dinuclear complexes [M2(µ-salmp)2], M = Mn (1a), Fe (2a), [M2(µ-salmen)2(µ-OR)2)], R = Et, Me, H and M = Mn (3a-c) or Fe (4a-c), and (M2(µ-sal[p-X]ben)2(µ-OMe)2), X = tBu, Me, H, F, Cl, CF3, NO2 and M = Mn (5a-g) or Fe (6a-g), could be identified by reaction of the Schiff bases with metal salts and the base NEt3, and their characterization through elemental analysis, infrared spectroscopy, mass spectrometry and single-crystal X-ray diffraction of 2a·2AcOEt, 2a·2CH3CN and 3c·2DMF was performed. In the case of iron(III) and H3salmp, when using NaOH as a base instead of NEt3, the dinuclear complexes [Fe2(µ-salmp)(µ-OR)(salim)2], R = Me, H (2b,c) could be isolated and spectroscopically characterized, including the crystal structure of 2b·1.5H2O, which showed that rupture of one salmp3- to two coordinated salim- ligands and release of one salH molecule occurred. The same hydrolytic tendency could be identified with sal(p-X)ben ligands in the case of iron(III) also by using NEt3 or upon standing in solution, while manganese(III) did not promote such a C-N bond breakage. Cyclic voltammetry studies were performed for 3b, 4b, 5a and 6a, revealing that the iron(III) complexes can be irreversibly reduced to the mixed-valence FeIIFeIII and FeII2 dinuclear species, while the manganese(III) derivatives can be reversibly oxidized to either the mixed-valence MnIIIMnIV or to the MnIV2 dinuclear species. The super-exchange interaction between the metal centers, mediated by the bridging ligands, resulted in being antiferromagnetic (AFM) for the selected dinuclear compounds 3b, 4b, 5a, 5e,5f, 6a and 6e. The coupling constants J (-2JS1·S2 formalism) had values around -13 cm-1 for manganese(III) compounds, among the largest AFM coupling constants reported so far for dinuclear MnIII2 derivatives, while values between -3 and -10 cm-1 were obtained for iron(III) compounds.

Clinical effectiveness of surgical treatment with polyester tapes and temporary K-wires on complete acromioclavicular dislocation.

INTRODUCTION: Ideal treatment of acute acromioclavicular joint (ACJ) dislocation remains unresolved. We evaluated ACJ reconstruction using polyester tapes and temporary Kirschner wire (KW) and presented clinical and radiological outcomes. MATERIALS AND METHODS: Patients were retrospectively evaluated and classified according to Rockwood classification, clinical and sportive characteristics. Constant Score (CS) and ACJ joint instability (ACJI) score were collected. Zanca's, Alexander, axillary, standard, and stress AP views were collected. Radiographic coracoclavicular distance (CCd) of healthy and injured shoulders was measured pre-operatively, at 3 months and at minimum 2-year follow-up. Heterotopic ossifications and clavicular osteolysis were evaluated. Influence of patients' characteristics and AC joint type on clinical and radiological outcomes were determined. RESULTS: Sixteen patients (13 type V and 3 type III ACJ dislocation) reached the end of follow-up (mean 2.4 years; range 22-72 months). Mean CS was 99.63 (range 96-100), while the mean ACJI score was 96.19 (range 85-100). The CCd of the treated shoulder was comparable with the healthy shoulder at 3 months and at last follow-up; moreover, there was no difference in CCd scores at 3 months and at 2 years. CCd scores were lower in sedentary patients compared with physically active (sporty) patients. Heterotopic ossifications were observed in three patients. No osteolysis was reported. CONCLUSION: This technique provides good results with few complications and should be considered as an effective method to treat ACJ acute dislocation. CCd scores correlate with overuse factors but not with other clinical scores.

A Pseudo-Octahedral Cobalt(II) Complex with Bispyrazolylpyridine Ligands Acting as a Zero-Field Single-Molecule Magnet with Easy Axis Anisotropy.

The homoleptic mononuclear compound [Co(bpp-COOMe)2 ](ClO4 )2  (1) (bpp-COOMe=methyl 2,6-di(pyrazol-1-yl)pyridine-4-carboxylate) crystallizes in the monoclinic C2/c space group, and the cobalt(II) ion possesses a pseudo-octahedral environment given by the two mer-coordinated tridentate ligands. Direct-current magnetic data, single-crystal torque magnetometry, and EPR measurements disclosed the easy-axis nature of this cobalt(II) complex, which shows single-molecule magnet behavior when a static field is applied in alternating-current susceptibility measurements. Diamagnetic dilution in the zinc(II) analogue [Zn(bpp-COOMe)2 ](ClO4 )2  (2) afforded the derivative [Zn0.95 Co0.05 (bpp-COOMe)2 ](ClO4 )2  (3), which exhibits slow relaxation of magnetization even in zero field thanks to the reduction of dipolar interactions. Theoretical calculations confirmed the overall electronic structure and the magnetic scenario of the compound as drawn by experimental data, thus confirming the spin-phonon Raman relaxation mechanism, and a direct quantum tunneling in the ground state as the most plausible relaxation pathway in zero field.

Filling the Gap in Extended Metal Atom Chains: Ferromagnetic Interactions in a Tetrairon(II) String Supported by Oligo-α-pyridylamido Ligands.

The stringlike complex [Fe4(tpda)3Cl2] (2; H2tpda = N2, N6-bis(pyridin-2-yl)pyridine-2,6-diamine) was obtained as the first homometallic extended metal atom chain based on iron(II) and oligo-α-pyridylamido ligands. The synthesis was performed under strictly anaerobic and anhydrous conditions using dimesityliron, [Fe2(Mes)4] (1; HMes = mesitylene), as both an iron source and a deprotonating agent for H2tpda. The four lined-up iron(II) ions in the structure of 2 (Fe···Fe = 2.94-2.99 Å, Fe···Fe···Fe = 171.7-168.8°) are wrapped by three doubly deprotonated twisted ligands, and the chain is capped at its termini by two chloride ions. The spectroscopic and electronic properties of 2 were investigated in dichloromethane by UV-vis-NIR absorption spectroscopy, 1H NMR spectroscopy, and cyclic voltammetry. The electrochemical measurements showed four fully resolved, quasi-reversible one-electron-redox processes, implying that 2 can adopt five oxidation states in a potential window of only 0.8 V. Direct current (dc) magnetic measurements indicate dominant ferromagnetic coupling at room temperature, although the ground state is only weakly magnetic. On the basis of density functional theory and angular overlap model calculations, this magnetic behavior was explained as being due to two pairs of ferromagnetically coupled iron(II) ions ( J = -21 cm-1 using JS i·S j convention) weakly antiferromagnetically coupled with each other. Alternating-current susceptibility data in the presence of a 2 kOe dc field and at frequencies up to 1.5 kHz revealed the onset of slow magnetic relaxation below 2.8 K, with the estimated energy barrier Ueff/ kB = 10.1(1.3) K.

Curcumin derivatives and Aß-fibrillar aggregates: An interactions' study for diagnostic/therapeutic purposes in neurodegenerative diseases.

Several neurodegenerative diseases, like Alzheimer's (AD), are characterized by amyloid fibrillar deposition of misfolded proteins, and this feature can be exploited for both diagnosis and therapy design. In this paper, structural modifications of curcumin scaffold were examined in order to improve its bioavailability and stability in physiological conditions, as well as its ability to interfere with ß-amyloid fibrils and aggregates. The acid-base behaviour of curcumin derivatives, their pharmacokinetic stability in physiological conditions, and in vitro ability to interfere with Aß fibrils at different incubation time were investigated. The mechanisms governing these phenomena have been studied at atomic level by means of molecular docking and dynamic simulations. Finally, biological activity of selected curcuminoids has been investigated in vitro to evaluate their safety and efficiency in oxidative stress protection on hippocampal HT-22 mouse cells. Two aromatic rings, π-conjugated structure and H-donor/acceptor substituents on the aromatic rings showed to be the sine qua non structural features to provide interaction and disaggregation activity even at very low incubation time (2h). Computational simulations proved that upon binding the ligands modify the conformational dynamics and/or interact with the amyloidogenic region of the protofibril facilitating disaggregation. Significantly, in vitro results on hippocampal cells pointed out protection against glutamate toxicity and safety when administered at low concentrations (1 µM). On the overall, in view of its higher stability in physiological conditions with respect to curcumin, of his rapid binding to fibrillar aggregates and strong depolymerizing activity, phtalimmide derivative K2F21 appeared a good candidate for both AD diagnostic and therapeutic purposes.

Intra-Articular Cytokine Levels in Adolescent Patients after Anterior Cruciate Ligament Tear.

The treatment of anterior cruciate ligament (ACL) injuries in children and adolescents is challenging. Preclinical and clinical studies investigated ACL repairing techniques in skeletally immature subjects. However, intra-articular bioenvironment following ACL tear has not yet been defined in skeletally immature patients. The aim of this study was to measure cytokine concentrations in the synovial fluid in adolescent population. Synovial levels of IL-1ß, IL-1ra, IL-6, IL-8, IL-10, and TNF-α were measured in 17 adolescent patients (15 boys) with ACL tears who underwent ACL reconstruction including acute (5), subacute (7), and chronic (5) phases. Femoral growth plates were classified as "open" in three patients, "closing" in eight, and "closed" in six. Eleven patients presented an ACL tear associated with a meniscal tear. The mean Tegner and Lysholm scores (mean ± SD) of all patients were 8 ± 1 and 50.76 ± 26, respectively. IL-8, TNF-α, and IL-1ß levels were significantly greater in patients with "open" physes. IL-1ra and IL-1ß levels were significantly higher in patients with ACL tear associated with a meniscal tear. Poor Lysholm scores were associated with elevated IL-6 and IL-10 levels. IL-10 levels positively correlated with IL-6 and IL-8 levels, whereas TNF-α concentration negatively correlated with IL-6 levels. Skeletally immature patients with meniscal tears and open growth plates have a characteristic cytokine profile with particularly elevated levels of proinflammatory cytokines including IL-8, TNF-α, and IL-1ß. This picture suggests that the ACL tear could promote an intra-articular catabolic response in adolescent patients greater than that generally reported for adult subjects. The study lacks the comparison with synovial samples from healthy skeletally immature knees due to ethical reasons. Overall, these data contribute to a better knowledge of adolescent intra-articular bioenvironment following ACL injuries.

Diamondoid Structure in a Metal-Organic Framework of Fe4 Single-Molecule Magnets.

A 3D metal-organic framework (MOF) having single-molecule magnet (SMM) linkers was prepared in crystalline form by using a tetrairon(III) complex functionalised with two divergent pyridyl groups, namely [Fe4 (pPy)2 (dpm)6 ] (1; H3 pPy=2-(hydroxymethyl)-2-(pyridin-4-yl)propane-1,3-diol, Hdpm=dipivaloylmethane). Reaction of 1 with silver(I) perchlorate afforded {[Fe4 (pPy)2 (dpm)6 ]2 Ag}ClO4 (2), which crystallises in a cubic face-centred lattice and exhibits two interlocked diamondoid networks. In 2, the SMMs act as linear ditopic synthons, and silver(I) ions as tetrahedral nodes coordinated by four pyridyl nitrogen atoms. The magnetic properties of 1 (S=5 and D≈-0.4 cm(-1) in the ground spin state) are largely preserved in 2, which shows slow magnetic relaxation with an anisotropy barrier of Ueff /kB =11.46(10) K in zero field and 14.25(8) K in an applied field of 1 kOe. However, crystal symmetry triggers highly noncollinear magnetic anisotropy contributions oriented at 109.47° from each other along the threefold axes of AgN4 tetrahedra, a unique scenario fully confirmed by a single-crystal cantilever torque magnetometry investigation. Magnetisation curves down to 0.03 K demonstrated the occurrence of a wide hysteresis loop when the magnetic field was swept along one of the four Ag-N bonds. By symmetry, the crystalline compound can then be persistently magnetised parallel or antiparallel to the four main diagonals of the unit cell, although the crystals have no overall second-order anisotropy.

Experimental and Theoretical Studies on the Magnetic Anisotropy in Lanthanide(III)-Centered Fe3 Ln Propellers.

Compounds [Fe3 Ln(tea)2 (dpm)6 ] (Fe3 Ln; Ln= Tb-Yb, H3 tea=triethanolamine, Hdpm=dipivaloylmethane) were synthesized as lanthanide(III)-centered variants of tetrairon(III) single-molecule magnets (Fe4 ) and isolated in crystalline form. Compounds with Ln=Tb-Tm are isomorphous and show crystallographic threefold symmetry. The coordination environment of the rare earth, given by two tea(3-) ligands, can be described as a bicapped distorted trigonal prism with D3 symmetry. Magnetic measurements showed the presence of weak ferromagnetic Fe⋅⋅⋅Ln interactions for derivatives with Tb, Dy, Ho, and Er, and of weak antiferromagnetic or negligible coupling in complexes with Tm and Yb. Alternating current susceptibility measurements showed simple paramagnetic behavior down to 1.8 K and for frequencies reaching 10000 Hz, despite the easy-axis magnetic anisotropy found in Fe3 Dy, Fe3 Er, and Fe3 Tm by single-crystal angle-resolved magnetometry. Relativistic quantum chemistry calculations were performed on Fe3 Ln (Ln=Tb-Tm): the ground J multiplet of Ln(3+) ion is split by the crystal field to give a ground singlet state for Tb and Tm, and a doublet for Dy, Ho, and Er with a large admixture of mJ states. Gyromagnetic factors result in no predominance of gz component along the threefold axis, with comparable gx and gy values in all compounds. It follows that the environment provided by the tea(3-) ligands, though uniaxial, is unsuitable to promote slow magnetic relaxation in Fe3 Ln species.

A prospective video-controlled study of genito-urinary disorders in 35 consecutive laparoscopic TMEs for rectal cancer.

INTRODUCTION: Genito-urinary disorders (GUD) for radical rectal cancer surgery range from 10 to 30%. In this study, primary endpoint is to prospectively assess their incidence in patients undergoing Laparoscopic Total Mesorectal Excision (LTME) without neoadjuvant chemo-radiation (NCR). Secondary endpoint is to detect the potential lesion site evaluating video-recordings of surgery. PATIENTS AND METHODS: A study of 35 consecutive patients treated by LTME for extra-peritoneal rectal cancer not subjected to NCR, M:F = 23:12, median age 70, was evaluated preoperatively by Uroflowmetry and US postvoid residual urine measurement (PVR), International Prostatic Symptoms Score (IPSS), and International Consultation on Incontinence Modular Questionnaire (ICIQ) at 1 and 9 months post-operatively. Evaluation of sexual function was carried out by International Index of Erectile Function (IIEF) in males. Data were analyzed performing Fisher and paired samples t tests. Surgical videos of patients affected by GUD were reviewed to identify lesion sites. RESULTS: Urinary function:IPSS average score: baseline 6.03 ± 5.51, 8.93 ± 6.42 (p = .005) at 1 month, and 7.26 ± 5.55 (p = .041) at 9 months. ICIQ baseline 2.67 ± 5.42, 4.27 ± 6.19 (p = NS) at 1 month, and 3.63 ± 5.23 (p = NS) at 9 months. Maximum urine flow rate baseline 15.95 ± 4.78 ml/s, 14.23 ± 5.27 after 1 month (p = .041), and 15.22 ± 4.01 after 9 months (p = NS). Mean urine flow rate baseline 9.15 ± 2.96 ml/s, 7.99 ± 4.12 ml/s at 1 month (p = .044), and 8.54 ± 4.19 ml/s at 9 months (p = NS). PVR baseline 59.62 ± 54.49, 64.59 ± 58.71 (p = NS) at 1 month, and 68.82 ± 77.72 (p = NS) at 9 months. Sexual function: IIEF baseline 19.38 ± 6.25, 14.06 ± 8.65 at 1 month (p = .011), and 15.4 ± 8.41 at 9 months, (p = NS). Video review of patients with disorders showed potential damage at the site of ligation of IMA (high hypogastric plexus) in 1 case, lateral and posterior mesorectum dissection (hypogastric nerves) in 2 cases, anterior dissection of the Denonvilliers fascia from seminal vesicles in 2 cases. CONCLUSIONS: GUD at 1 month from LTME for rectal cancer are significant but improve at 9 months. Surgical video review of patients with GUD provides an important tool for detection of lesion sites.

Small bowel perforation caused by pancreaticojejunal anastomotic stent migration after pancreaticoduodenectomy for periampullary carcinoma.

CONTEXT: Pancreaticoduodenectomy is the gold standard for patients with resectable periampullary carcinoma. The protection of the anastomosis by positioning of an intraluminal stent is a technique used to lower the frequency of anastomotic fistulas. However the use of anastomotic stents is still debated and stent related complications are reported. CASE REPORT: A fifty-three-year old male underwent pancreaticoduodenectomy (PD) for a T2N0 periampullary carcinoma with a pancreaticojejunal (duct to mucosa) anastomosis protected by a free floating 6 Fr Nelaton stent in the Wirsung duct. Twenty-three months after surgery the patient accessed Emergency Department for severe abdominal pain associated to temperature, high white blood cell count and an significant increase in C reactive protein. Method Abdominal CT scan shown the presence of a tubular stent in the mesogastrium/lower right quadrant. No evident free intra-abdominal air was detected. The patient was submitted to explorative laparotomy. After debridement for localized peritonitis the Nelaton trans anastomotic stent was found in the abdomen. There was no evidence of bowel perforation, but intestinal loops covered with fibrin and suspect for impending perforation were resected. CONCLUSION: There is a lack of evidence about the true rate of post-operative complications related to pancreatic stenting. We believe that in patients presenting with abdominal pain or peritonitis that previously underwent PD with stent-guided pancreaticojejunal anastomosis, the hypothesis of stent migration should at least be taken into consideration.

Redox-Controlled Exchange Bias in a Supramolecular Chain of Fe4 Single-Molecule Magnets.

Tetrairon(III) single-molecule magnets [Fe4(pPy)2(dpm)6] (1) (H3pPy=2-(hydroxymethyl)-2-(pyridin-4-yl)propane-1,3-diol, Hdpm=dipivaloylmethane) have been deliberately organized into supramolecular chains by reaction with Ru(II)Ru(II) or Ru(II)Ru(III) paddlewheel complexes. The products [Fe4(pPy)2(dpm)6][Ru2(OAc)4](BF4)x with x=0 (2 a) or x=1 (2 b) differ in the electron count on the paramagnetic diruthenium bridges and display hysteresis loops of substantially different shape. Owing to their large easy-plane anisotropy, the s=1 diruthenium(II,II) units in 2 a act as effective s(eff)=0 spins and lead to negligible intrachain communication. By contrast, the mixed-valent bridges (s=3/2, s(eff)=1/2) in 2 b introduce a significant exchange bias, with concomitant enhancement of the remnant magnetization. Our results suggest the possibility to use electron transfer to tune intermolecular communication in redox-responsive arrays of SMMs.

Mapping of single-site magnetic anisotropy tensors in weakly coupled spin clusters by torque magnetometry.

Single-crystal torque magnetometry performed on weakly-coupled polynuclear systems provides access to a complete description of single-site anisotropy tensors. Variable-temperature, variable-field torque magnetometry was used to investigate triiron(III) complex [Fe3La(tea)2(dpm)6] (Fe3La), a lanthanum(III)-centred variant of tetrairon(III) single molecule magnets (Fe4) (H3tea = triethanolamine, Hdpm = dipivaloylmethane). Due to the presence of the diamagnetic lanthanoid, magnetic interactions among iron(III) ions (si = 5/2) are very weak (<0.1 cm(−1)) and the magnetic response of Fe3La is predominantly determined by single-site anisotropies. The local anisotropy tensors were found to have Di > 0 and to be quasi-axial with |Ei/Di| ~ 0.05. Their hard axes form an angle of approximately 70° with the threefold molecular axis, which therefore corresponds to an easy magnetic direction for the molecule. The resulting picture was supported by a High Frequency EPR investigation and by DFT calculations. Our study confirms that the array of peripheral iron(III) centres provides substantially noncollinear anisotropy contributions to the ground state of Fe4 complexes, which are of current interest in molecular magnetism and spintronics.