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Claudius Amyand's hernia is defined by the incarceration of the vermicular appendix through the hernial sac. The first appendectomy was performed in 1735. It is a very rare pathology. Therefore, the frequency of this pathology is not yet established. We report the observation of a 54-year-old patient with an estimated BMI of 25.5 kg: height2 with a simple inguinal hernia that was not followed up and admitted to the emergency room with a painless and impulsive inguinal swelling when coughing. The management consisted of a conditioning and a pre-anesthetic assessment. The intraoperative exploration revealed a right inguinal hernia with caecal and appendicular contents of viable appearance. The procedure included an appendectomy and cure of the hernia using the Lichtenstein technique. The evolution was marked by a resumption of transit 24 hours postoperatively, Appendicitis complicating an Amyand's hernia is a rare pathology that often presents in an atypical clinical picture of an inguinal painful mass without the occlusive syndrome. Its preoperative radiological diagnosis, although exceptional, is of interest given the atypical presentation allowing the elimination of local pathologies that sometimes do not require emergency surgery.

Idiopathic small bowel volvulus is a rare cause of acute intestinal obstruction by strangulation in adults and is defined by the twisting of a segment of the small bowel around its mesenteric axis with no obvious underlying congenital or acquired cause. This article reports the case of a 56-year-old patient, chronic smoker and cannabis user, who was admitted with febrile occlusive syndrome and generalized abdominal contracture. The abdominal CT scan showed a distension of the small intestines upstream of a probable small bowel volvulus, associated with signs of digestive distress. Surgical exploration revealed a large peritoneal effusion of distressed fluid, with a volvulus of the distal small bowel causing 1.80 m of small bowel and coecum necrosis from 2.20 ADJ without rotational abnormality or docking defect.

Trauma to the pancreas is rare, occurring in 0.2 to 3% of abdominal injuries. They are associated with high mortality and morbidity if diagnosis is delayed. Their clinical symptomatology is atypical. Abdominal CT scans can diagnose pancreatic injury and rupture of the main pancreatic duct. It is important that surgeons are aware of the issues and principles of management of pancreatic injury. We report the case of a 33-year-old patient with no previous pathological history. Admitted for a closed abdominal contusion following a road traffic accident with an abdominal impact point without initial loss of consciousness and generalized abdominal contracture. Abdominal CT scan showed a hypodense area in the tail of the pancreas not enhanced after contrast injection, possibly related to a pancreatic fracture and a medium-sized peritoneal effusion. The patient underwent corporo-caudal pancreatectomy with splenic preservation. Postoperative follow-up was favorable. The clinical evolution judged on regular controls was favorable over a period of 2 years. We would like to share a very difficult clinical case and our experience with the support of the literature. This is a challenge to clinicians and surgeons above all.

Gastrointestinal trichobezoar is a rare syndrome, defined by the accumulation inside the digestive tract of non-digestible material usually formed by hair rarely by textile fibers (wool of carpets or clothes), and source of many diagnostic and therapeutic errors and delays in the absence of evocative psychic context. We report the case of a 15-year-old adolescent with a history of carpet wool ingestion, who presented to the visceral emergency department with an occlusive syndrome, evolving since 4 days of his admission with alteration of his general state. Abdominal examination found a painful abdominal meteorism with no clinically palpable mass. The abdominal scan showed a distension of small intestine, suggesting an intestinal invagination. The surgical intervention was an extraction of a trichobezoard (wool from carpets) by the anal way.

The hemiterpene isoprene is a volatile C5 hydrocarbon with industrial applications. It is generated today from fossil resources, but can also be made in biological processes. We have utilized engineered photosynthetic cyanobacteria for direct, light-driven production of bio-isoprene from carbon dioxide, and show that isoprene in a subsequent photochemical step, using either near-UV or simulated or natural solar light, can be dimerized into limonene, paradiprene, and isomeric C10H16 hydrocarbons (monoterpenes) in high yields under photosensitized conditions (above 90% after 44 hours with near-UV and 61% with simulated solar light). The optimal sensitizer in our experiments is di(naphth-1-yl)methanone which we use with a loading of merely 0.1 mol%. It can also easily be recycled for subsequent photodimerization cycles. The isoprene dimers generated are a mixture of [2+2], [4+2] and [4+4] cycloadducts, and after hydrogenation this mixture is nearly ideal as a drop-in jet fuel. Importantly the photodimerization can be carried out at ambient conditions. However, the high content of hydrogenated [2+2] dimers in our isoprene dimer mix lowers the flash point below the threshold (38 °C), yet, these dimers can be converted thermally into [4+2] and [4+4] dimers. When hydrogenated these monoterpenoids fully satisfy the criteria for drop-in jet fuels with regard to energy density, flashpoint, kinematic viscosity, density, and freezing point. Life-cycle assessment results show a potential to produce the fuel in an environmentally sustainable way.

Organogenesis is an in vitro regeneration method used for rapid and large-scale propagation of a number of plant species. During the last decade, organogenesis has been used as a tool to rehabilitate date palm groves in Morocco, and resulted in the production of millions of date palm plantlets. In the present study, the production cost of date palm plantlets (cv. Mejhoul) obtained through direct organogenesis was estimated. The organogenesis protocol used was based on previously published studies. The cost analysis included the costs of offshoots, culture medium components, chemicals, equipment maintenance, water, fuel and electricity consumption as well as staff salaries and all the consumables used during in vitro work and plantlet acclimatization. The hardware (infrastructure, laboratory equipment and vessels) cost was not included. During the production process, the loss of plant material due to endophytic bacteria, tissue browning and hyperhydricity was taken into account. At the end of the organogenesis process, an average of 947.6 plantlets were produced from one offshoot. It was found that staff salaries (46.05%) and electricity consumption (26.16%) account for the majority of expenses. The production cost of one plantlet was estimated to be US$ 3.84. The findings of the present study highlight the economic feasibility of using organogenesis for date palm propagation. The production cost of date palm plantlets through organogenesis was estimated. The economic feasibility of this technique was highlighted when compared with conventional propagation through offshoots.

The aromaticity of cyclic 4n pi-electron molecules in their first pi pi* triplet state (T-1), labeled Baird aromaticity, has gained growing attention in the past decade. Here we explore computationally the limitations of T-1 state Baird aromaticity in macrocyclic compounds, [n]CM's, which are cyclic oligomers of four different monocycles (M = p-phenylene (PP), 2,5-linked furan (FU), 1,4-linked cyclohexa-1,3-diene (CHD), and 1,4-linked cyclopentadiene (CPD)). We strive for conclusions that are general for various DFT functionals, although for macrocycles with up to 20 pi-electrons in their main conjugation paths we find that for their T-1 states single-point energies at both canonical UCCSD(T) and approximative DLPNO-UCCSD(T) levels are lowest when based on UB3LYP over UM06-2X and UCAM-B3LYP geometries. This finding is in contrast to what has earlier been observed for the electronic ground state of expanded porphyrins. Yet, irrespective of functional, macrocycles with 2,5-linked furans ([n]CFU's) retain Baird aromaticity until larger n than those composed of the other three monocycles. Also, when based on geometric, electronic and energetic aspects of aromaticity, a (3)[n]CFU with a specific n is more strongly Baird-aromatic than the analogous (3)[n]CPP while the magnetic indices tell the opposite. To construct large T-1 state Baird-aromatic [n]CM's, the design should be such that the T-1 state Baird aromaticity of the macrocyclic perimeter dominates over a situation with local closed-shell Hiickel aromaticity of one or a few monocycles and semilocalized triplet diradical character. Monomers with lower Hiickel aromaticity in S-0 than benzene (e.g., furan) that do not impose steric congestion are preferred. Structural confinement imposed by, e.g., methylene bridges is also an approach to larger Baird-aromatic macrocycles. Finally, by using the Zilberg-Haas description of T-1 state aromaticity, we reveal the analogy to the Bickel aromaticity of the corresponding closed-shell dications yet observe stronger Hiickel aromaticity in the macrocyclic dications than Baird aromaticity in the T-1 states of the neutral macrocycles.

The aim of the present study was to estimate the production cost of dates of cv. Majhoul (Phoenix dactylifera L.) as part of the Moroccan strategy to develop the date palm sector, and to compare it to that reported in the main exporting regions. Data were collected through surveys of farmers and farm owners carried out in the “Meski Boudnib” extension zone during 2018 and 2019, as well as from studies performed by some governmental organizations. The surveys were conducted on 30 modern and productive date palm farms, managed in monoculture and equipped with localized irrigation systems. All fixed and variable costs were calculated. It was found, through our calculations, that the subsidies from the Moroccan government reduce the average investment cost of a modern date palm farm by 56%. It was also shown that the production cost of one ton of date fruits of cv. Majhoul in the extension zone “Meski Boudnib” (Morocco) is estimated at about 6060 MAD (US$ 634.5), out of which 28% represents the labor cost and 23% represents mineral and organic fertilization costs. The findings of the present study revealed that the production cost of one ton of cv. Majhoul dates in “Meski Boudnib” is lower than those reported in the Coachella Valley (20,189 MAD/ton; US$ 2114) and the Jordan Valley (10,536 MAD/ton; US$ 1103).

and importance: Acute appendicitis is one of the most common causes of acute abdomen in surgical patients. The objectives of the study were to evaluate efficacy of Alvarado scoring system in preoperative diagnosis of acute appendicitis and correlating it with postoperative findings.The present study was a prospective study of 208 patients presenting with symptoms and signs of acute appendicitis to the emergency department during a period of 10 months. Patients who met the inclusion criteria were evaluated using Alvarado scoring system. The efficacy of Alvarado scoring system was assessed by calculating sensitivity, specificity, positive predictive value, negative predictive value and negative appendectomy rate.Total 208 patients were included in the study, which included 142 males and 66 females, at score of 7 or more, appendicitis was confirmed in 187/190 patients, while at scores7 appendicitis was confirmed in 10/18 patients. The sensitivity was 94.9%, the specificity was 72.7%, the positive predictive value was 98.4% and the negative predictive value was 44.4%. In the present study, negative appendectomy rate was 4.8.Clinical experience remains of major importance in diagnosing acute appendicitis. The Alvarado score is a simple, easy scoring system at both end of scale.

Highlights • Polysplenia is a complex polymalformative syndrome that includes a spectrum of visceral and vascular anatomical abnormalities; extremely undiscovered in adulthood. • A rare case of polysplenia syndrome showing an exceptional association between preduodenal portal vein, dorsal pancreas agenesis and polysplenia on gastric adenocarcinoma. • Surgeons must be aware of their possible existence and be able to recognize them to avoid major intraoperative injuries. • Surgeons must have a perfect knowledge of the reference anatomy and the exploration of anatomical variations in imaging before surgical exploration. • PDPV is believed to pose increased risk to gastric cancer patients during gastrectomy and lymph node dissection around the hepatoduodenal ligament., Purpose of the study Polysplenia is a complex polymalformative syndrome that is frequently accompanied by an inconsistent spectrum of visceral and vascular anatomical abnormalities and is extremely undiscovered in adulthood. The objective of this article is to limit the intraoperative risks generated by the lack of knowledge of these anatomical variations by insisting on the inconstancy of all these variations and the perfect knowledge of the reference anatomy and the exploration of the anatomical variations in imaging before the surgery. Patient and methods The patient was 50-year-old who was hospitalized in our department for gastric adenocarcinoma. During her extension assessment, a polysplenia syndrome was accidentally discovered on the scan images, which showed an exceptional association between preduodenal portal vein, agenesis of the dorsal pancreas, and polysplenia. Conclusion There are neither specific clinical symptoms of the polysplenia syndrome, nor any biological sign; hence, the interest of recognizing this pathology is to avoid diagnostic errors, but also to guide the surgeon during the surgical act performed.

Several fully pi-conjugated macrocycles with puckered or cage-type structures were recently found to exhibit aromatic character according to both experiments and computations. We examine their electronic structures and put them in relation to 3D-aromatic molecules (e.g., closo-boranes) and to 2D-aromatic polycyclic aromatic hydrocarbons. Using qualitative theory combined with quantum chemical calculations, we find that the macrocycles explored hitherto should be described as 2D-aromatic with three-dimensional molecular structures (abbr. 2D-aromatic-in-3D) and not as truly 3D-aromatic. 3D-aromatic molecules have highly symmetric structures (or nearly so), leading to (at least) triply degenerate molecular orbitals, and for tetrahedral or octahedral molecules an aromatic closed-shell electronic structure with 6n + 2 electrons. Conversely, 2D-aromatic-in-3D structures exhibit aromaticity that results from the fulfillment of Hückel's 4n + 2 rule for each macrocyclic path, yet, their -electron counts are coincidentally 6n + 2 numbers for macrocycles with three tethers of equal lengths. It is notable that 2D-aromatic-in-3D macrocyclic cages can be aromatic with tethers of different lengths, i.e., with p-electron counts different from 6n + 2, and they are related to naphthalene. Finally, we identify tetrahedral and cubic pi-conjugated molecules that fulfill the 6n + 2 rule and exhibit significant electron delocalization. Yet, their properties resemble those of analogous compounds with electron counts that differ from 6n + 2. Thus, despite that these molecules show substantial pi-electron delocalization they cannot be classified as true 3D-aromatics O.E.B. is grateful to the Wenner-Gren Foundations for a postdoctoral fellowship (UPD 2018-0305), and H.O., K.J., and R.A. acknowledge the Swedish Research Council for financial support (grants 2015-04538 and 2019-05618). M.S. is grateful for the financial support from the Spanish MICINN (project PID2020-113711GB-I00) and the Catalan DIUE (project 2017SGR39). D.W.S. acknowledges the financial support by the National Science Centre, Poland (2021/42/E/ST4/ 00332) and the PL-Grid Infrastructure of the Academic Computer Centre (CYFRONET). The computations were enabled by resources provided by the Swedish National Infrastructure for Computing (SNIC) at the National Supercomputer Center (NSC), Linköping, partially funded by the Swedish Research Council through grants 2015-04538 and 2019-05618

The exact energies of the lowest singlet and triplet excited states in organic chromophores are crucial to their performance in optoelectronic devices. The possibility of utilizing singlet fission to enhance the performance of photovoltaic devices has resulted in a wide demand for tuneable, stable organic chromophores with wide S1–T1 energy gaps (>1 eV). Cibalackrot-type compounds were recently considered to have favorably positioned excited state energies for singlet fission, and they were found to have a degree of aromaticity in the lowest triplet excited state (T1). This work reports on a revised and deepened theoretical analysis taking into account the excited state Hückel-aromatic (instead of Baird-aromatic) as well as diradical characters, with the aim to design new organic chromophores based on this scaffold in a rational way starting from qualitative theory. We demonstrate that the substituent strategy can effectively adjust the spin distribution on the chromophore and thereby manipulate the excited state energy levels. Additionally, the improved understanding of the aromatic characters enables us to demonstrate a feasible design strategy to vary the excited state energy levels by tuning the number and nature of Hückel-aromatic units in the excited state. Finally, our study elucidates the complications and pitfalls of the excited state aromaticity and antiaromaticity concepts, highlighting that quantitative results from quantum chemical calculations of various aromaticity indices must be linked with qualitative theoretical analysis of the character of the excited states., Cibalackrot-type compounds are Hückel instead of Baird aromatic in their first triplet states (T1). By choice of substituents and additional benzannelation we adjust the T1 energies, providing a new strategy for singlet fission chromophore design.

Recently, several fully pi-conjugated macrocycles with strongly puckered or cage-type structures have been synthesized and found to exhibit aromatic character according to both experiments and computations. Herein, we examine their electronic structures and put them in relation to truly 3D-aromatic molecules (e.g., closo-boranes and certain charged fullerenes) as well as 2D-aromatic polycyclic aromatic hydrocarbons. We use qualitative theory combined with quantum chemical calculations, and find that the macrocycles explored thus far should be described as 2D-aromatic with three-dimensional structures (abbr. 2D-aromatic-in-3D) instead of truly 3D-aromatic. Besides fulfilling the 6n + 2 pi-electron rule, 3D-aromatic molecules with highly symmetric structures (e.g., Td and Oh) have a number of molecular orbital (MO) levels that are (at least) triply degenerate. At lower symmetries, the triple (or higher) orbital degeneracies should be kept in approximate sense. This last criterion is not fulfilled by macrocyclic cage molecules that are 2D-aromatic-in-3D. Their aromaticity results from a fulfillment of Hückel’s 4n + 2 rule for each individual macrocyclic path, yet, their pi-electron counts are coincidentally 6n + 2 numbers for macrocycles with three tethers of equal lengths. We instead link the 3D-macrocyclic molecules explored earlier to naphthalene, motivating their description as 2D-aromatics albeit with 3D structures. It is notable that macrocyclic cages which are 2D-aromatic-in-3D can be aromatic also when the tethers are of different lengths, i.e., when their pi-electron counts differ from 6n + 2. Finally, we identify tetrahedral and cubic pi-conjugated molecules that fulfill the 6n + 2 rule and which exhibit significant electron delocalization. Yet, their properties are similar to those of analogous compounds with electron counts that differ from 6n + 2. Thus, despite that these tetrahedral and cubic molecules show substantial pi-electron delocalization they should not be classified as true 3D-aromatics.

International audience; The relaxation volume ( rel), here determined per extra-atom or vacant site, of common crystalline defects in bcc iron (Fe) was calculated from molecular dynamics simulation (MD) cells containing defects of varying size and/or density. To this end, we used both real and reciprocal space data: for the former, the change in the MD cell volume was calculated, while for the latter, we computed X-ray diffraction reciprocal space maps to evaluate the change in the lattice parameter. We show that dumbbell self-interstitial atoms have the largest  rel , ~1.5 atomic volume (~1.5 0). C15 clusters of size 12 and 48 atoms show  rel of ~0.91 0 and ~0.98 0, respectively, and similar values are found for ½ and interstitial dislocation loops, with  rel ~0.905 0 and  rel ~0.873 0, respectively. Single vacancies are characterized by a negative  rel , ~-0.11 0. For cavities,  rel rapidly increases to approach zero as the clusters grow. Using these values, we managed to predict (with an accuracy better than 2 %) the lattice strain in MD cells containing several types of defects, which indicates that the relaxation volumes can be summed up to estimate the microscopic (i.e., lattice) volume change.

The synthesis and properties of a series of unsymmetrical thienopentalenes are explored, including both monoareno and diareno derivatives. For the synthesis of monoareno pentalenes, a carbopalladation cascade reaction between alkynes and

Primary lymphomas of appendix are extremely rare tumors. The incidence is 0.015% out of all gastrointestinal lymphomas; furthermore, limited data is available in literature. The appendiceal neoplasms are most commonly presented as acute appendicitis followed intestinal obstruction, intussusception or perforation. We present a case of a 22 year-old male patient who presented with acute appenditis and underwent emergency laparotomy. On abdominal exploration, swollen and enlarged appendix measured 3cm was present for which appendectomy were performed. The histopathological examination of appendectomy specimen revealed a Burkitt's Lymphoma. The patient received R-COPADEM protocol of chemotherapy. Primary gastrointestinal lymphoma is a extremely rare neoplasm without guidelines for therapy., Highlights • Burkitt lymphoma is an aggressive non-hodgkin b-cell lymphoma. • The occurrence of primary Burkitt's lymphoma of appendix is extremely rare. • The appendiceal neoplasms are most commonly presented as acute appendicitis. • The diagnosis of kimura disease is confirmed by surgical biopsy. • The diagnostic of Burkitt's lymphoma was only made after histopathological examination, so should be done. • The surgery and chemotheray constitue a best traitement for burkitt's lymphoma of appendix presenting as acute appendicitis.

Phytobezoars are concretions of indigested fruit and vegetables fibers in the gastrointestinal tract. The past of gastric surgery is most common risk factor of phytobezoar. We present the case of a 39-year-old female was admitted to the emergency department and who presented with small bowel obstruction due to phytobezoar, her past medical history was marqued by truncal vagotomy and simple suture recurrent perforated gastric ulcer 15 years earlier. Her postoperative recovery was uneventful., Highlights • The phytobezoar are concretion on undigested fruits and vegetables fibers in the gastrointestinal tract. • The occurrence of small bowel obstruction caused by phytobezoar is extremely rare. • The past of gastric surgery is most commun factor of phytobezoar.

Post-operative incisional hernias are parietal complications occurring after laparotomy or laparoscopy. The incisional hernias after laparoscopy (IHAL) were first described in 1968, with the incidence increasing due to the generalization of the laparoscopic practice. We report the case of a women, with history of laparoscopic cholecystectomy three months earlier, admitted to the visceral emergency for a Richter’s hernia strangulated on the left para-rectal trocar port of 10 mm in diameter. The abdominal computed tomography (CT) scan permits to make the diagnosis. The cure of the hernia was made by laparotomic repair in emergency after reintroduction of its content. The patient was discharged without adverse event. Les hernies incisionnelles post chirurgicales sont des complications pariétales survenant après une laparotomie ou une laparoscopie. Les hernies incisionnelles post cœlioscopie(HIPC) étaient décrites pour la première fois en 1968. Leur incidence est de plus en plus marquée par la généralisation d’utilisation de la cœlioscopie. Nous rapportons le cas d’une patiente, opérée pour lithiase de la vésicule biliaire par cœlioscopie, trois mois avant son admission aux urgences viscérales pour une hernie de Richter étranglée sur orifice de trocart para rectal gauche de 10 mm de diamètre. La tomodensitométrie abdominale a posé le diagnostic de certitude. La cure de la hernie par raphie a été faite par laparotomie en urgence après réintroduction de son contenu.

Introduction Retroperitoneal Retrocecal hernias are a rare variety of internal hernias and represent an unusual cause of bowel obstruction. Early diagnosis is based on CT scan and requires knowledge of the pathology in order to avoid small bowel resection. We report a case of retrocecal hernia treated surgically and review the characteristics and treatment of retrocecal hernias in the literature. Materials and methods Our work is a retrospective case report with a descriptive aim concerning a patient operated for retrocecal hernia within the department of general surgery of CHU Ibn Rochd Casablanca. Case report A 72-year-old man presented to the emergency department with abdominal pain and vomiting that have been evolving for 9 days complicated by an occlusive syndrome 36 hours before the admission. The patient was apyretic, and the abdominal examination noted abdominal meteorism predominantly in the right iliac fossa, absence of abdominal scarring, and free hernial orifices. The abdominal X-ray showed air-fluid levels and the abdominopelvic CT scan found clumping of the dilated small intestines posteriorly and below the cecum. The diagnosis of retrocecal hernia was suspected and the patient was taken to the operating room. The operation was performed by laparotomy through a midline incision. On exploration, the cecum and ascending colon were pushed forward and viable bowel loops were incarcerated in a fossa located posteriorly and below the cecum. The procedure consisted of a collapse of the retrocecal ligaments by right coloparietal collapse. Conclusion A bowel obstruction in an apyretic patient without abdominal scarring or parietal hernia should suggest the diagnosis of internal hernia, which must be investigated., Highlights • Retrocecal hernias are a rare variety of internal hernias and represent an unusual cause of bowel obstruction. • Early diagnosis is based on CT scan and requires knowledge of the pathology. • The procedure consisted of a collapse of the retrocecal ligaments by right coloparietal collapse. • We report the case of a retrocecal hernia in an elderly man and describe the anatomy and the characteristic features of this pathology.

The Sebou Watershed, contains an area of 40000 km2, it represents a third of the surface flows of Morocco it is characterized by a varied topography from North to South, their extent and their lithology. This variation has a strong effect on the distribution of precipitation and the flow regimes of rivers. The current study is an attempt to delineate the hydrodynamic of the different aquifers and watercourses of this Watershed. In the Rif in the north of the basin, the slopes are steep, with significant hydrographic networks, characterized by a torrential water volume, on the other hand in the south by water tables which allows the retention of a very large quantity of water of precipitation and runoff.

Due to the reversal in electron counts for aromaticity and antiaromaticity in the closed-shell singlet state (normally ground state, S0 ) and lowest ππ* triplet state (T1 or T0 ), as given by Huckel's and Baird's rules, respectively, fulvenes are influenced by their substituents in the opposite manner in the T1 and S0 states. This effect is caused by a reversal in the dipole moment when going from S0 to T1 as fulvenes adapt to the difference in electron counts for aromaticity in various states; they are aromatic chameleons. Thus, a substituent pattern that enhances (reduces) fulvene aromaticity in S0 reduces (enhances) aromaticity in T1 , allowing for rationalizations of the triplet state energies (ET ) of substituted fulvenes. Through quantum chemical calculations, we now assess which substituents and which positions on the pentafulvene core are the most powerful for designing compounds with low or inverted ET . As a means to increase the π-electron withdrawing capacity of cyano groups, we found that protonation at the cyano N atoms of 6,6-dicyanopentafulvenes can be a route to on-demand formation of a fulvenium dication with a triplet ground state (T0 ). The five-membered ring of this species is markedly Baird-aromatic, although less than the cyclopentadienyl cation known to have a Baird-aromatic T0 state.

1,3,2,4-Diazadiboretidine, an isoelectronic heteroanalogue of cyclobutadiene, is an interesting chemical species in terms of comparison with the carbon system, whereas its properties have never been investigated experimentally. According to Baird's rule, Huckel antiaromatic cyclobutadiene acquires aromaticity in the lowest triplet state. Here we report experimental and theoretical studies on the ground- and excited-state antiaromaticity/aromaticity as well as the photophysical properties of an isolable 1,3,2,4-diazadiboretidine derivative. The crystal structure of the diazadiboretidine derivative revealed that the B2 N2 ring adopts a planar rhombic geometry in the ground state. Yet, theoretical calculations showed that the B2 N2 ring turns to a square geometry with a nonaromatic character in the lowest triplet state. Notably, the diazadiboretidine derivative has the lowest singlet and triplet states lying at close energy levels and displays blue phosphorescence.

Internal hernias are a rare cause of acute intestinal obstruction. Supravesical hernia is an exceptional form of hernia that is often diagnosed intraoperatively. The abdominal CT scan performed in the emergency guides the preoperative diagnosis. Our work concerns a patient admitted to the visceral surgical department of the university hospital ibn Rochd of Casablanca for an occlusion dating back to 05 days, the abdmonial x-ray objectified hydro-aerial levels in the small intestine, and the CT scan found an invagination at the left fossa iliaca associated with a double hernia: internal supravesical and left inguinal. The patient was then operated after conditioning and the diagnosis of an internal supravesical hernia was retained per operatively. Internal supravesical hernia is a very rare cause of acute intestinal occlusion and is often diagnosed at the time of surgical exploration., Highlights • Supravesical hernias are rare but potential causes of intestinal. • Internal hernia of the supravesical fossa is an unusual cause of small bowel obstruction. • Pre-operative diagnosis of this condition is very difficult. • The surgical management can be conducted indiscriminately by laparoscopy or laparotomy. • The treatment is release of the intestinal obstruction and closing the hernial defect to prevent future recurrences.

Introduction Cushing's syndrome (CS) is a rare and severe disease. Acute pancreatitis is the leading cause of hospitalization. The association of the two disease is rare and uncommon. We report the case of a 37-year-old woman admitted in our service for acute pancreatitis and whose Cushing syndrome was diagnosed during hospiatilisation. The aim of this work is to try to understand the influence of de Cushing in acute pancreatitis and to establish a causative relationship between the two diseases. Observation It is a 37-year-old woman with a history of corticosteroid intake for six months, stopped three months ago who consulted for epigastralgia and vomiting. The physical exam found epigastric sensitivity with Cushing syndrome symptoms. A CT scan revealed acute edematous-interstitial pancreatitis stage E of Balthazar classification. 24 h free cortisol of 95 μg/24 h and cortisolemia of 3.4 μg/dl. The patient was treated symptomatically and referred after to endocrinology service for further treatment. Conclusion The association with acute pancreatitis and CS is rare and uncommon. Although detailed studies and evidence are lacking, it can therefore be inferred that CS is one of the risk factors for the onset of acute pancreatitis. The medical treatment and management of acute pancreatitis in those patients do not differ from other pancreatitis of any etiologies., Highlights • There is a highs suspicion of acute pancreatitis complications for patients with Cushing syndrome. • Corticosteroids are a common cause for both Cushing syndrome and acute pancreatitis. • There are many common etiologies between Cushing syndrome and acute pancreatitis. • Cushing syndrome is a risk factor of acute pancreatitis, need further detailed studies.

The hemiterpene isoprene is a volatile C5 hydrocarbon, with industrial applications. It is generated today from fossil resources, but can also be made in biological processes. We have utilized engineered photosynthetic cyanobacteria for direct, light-driven production of bio-isoprene from carbon dioxide, and show that isoprene in a subsequent photochemical step, using simulated or natural solar light, can be dimerized into limonene, paradiprene, and isomeric C10H16 hydrocarbons (monoterpenes) in very high yields (above 90% after 44 hours) under sensitized conditions. The optimal sensitizer in our experiments is di(naphth-1-yl)methanone which we can use with a loading of merely 0.1 mol%, and it is easily recycled for subsequent photodimerization cycles. The isoprene dimers generated are a mixture of [2+2], [4+2] and [4+4] cycloadducts, and after hydrogenation this mixture is nearly ideal as a jet fuel drop-in. Importantly, the photodimerization can be carried out at ambient conditions. The high content of hydrogenated [2+2] dimers in our isoprene dimer mix lowers the flash point below the threshold (38 °C), yet, these dimers can be converted thermally into [4+2] and [4+4] dimers. When hydrogenated these monoterpenoids fully satisfy the criteria for drop-in jet fuels with regard to energy density, flashpoint, kinematic viscosity, density, and freezing point.

Highlights • Intestinal endometriosis as a cause of intestinal obstruction is often a diagnostic challenge mimicking a wide spectrum of diseases. • Its diagnosis is still very difficult. • The treatment of intestinal endometriosis is in most cases surgical. • The diagnosis of endometriosis is histological., The gastrointestinal tract is the most common site of extra pelvic endometriosis, with the rectum and sigmoid colon being the most frequently affected areas. Its diagnosis is still very difficult, especially when it manifests itself as an acute occlusion. We report the case of a patient admitted to the emergency room for an occlusive syndrome on a sigmoid process and who was operated on with colorectal resection and it was the anatomopathological examination that led to the diagnosis of endometriosis.

The exact energies of the lowest singlet and triplet excited states in organic chromophores are crucial to their performance in optoelectronic devices. The possibility of utilizing singlet fission to enhance the performance of photovoltaic devices has resulted in a wide demand for tuneable, stable organic chromophores with wide S1 – T1 energy gaps (>1 eV). Cibalackrot-type compounds were recently considered to have favorably positioned excited state energies for singlet fission, and they were found to have a degree of aromaticity in the lowest triplet excited state (T1). This work reports on a revised and deepened theoretical analysis taking into account the excited state Hückel-aromatic (instead of Baird-aromatic) as well as diradical characters, with the aim to design new organic chromophores based on this scaffold in a rational way starting from qualitative theory. We demonstrate that the substituent strategy can effectively adjust the spin populations on the chromophore moieties and thereby manipulate the excited state energy levels. Additionally, the improved understanding of the aromatic characters enables us to demonstrate a feasible design strategy to vary the excited state energy levels by tuning the number and nature of Hückel-aromatic units in the excited state. Finally, our study elucidates the complications and pitfalls of the excited state aromaticity and antiaromaticity concepts, highlighting that quantitative results from quantum chemical calculations of various aromaticity indices must be linked with qualitative theoretical analysis of the character of the excited states.

Acute pancreatitis is an inflammation of the pancreas that can be caused in rare situations by ansa pancreatica, it is a rare anatomic variation of the pancreatic ducts. It is a communication between the main pancreatic duct (Wirsung) and the accessory pancreatic duct (Santorini). We report a case of the patient, in a 44-year-old, non-alcoholic, hospitalized for acute pancreatitis stage C of Baltazar. A magnetic resonance Cholangiopancreatography (MRCP) was performed which showed a gallstone and ansa pancreatica, than an endoscopic retrograde cholangiopancreatography (ERCP) revealed an ansa pancreatica with a common bile duct clear, a sphincterotomy of the major papilla was performed. It is still not clear whether the presence of these two pathologies is a coincidence or if the ansa pancreatica is the cause of acute pancreatitis. New studies are necessary to clarify these points.

The association of Enterobius vermicularis and appendicitis were recognized in the late XIXe century, when an incidence of 19% of appendicular infestation in children with appendicitis was reported. Other studies showed that the relationship between this parasitosis and appendicitis varied from 0.2 to 41.8 worldwid. In this paper we present an adult patient with acute appendicitis caused by Enterobius Vermicularis discovered in per-surgical procedure, and we’re going to discuss on the bases of the literature the epidemiological, clinical, and therapeutic characteristics of the appendicular localization of oxyurosis.

Due to the reversal in electron counts for aromaticity and antiaromaticity in the closed-shell singlet state (normally ground state, S0) and lowest * triplet state (T1 or T0), as given by Hückel's and Baird's rules, respectively, fulvenes are influenced by their substituents in the opposite manner in the T1 and S0 states. This effect is caused by a reversal in the dipole moment when going from S0 to T1 as fulvenes adapt to the difference in electron counts for aromaticity in various states; they are aromatic chameleons. Thus, a substituent pattern that enhances (reduces) fulvene aromaticity in S0 reduces (enhances) aromaticity in T1, allowing for rationalizations of the triplet state energies (ET) of substituted fulvenes. Through quantum chemical calculations we now assess which substituents and which positions on the pentafulvene core are the most powerful for designing compounds with low or inverted ET. As a means to increase the -electron withdrawing capacity of cyano groups we found that protonation at the cyano N atoms of 6,6-dicyanopentafulvenes can be a route to on-demand formation of a fulvenium dication with a triplet ground state (T0). The five-membered ring of this species is markedly Baird-aromatic, although less than the cyclopentadienyl cation known to have a Baird-aromatic T0 state M.S. is grateful for financial support from the Spanish MINECO (project CTQ2017-85341-P), the Catalan DIUE (2017SGR39, XRQTC, and ICREA Academia 2014 Award), and the FEDER fund (UNGI10-4E-801)

Compounds with dibenzannelated heterocycles with eight π-electrons are found in a range of applications. These molecules often adopt a bent structure in the ground state (S0 ) but can become planar in the first excited states (S1 and T1 ) because of the cyclically conjugated 4nπ central ring, which fulfils the requirements for excited state aromaticity. We report on a quantum chemical investigation of the aromatic character in the S1 and T1 states of dibenzannelated seven- and six-membered heterocycles with one, two, or three heteroatoms in the 8π-electron ring. These states could have ππ* or nπ* character. We find that compounds with one or two heteroatoms in the central ring have ππ* states as their S1 and T1 states. They are to a significant degree influenced by excited state aromaticity, and their optimal structures are planar or nearly planar. Among the heteroatoms, nitrogen provides for the strongest excited state aromaticity whereas oxygen provides for the weakest, following the established trend of the S0 state. Yet, dibenzannelated seven-membered-ring compounds with N=N bonds have non-aromatic nπ* states with strongly puckered structures as their S1 and T1 states.

Singlet exciton fission photovoltaics requires chromophores with their lowest excited states arranged so that 2E(T1) < E(S1) and E(S1) < E(T2). Herein, qualitative theory and quantum chemical calculations are used to develop explicit strategies on how to use Baird’s 4n rule on excited state aromaticity, combined with Hückel’s 4n+2 rule for ground state aromaticity, to tailor new potential chromophores for singlet fission. We first analyze the E(T1), E(S1) and E(T2) of benzene and cyclobutadiene (CBD) as, respectively, excited state antiaromatic and aromatic archetypes, and reveal that CBD fulfils the criteria on the state ordering for a singlet fission chromophore. We then look at fulvenes, a class of compounds that can be tuned by choice of substituents from Baird-antiaromatic to Baird-aromatic in T1 and S1, and from Hückel-aromatic to Hückel-antiaromatic in S0. The T1 and S1 states of most substituted fulvenes (159 of 225) are described by singly excited HOMO→LUMO configurations, providing a rational for the simultaneous tuning of E(T1) and E(S1) along an approximate (anti)aromaticity coordinate. Key to the tunability is the exchange integral (KH,L), which ideally is constant throughout the compound class, providing a constant DE(S1-T1). This leads us to a geometric model for identification of singlet fission chromophores, and we explore what factors limit the model. Candidates with calculated E(T1) of ~1 eV or higher are identified among benzannelated 4npi-electron compound classes and siloles. In brief, it is clarified how the joint utilization of Baird’s 4n and Hückel’s 4n+2 rules, together with substituent effects (electronic and steric) and benzannelation, can be used to tailor new chromophores with potential use in singlet fission photovoltaics.

According to the currently accepted structure-property relationships, aceno-pentalenes with angular shape (fused to the 1,2-bond of the acene) exhibit higher antiaromaticity than those with linear shape (fused to the 2,3-bond of the acene). To explore and expand the current view, we designed and synthesized molecules where two isomeric, yet, different, 8π antiaromatic subunits, a benzocyclobutadiene (BCB) and a pentalene are combined into, respectively, an angular and a linear topology via an unsaturated 6-membered ring. The antiaromatic character of the molecules are supported experimentally by 1H NMR, UV-Vis and cyclic voltammetry measurements and X-ray crystallography. The experimental results are further confirmed by theoretical studies including the calculation of several aromaticity indices (NICS, ACID, HOMA, FLU, MCI). In the case of the angular molecule, double bond-localization within the connecting 6-membered ring resulted in reduced antiaromaticity of both the BCB and pentalene subunits, while the linear structure provided a competitive situation for the two unequal [4n]π subunits. We found that in the latter case pentalene drew the shorter straw. The BCB unit alleviated its unfavorable antiaromaticity more efficiently, leaving the pentalene with enhanced antiaromaticity. Thus, a reversed structure-antiaromaticity relationship when compared to aceno-pentalenes was achieved.

Significance Fluorescence imaging, a central pillar of medical and fundamental research, is hampered by stochastic blinking, limited photon budgets, and phototoxicities of organic fluorophores. Here, we use quantum chemical calculations and targeted synthetic strategies to tune the Baird aromatic triplet-state energy of cyclooctatetraene to enhance its capacity to mediate intramolecular triplet−triplet energy transfer with distinct organic fluorophores spanning the visible spectrum. By tuning the efficiency of the self-healing mechanism, we generate cyanine-class fluorophore derivatives with improved intrinsic brightness and photostability, and reduced reactive oxygen species generation. We leverage these advances to extend the time scale of camera-based, single-molecule imaging techniques, including Förster (fluorescence) resonance energy transfer methods, to the kilohertz regime in fully oxygenated physiological buffers., Bright, photostable, and nontoxic fluorescent contrast agents are critical for biological imaging. “Self-healing” dyes, in which triplet states are intramolecularly quenched, enable fluorescence imaging by increasing fluorophore brightness and longevity, while simultaneously reducing the generation of reactive oxygen species that promote phototoxicity. Here, we systematically examine the self-healing mechanism in cyanine-class organic fluorophores spanning the visible spectrum. We show that the Baird aromatic triplet-state energy of cyclooctatetraene can be physically altered to achieve order of magnitude enhancements in fluorophore brightness and signal-to-noise ratio in both the presence and absence of oxygen. We leverage these advances to achieve direct measurements of large-scale conformational dynamics within single molecules at submillisecond resolution using wide-field illumination and camera-based detection methods. These findings demonstrate the capacity to image functionally relevant conformational processes in biological systems in the kilohertz regime at physiological oxygen concentrations and shed important light on the multivariate parameters critical to self-healing organic fluorophore design.

Singlet exciton fission photovoltaic technology requires chromophores with their lowest excited states arranged so that 2E(T-1) < E(S-1) and E(S-1) < E(T-2). Herein, qualitative theory and quantum chemical calculations are used to develop explicit strategies on how to use Baird's 4n rule on excited-state aromaticity, combined with Huckel's 4n + 2 rule for ground-state aromaticity, to tailor new potential chromophores for singlet fission. We first analyze the E(T-1), E(S-1), and E(T-2) of benzene and cyclobutadiene (CBD) as excited-state antiaromatic and aromatic archetypes, respectively, and reveal that CBD fulfills the criteria on the state ordering for a singlet fission chromophore. We then look at fulvenes, a class of compounds that can be tuned by choice of substituents from Baird-antiaromatic to Baird-aromatic in T-1 and S-1 and from Huckel-aromatic to Huckel-antiaromatic in S-0. The T-1 and S-1 states of most substituted fulvenes (159 of 225) are described by singly excited HOMO -> LUMO configurations, providing a rational for the simultaneous tuning of E(T-1) and E(S-1) along an approximate (anti)aromaticity coordinate. Key to the tunability is the exchange integral (K-H,K-L), which ideally is constant throughout the compound class, providing a constant.E(S-1 - T-1). This leads us to a geometric model for the identification of singlet fission chromophores, and we explore what factors limit the model. Candidates with calculated E(T-1) values of similar to 1 eV or higher are identified among benzannelated 4npelectron compound classes and siloles. In brief, it is clarified how the joint utilization of Baird's 4n and Huckel's 4n + 2 rules, together with substituent effects (electronic and steric) and benzannelation, can be used to tailor new chromophores with potential use in singlet fission photovoltaics.

Introduction Small bowel adenocarcinoma is a rare but increasing disease. It poses both a diagnostic and therapeutic challange. Small bowel adenocarcinoma is a rare cause of small bowel obstruction. We present the case of a patient admitted to our emergency department for a bowel obstruction due to a mass of the jejunum and whose anatomopathological diagnosis was adenocarcinoma. Patient and method It is a 62-year-old woman with unparticular history, admitted to the emergency of visceral surgery of Ibn Rochd University Hospital for subocclusive syndrome evolving for one year, with early postprandial vomiting becoming stenosing two months ago. The abdominal CT scan showed thickening jejunal wall of 46 mm with upstream distension. She underwent a segmental bowel resection of 50 cm of small bowel with 3 cm stenotic mass located at 40 cm from the duodenojejunal angle. The pathophysiology revealed an invasive liberkhunian adenocarcinoma. The postoperative follow-up was simple, feeding allowed at D4 with discharge allowed at D6 and functional improvement at the time of the control performed three months after the intervention. Discussion Small bowel adenocarcinoma is rare and represents only 1–3% of all gastrointestinal cancers. The incidence of SBA is 24 to 66 times lower than that of colorectal cancer (CRC). Due to its non-specific clinical manifestation and less accessible location, SBA is diagnosed at an advanced stage, and often at specimen analysis. The treatment is resection and the overall survival is increased when diagnostic is early made. Conclusion Small bowel adenocarcinoma is a rare but increasing cause of gastrointestinal malignancy, being both a diagnostic and therapeutic challenge. In front of the occlusive syndrome of small bowel appearance, adenocarcinoma must be ruled out., Highlights • Small bowel adenocarcinoma is rare and has a poor overall survival. • Small bowel obstruction caused by adenocarcinoma is a rare clinical situation. • The diagnosis and management of small bowel adenocarcinoma is a challenge to the physicians. • The R0 resection with complete lymph node dissection are the cornerstone of the treatment.

A change in regioselectivity is predicted in the Diels–Alder reaction when going from the singlet to triplet state., Controlling the regioselectivity in the exohedral functionalization of fullerenes and endohedral metallofullerenes is essential to produce specific desired fullerene derivatives. In this work, using density functional theory (DFT) calculations, we show that the regioselectivity of the Diels–Alder (DA) cycloaddition of cyclopentadiene to 2S+1C60 changes from the usual [6,6] addition in the singlet ground state to the [5,6] attack in high spin states of C60. Changes in the aromaticity of the five- and six-membered rings when going from singlet to high spin C60 provide a rationale to understand this regioselectivity change. Experimentally, however, we find that the DA cycloaddition of isoindene to triplet C60 yields the usual [6,6] adduct. Further DFT calculations and computational analysis give an explanation to this unanticipated experimental result by showing the presence of an intersystem crossing close to the formed triplet biradical intermediate.

Introduction This work aims to describe and discuss the epidemiological, clinical, therapeutic and evolution of Fournier's gangrene. Materials and methods Case series with retrospective data collection of patients treated for Fournier's gangrene between January 2010 and March 2017. The main etiologies, risk factors, postoperative complications outcomes and long term follow up results were analyzed. Results Eight four (84) patients were recruited. The average age of our patients was 49 years (with limits of 20–76), the male gender dominates our series (83.33%) with a sex ratio of 5 M/1W, the most frequently found risk factor was diabetes mellitus (37%). The most common etiology was anal abscesses (32%). The average time to consultation was 8 days (limits ranges from 3 to 30 days). All patients were admitted at a necrosis stage (100%). Anemia was identified in 85% of cases. The low platelets were noticed in 44.03% of cases. Hypoalbuminemia was found in 93% of cases. All patients (100%) benefited resuscitation initially and antibiotic therapy on their admission. They received emergency surgical debridement with a cleansing stoma. The average length of hospital stay was 13 days and complications occurred in 33% of cases. The mortality rate was 7.14%. Conclusion Fournier's gangrene is a medico-surgical emergency with a high morbidity and mortality rate. Early diagnosis as well as antibiotic therapy and the quality of debridement save the patients., Highlights • Fournier's gangrene is a rare but severe disease. • The diagnosis and treatment delay and lesions extension increase mortality. • The treatment is multidisciplinary. • Early diagnosis and treatment improve prognosis. • Tobacco intoxication is suspected to be risk factor.

Introduction Rectovaginal fistula (RVF) is an abnormal communication between the vagina and the rectum. RVFs caused by Bartholin's gland infection are very rare. We present the case of recurrent rectovaginal fistula complicating a bartholin's gland abcess successfully treated with a Martius flap. The aim of this work is to demonstrate the possibility of complication of bartholin's gland infection by a rectovaginal fistula and the efficacy of Martius flap procedure for recurrent RVF of the low third part of the vagina. Observation It is a 30-year-old woman admitted to our department for recurrent RVF due to an abscess of the Bartholin's glands. She was previously treated with a vaginal advancement flap which failed with persistence of the fistula and its symptoms. The patient underwent a RVF repair by Martius flap with complete healing of the fistula. Discussion Rectovaginal fistula is a complex pathology with psycho-social, individual, family, religious and ethno-environmental repercussions. Its main aetiologies are obstetric, rectal surgery. Several techniques including the vaginal or anal advancement flap and the Martius flap are used for the treatment of rectovaginal fistulas. For recurrent fistulas, the Martius flap seems to be the most indicated with better results. Conclusion Rectovaginal fistula remain a challenge for surgeons and have major psycho-socio-economic repercussions for the patient. The complication of Bartholin's gland infection by rectovaginal fistula is rare. The Martius flap technique is the method of choice for recurrent rectovaginal fistulas of the lower third of the vagina or in association with other pathologies., Highlights • Recovaginal fistula is a challenge for surgeons. • The rectovaginale fistula due to Bartholin’s gland abcess is very rare • Care must be taken during the management of this pathology which affetcs 2% of women during their life for avoiding that complication • The Martius flap is the method of choice for the treatment of rectovaginale fistula of the low third inferior part of the vagina