Oxidative Cross Dehydrogenative Coupling of N-Heterocycles with Aldehydes through C(sp3)-H Functionalization.

Existing methodologies for metal-catalyzed cross-couplings typically rely on preinstallation of reactive functional groups on both reaction partners. In contrast, C-H functionalization approaches offer promise in simplification of the requisite substrates; however, challenges from low reactivity and similar reactivity of various C-H bonds introduce considerable complexity. Herein, the oxidative cross dehydrogenative coupling of α-amino C(sp3)-H bonds and aldehydes to produce ketone derivatives is described using an unusual reaction medium that incorporates the simultaneous use of di-tert-butyl peroxide as an oxidant and zinc metal as a reductant. The method proceeds with a broad substrate scope, representing an attractive approach for accessing α-amino ketones through the formal acylation of C-H bonds α to nitrogen in N-heterocycles. A combination of experimental investigation and computational modeling provides evidence for a mechanistic pathway involving cross-selective nickel-mediated cross-coupling of α-amino radicals and acyl radicals.

Synthesis, antibacterial and QSAR evaluation of 5-oxo and 5-thio derivatives of 1,4-disubstituted tetrazoles.

A series of 1,4-disubstituted tetrazol-5-ones 3a, 5, 7, 12, 13 and 1,4-disubstituted tetrazol-5-thiones 3b, 9, 10 was synthesized and fully characterized by IR, MS, (1)H NMR and (13)C NMR. The series was evaluated for in vitro antibacterial activity against four Gram negative (Escherichia coli, Proteus mirabilis, Klebsiella pneumonia, and Pseudomonas aeruginosa) and three Gram positive (Staphylococcus aureus, Enterococcus faecalis, and Bacillus subtilis) bacteria. The zone of inhibition was measured using the well-diffusion assay, and in vitro minimum inhibitory concentration (MIC) was determined by microbroth dilution assay. MIC values indicate that compounds exhibited a varied range (0.2-37 µg/mL) of antibacterial activity against the tested bacterial strains. Statistically significant QSAR models were developed by the simple linear regression analysis for the correlation of MIC with computed descriptors. The concluded cross validated regression factors are 0.953 and 0.986 for E. coli, and S. aureus, respectively.

Hereditary parkinsonism with dementia is caused by mutations in ATP13A2, encoding a lysosomal type 5 P-type ATPase.

Neurodegenerative disorders such as Parkinson and Alzheimer disease cause motor and cognitive dysfunction and belong to a heterogeneous group of common and disabling disorders. Although the complex molecular pathophysiology of neurodegeneration is largely unknown, major advances have been achieved by elucidating the genetic defects underlying mendelian forms of these diseases. This has led to the discovery of common pathophysiological pathways such as enhanced oxidative stress, protein misfolding and aggregation and dysfunction of the ubiquitin-proteasome system. Here, we describe loss-of-function mutations in a previously uncharacterized, predominantly neuronal P-type ATPase gene, ATP13A2, underlying an autosomal recessive form of early-onset parkinsonism with pyramidal degeneration and dementia (PARK9, Kufor-Rakeb syndrome). Whereas the wild-type protein was located in the lysosome of transiently transfected cells, the unstable truncated mutants were retained in the endoplasmic reticulum and degraded by the proteasome. Our findings link a class of proteins with unknown function and substrate specificity to the protein networks implicated in neurodegeneration and parkinsonism.

Electrocardiographic Effects of Bupropion Toxicity Suggesting Dysfunction of the Gap Junction or Connexin 43.

This is a case of a 20-year-old pregnant female presenting EKG abnormalities associated with an overdose of bupropion. These ECG abnormalities are prolongation of the QRS, prolongation of the corrected QT interval (QTc), right axis deviation, and a terminal R wave. The propagation of electricity through the myocardium is dependent on many factors. It is dependent on the flow of sodium from the extracellular to intracellular space, flow of potassium from intracellular to extracellular space, and ultimately the propagation of the signal at the gap junction by Connexin 43 (Cx-43). We postulate that the ECG abnormalities in this case are secondary to bupropion's effect on the potassium rectifier channels (Kir) and or Cx-43 at the gap junction.

Brugada Phenotype Following a Cocaine Overdose.

Brugada syndrome is a rare cardiac condition characterized by distinctive electrocardiogram patterns, predisposing individuals to fatal arrhythmias. While primarily linked to a loss-of-function mutation in the SCN5A gene, acquired forms of the syndrome have been associated with various factors, including drug use. We present a case of a 31-year-old female who presented to the emergency department unresponsive following cocaine use and developed type 1 Brugada ECG patterns alongside an incomplete right bundle branch block in V1-V3, ST elevations with biphasic waves, and diffuse repolarization abnormalities with J point deviations while in the intensive care unit. This study aimed to discuss the complexity of managing drug-induced Brugada-like findings and highlights the need for further research into the mechanisms underlying cocaine-induced cardiac effects. We aimed to discuss potential mechanisms for the impact of cocaine as its role as a sodium channel blocker and its potential effects on connexin 43 in the context of Brugada syndrome. This study also reinforced the importance of differentiating between true Brugada syndrome and other similar ECG changes for appropriate care management.

Electrocatalytic Nitrogen Reduction on a Molybdenum Complex Bearing a PNP Pincer Ligand.

Electrocatalytic nitrogen reduction (N2R) mediated by well-defined molecular catalysts is poorly developed by comparison with other reductive electrocatalytic transformations. Herein, we explore the viability of electrocatalytic N2R mediated by a molecular Mo-PNP complex. A careful choice of acid, electrode material, and electrolyte mitigates electrode-mediated HER under direct electrolysis and affords up to 11.7 equiv of NH3 (Faradaic efficiency < 43%) at -1.89 V versus Fc+/Fc. The addition of a proton-coupled electron transfer (PCET) mediator has no effect. The data presented are rationalized by an initial electron transfer (ET) that sets the applied bias needed and further reveal an important impact of [Mo] concentration, thereby pointing to potential bimolecular steps (e.g., N2 splitting) as previously proposed during chemically driven N2R catalysis. Finally, facile reductive protonation of [Mo(N)Br(HPNP)] with pyridinium acids is demonstrated.

Hyalinizing Trabecular Tumor of the Thyroid Gland: A Case Report and Literature Review.

A hyalinizing trabecular tumor (HTT) of the thyroid gland is a very rare type of tumor. It is usually diagnosed incidentally during the examination for thyroid gland diseases that need thyroidectomy. Here we report a case of HTT in a 60-year-old male patient who presented with anterior neck swelling and underwent total thyroidectomy for a Bethesda category V nodule. The final histologic diagnosis of the left lobe was consistent with a hyalinized trabecular adenoma of the thyroid gland, or paraganglioma-like adenoma. We discuss the clinical picture and diagnostic approach, including the role of fine needle aspiration biopsy, and the pathologic features of HTT, with particular reference to the possible differential diagnosis.

Etiology of trauma-related acute compartment syndrome of the forearm: a systematic review.

OBJECTIVES: Acute compartment syndrome (ACS) can be caused by multiple causes that affect people of different ages. It is considered an orthopedic emergency condition that requires immediate diagnosis and surgical intervention to avoid devastating complications and irreversible damages. This systematic review aimed to present the etiology of trauma-related forearm ACS. METHODS: A systematic review was performed on four different databases: Embase, Medline, Cochrane Central Register of Controlled Trials (CENTRAL) and Cochrane Database of systematic review register databases via Ovid, with no restriction on dates (last date was June 30, 2021). It included all the studies containing data about the etiology of trauma-related forearm ACS. RESULTS: A total of 4893 articles were retrieved: 122 met the inclusion criteria, 39 were excluded, 25 were out of scope and 14 had insufficient details. Hence, this review constituted 83 articles and 684 patients. The etiology of ACS causing forearm ACS was classified into three groups: fracture-related, soft tissue injury-related and vascular injury-related. The fracture-related group was the most common group (65.4%), followed by soft tissue injury (30.7%), then vascular injuries (3.9%). Furthermore, supracondylar humerus fractures were the most common cause of fractures related to forearm ACS. Blunt traumas were the most common cause of soft tissue injuries-related forearm ACS, and brachial artery injuries were the most common cause of vascular-related forearm ACS. CONCLUSION: Frequent assessment of patients with the most prevalent etiologies of forearm ACS is recommended for early detection of forearm ACS and to save limbs.

[Multiple tuberculous aortic aneurysms in a child. A case report]. / Multiples anévrismes aortiques d'origine tuberculeuse chez un enfant. A propos d'un cas.

INTRODUCTION: Tuberculous aortic aneurysms are rarely seen. Their major complication is unforeseeable and lethal aneurysmal rupture. We report an exceptional case of multiple tuberculous aortic aneurysms in a child. CASE REPORT: A 13-year-old girl was admitted to our hospital with abdominal pain. She reported a history of fever, night sweats and weight loss. Physical examination showed a pulsatile mass over the umbilicus. Thoracoabdominal angio-NMR revealed multiple pseudoaneurysms of the thoracic and abdominal aorta. The patient underwent elective laparotomy, resection of the abdominal aortic and in situ prosthetic repair with an aortic graft. The postoperative recovery was uneventful. The histopathologic examination of the aortic wall and para-aortic lymph nodes showed evident features of tuberculosis. Antituberculous chemotherapy was initiated. CONCLUSION: Tuberculous aortic aneurysms are rarely seen. Their major complication is rupture. Surgery must not be delayed just like antitubercular therapy.

[Giant aneurysm of the splenic artery. Case report and review of the literature]. / Anévrisme géant de l'artère splénique. A propos d'un cas et revue de la littérature.

INTRODUCTION: Giant splenic artery aneurysm is exceptional. We report a case and review the literature to ascertain the characteristic epidemiological, clinical and therapeutic features of this condition. CASE REPORT: A 62-year-old man was admitted for epigastric pain. Physical examination found an epigastric pulsatile mass. A contrast computed scan of the abdomen revealed a 10-cm thrombosed aneurysm of the splenic artery. An abdominal aortography, including selective celiac angiography, confirmed the presence of a 10-cm aneurysm originating from the medial third of the splenic artery. The patient underwent open surgical repair. The proximal and the distal splenic artery were ligated from within the aneurysm. The postoperative period was uneventful. CONCLUSION: Giant aneurysm of the splenic artery is a rare clinical entity. These aneurysms differ from usual splenic artery aneurysms in several ways involving the predominant gender, localization on the splenic artery, clinical presentation, and treatment.

Fibromyalgia Syndrome and Vitiligo: A Novel Association.

OBJECTIVES: This study aims to assess the relationship between fibromyalgia syndrome (FMS) and vitiligo in Iraqi patients and evaluate the predictors of this relationship, if present. PATIENTS AND METHODS: The case-control study included 100 Iraqi patients (46 males, 54 females; mean age 30.4±14 years; range 15 to 65 years) with vitiligo and 200 age- and sex-matched healthy controls (74 males, 126 females; mean age 30.3±9.4 years; range 15 to 62 years). Baseline characteristics of patients and controls were recorded. The 2012 Canadian Guidelines criteria were used for the diagnosis of FMS and applied to all patients and controls. RESULTS: Prevalence of FMS in vitiligo patients and controls was 12% and 7%, respectively (p=0.15, odds ratio=1.8, 95% confidence interval=0.8-4.08). FMS symptoms in vitiligo patients were fatigue (46%), diffuse body pain (34%), sleep disturbance (33%), cognitive dysfunction (30%), and mood disorders (23%), while visceral involvements were central nervous system (52%), skin (35%), gastrointestinal tract (32%), cardiovascular system- respiratory system (16%), genitourinary tract (8%), and ear nose throat (7%). Of vitiligo patients, FMS was significantly more common among females (22.2%) compared to none among males (0%) (p<0.05). Prevalence of FMS was restricted to female sex only and a significantly higher prevalence rate of FMS was found among female vitiligo patients (22.2%) compared to controls (9.5%). Receiving phototherapy significantly increased the risk of having FMS by 5 times compared to female patients not receiving phototherapy. Use of any steroid reduced the risk of having FMS by 2.5 times (inverse of odds ratio=0.4) among females patients (p>0/05). No significant association was found between FMS in vitiligo patients and age, disease duration, type of vitiligo, use of any immunosuppressant and body mass index (p>0.05). CONCLUSION: Fibromyalgia syndrome was more prevalent in vitiligo patients compared to controls, which was clinically important but statistically not significant. There was a significant association between FMS in vitiligo patients and female sex, severe form of vitiligo, and receiving phototherapy. This may suggest that early diagnosis of FMS in vitiligo patients may help in early treatment and subsequently improve patients' quality of life.

[Multiple paragangliomas: about two cases]. / Paragangliomes multiples: à propos de deux cas.

The multiple paragangliomas are rare tumours, with slow evolution, posing diagnostic and therapeutic problems. The carotid and jugulo-tympanic localization are the most frequent, and the aortic localization is very infrequent. The association of two, three and four localization is possible in the multiple forms. These multiple localizations are more frequent in familial forms. Surgical removal is the first intention treatment of these tumours. In the multiple forms, the therapeutic strategy must be adapted to each case: usually, the intervention begins by the carotid localization. We report two cases of chemodectoma with multiple localizations. The first case is a 44 years-old woman, who presented a double localization: carotid (bilateral) and aortic (arch). The second case is a patient with a double aortic localization, carotid and aortic, associated to a tympano-jugular localization. Surgical treatment was performed for all these localization, except for the tympano-jugular localization, treated by embolization. The post-operative periods were uneventful. The first case had adjunctive radiotherapy.

[Cerebral revascularisation in Takayasu's arteritis]. / Revascularisation cérébrale dans la maladie de Takayasu.

SUBJECT: Supraaortic angioplasty is often not feasible in patients with Takayasu's arteritis because of involvement of long segment of arteries. Consequently, the role of surgical treatment in the management of cerebral ischemia is important in this disease. The objective of this work is to specify the indications and surgical techniques in lesions of arteries to the head in this disease and to report our experience. METHODS: Seven patients with cervical arterial lesions due to Takayasu's arteritis were treated by bypass surgery in the department of vascular surgery, Ibn-Sina hospital on one period of 11 years. RESULTS: It is about 6 women and one man of middle age at the time of the diagnosis of 33,8 years. The revealing signs were essentially of neurological and ocular order. Six of our patients were in inflammatory thrust at the time of the diagnosis, and required a medical treatment first to basis of corticosteroids. Bypasses from the ascending aorta to the carotid artery were performed in six cases. In one case, the bypass was performed between the brachiocephalic artery and common carotid artery. A death in relation with a cerebral hemorrhage occurred 2 days after the revascularisation. A clean improvement of the functional signs was noted among 3 patients, whereas the improvement was partial at two other. A secondary thrombosis of the bypass surgery occurred in 3 cases. CONCLUSION: The natural history of Takayasu's arteritis and its evolution is badly known. The operative indications must not rest solely on the only anatomical balance, but based on a bundle of arguments in which, the assessment of the cerebral blood flow would be useful. Cerebral hyperperfusion syndrom constitutes a major risk that can be reduced by staged revascularisations.

Reference range of flaccid and stretched penile lengths of adult males in Baghdad: A cross-sectional study.

OBJECTIVES: To establish a baseline reference range for flaccid (FPL) and stretched penile lengths (SPL) in adult males and to compare with reports from different nationalities, as concerns over penile size are common among men and currently the number of men seeking help for the perceived problem of a 'short' penis is increasing. SUBJECTS AND METHODS: Over a 1-year period, FPL and SPL measurements were taken from males undergoing medical examination in the outpatient clinic of the Al-Karama Teaching Hospital, using a rigid centimetre ruler. The correlation between penile length and age was investigated. RESULTS: In all, 223 apparently healthy males were included in this study with a mean (SD; range) age of 41.3 (15.0; 20-77) years. The mean (SD; range) FPL was 9.8 (2.0; 5-17) cm and the SPL was 12.6 (1.9; 7.5-19.5) cm. Statistical analysis showed that penile length is increased in older age (>55 years). A penile length nomogram was constructed, showing that the 50th percentiles of FPL and SPL were 9.0 and 12.5 cm, respectively. CONCLUSION: Our data establish a baseline reference range for adult male penile lengths in the Capital of Iraq (Baghdad), which should be useful for urologists when counselling patients.

Temporal and Spatial Flap Variability in Laser In-Situ Keratomileusis by Optical Coherence Tomography.

PURPOSE: To study changes in flap thickness made with two different microkeratome heads across different corneal locations using anterior segment optical coherence tomography (OCT). METHODS: In this prospective, non-randomized, consecutive case series, subjects who had their laser in-situ keratomileusis (LASIK) flaps made using 90 µm (MSU90) or 130 µm (MSU130) disposable M2 microkeratome heads were examined using OCT. The measurements were performed at three locations (central and 2.5 mm to either side) at 1 day, 1 week, and 1 month postoperatively. RESULTS: The central flap thickness was 123 ± 15, 130 ± 14, and 127 ± 13 µm, respectively, at 1 day, 1 week, and 1 month postoperatively in the MSU90 group (41 eyes) and 142 ± 20, 147 ± 19, and 143 ± 15 µm, respectively, in the MSU130 group (47 eyes). At 1 month, peripheral flap thickness was 161 ± 17 and 159 ± 13 µm, respectively, at 2.5 mm to the right and left of corneal center in the MSU90 group. The corresponding figures were 170 ± 14 and 167 ± 13 µm, respectively, in the MSU130 group. There was a statistically significant difference between the two groups at all locations (P < 0.001). No statistically significant change in flap thickness was detected in either group at any assessment time. There was a partial positive correlation (after controlling for preoperative manifest refractive spherical equivalent) between central flap thickness and preoperative ultrasound central pachymetry (r = 0.739, P = 0.036) in the MSU90 group but not in the MSU130 group. CONCLUSION: Using OCT, changes in flap thickness were minimal in the first month after LASIK. Flap thickness correlated strongly with central corneal thickness if a 90 µm head was used.

[Superficial fungal infections. Epidemiologic, clinical and mycologic study over a three year period]. / Les mycoses superficielles. Etude épidémio-clinique et mycologique sur trois ans.

The object of our study is to release the epidemiological, clinical and mycological characteristics of superficial fugal infections. A retrospective study was carried out during three years (1996-1998). Direct microscopy was positive in 86% cases, the culture in 62% cases. Trichophyton rubrum accounts for 85% of the dermatophytic flora. The superficial fugal infections account for 15% of the reasons for consultation in our service. They would touch according to data's of literature 2 to 13% of the general population. Trichophyton rubrum in accordance with the various series published, is the fungi most frequently insulated with variable rates between 46 and 82% of the superficial fungal infections. Any time, Candida albicans is prevalent on the level of the hands.

Investigation of uranium geochemistry along groundwater flow path in the Continental Intercalaire aquifer (Southern Tunisia).

Environmental tracers ((2)H, (18)O, isotopes of Uranium) and geochemical processes occurring within groundwaters from the Continental Intercalaire (CI) in Southern Tunisia were used to understand the hydrodynamics and the recharge conditions of this aquifer. This study investigates the chemical and isotopic compositions of the CI groundwater. The water types are dominated by Na(+), SO4(2-), Cl(-) throughout most of the basin with a general increase in total dissolved solids from the Saharan Platform margins towards the Chotts region. Large scale groundwater flow paths are toward the Chotts region. The stable isotopes composition of the analyzed groundwater ranges from -8.8 to -6‰ vs V-SMOW for δ(18)O and from -67 to -40‰ vs V-SMOW for δ(2)H. The relatively enriched stable isotopes contents suggest the contribution of the Dahar sandstones outcrops in the current recharge of the CI aquifer in an arid context. However, the most depleted values in heavy isotopes indicate a paleorecharge of the aquifer under wetter conditions revealing a long residence time of groundwaters. The results from water samples using alpha spectrometry method indicate a range in (238)U concentrations and (234)U/(238)U activity ratios (AR) of 0.044-1.285 µg kg(-1) and 1.2 to 8.84 respectively. The geochemistry of uranium isotopes in groundwater is controlled by many factors, essentially, the influence of water rock interactions, the preferential dissolution of (234)U relative to (238)U due to alpha recoil and the mixing processes between different waters with distinct AR as well as (238)U concentrations.

Panniculitis is a common unrecognized histopathological feature of cutaneous leishmaniasis.

BACKGROUND: Cutaneous leishmaniasis (CL) is a parasitic cutaneous infection caused by Leishmania parasite. The histopathology is usually granulomatous in nature. AIMS: The aim of the present study is to elucidate the histology of CL and evaluate the presence and the frequency of panniculitis among the affected patients. SETTINGS AND DESIGN: Case series interventional study. MATERIALS AND METHODS: Thirty-five patients with CL were diagnosed clinically between December-2012 and May-2013. Diagnostic confirmation established by smears, culture, and polymerase chain reaction (PCR). The histopathological assessment was carried out to study the general pathology and to look for the presence of panniculitis. STATISTICAL ANALYSIS USED: Simple statistics utilized via SPSS version 16.0 (SPSS, Inc., Chicago, USA). RESULTS: Eighteen women and 17 men with CL were enrolled in the present work with a mean duration of their disease was 3 months. The results of the diagnostic tests were as follow: The smear was positive in 21 (60%) of cases, Leishman-Donovan (LD) bodies were seen in 7 (20%) patients, culture was positive in 24 (68%), and PCR was positive in 32 (91.4%) patients. The epidermal changes included acanthosis, pseudoepitheliomatous hyperplasia, ulceration, focal spongiosis, and interface dermatitis while the dermal changes were dependent on the spectrum of the disease, so in the ulcerative lesions there was lymphohistiocytic infiltration with foci of plasma cells and sometimes aggregate of LD bodies, whereas in the dry lesions the pathology is mainly of epithelioid granuloma. Panniculitis was seen in 16 (46%) cases as a diffuse lymphohistiocytic infiltration of both the septum and lobules of the subcutaneous layer of the skin. CONCLUSION: Panniculitis is an important feature of CL that must be differentiated from other diseases that can simulate CL such as chronic skin infections, Discoid lupus erythematosus, and cutaneous lymphoma.