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1.
J Vasc Bras ; 20: e20210012, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34290758

RESUMO

A 45-year-old woman with known hypothyroidism and no other comorbidities was incidentally found to have multiple right renal artery aneurysms. The largest aneurysm measured 5 x 4.5 cm and arose from an inferior segmental branch while two smaller aneurysms arose from an upper segmental branch of the right renal artery. We performed an ex-vivo repair with reverse saphenous vein graft under cold preservation followed by orthotopic kidney auto-transplantation. Her postoperative course was unremarkable and at 1-year follow-up her right kidney is preserved. In this article, we report successful treatment of complex multiple right renal artery aneurysms and describe the surgical technique used for successful repair.


Uma mulher de 45 anos com hipotireoidismo conhecido e sem outras comorbidades teve achado incidental de múltiplos aneurismas da artéria renal direita. O maior aneurisma media 5 x 4,5 cm e tinha origem no ramo segmentar inferior, juntamente com dois pequenos aneurismas originários do ramo segmentar superior da artéria renal direita. Realizamos o reparo ex vivo com enxerto reverso de veia safena, sob preservação a frio, seguido de autotransplante renal ortotópico. O pós-operatório ocorreu sem intercorrências, e a paciente teve o rim direito preservado no seguimento de 1 ano. Neste artigo, relatamos o tratamento bem-sucedido de múltiplos aneurismas complexos da artéria renal direita e descrevemos a técnica cirúrgica utilizada para o reparo bem-sucedido.

2.
Inorg Chem ; 55(9): 4278-95, 2016 05 02.
Artigo em Inglês | MEDLINE | ID: mdl-27104913

RESUMO

A new family of one-dimensional Fe(II) 1,2,4-triazole spin transition coordination polymers for which a modification of anion and crystallization solvent can tune the switching temperature over a wide range, including the room temperature region, is reported. This series of materials was prepared as powders after reaction of ethyl-4H-1,2,4-triazol-4-yl-acetate (αEtGlytrz) with an iron salt from a MeOH/H2O medium affording: [Fe(αEtGlytrz)3](ClO4)2 (1); [Fe(αEtGlytrz)3](ClO4)2·CH3OH (2); [Fe(αEtGlytrz)3](NO3)2·H2O (3); [Fe(αEtGlytrz)3](NO3)2 (4); [Fe(αEtGlytrz)3](BF4)2·0.5H2O (5); [Fe(αEtGlytrz)3](BF4)2 (6); and [Fe(αEtGlytrz)3](CF3SO3)2·2H2O (7). Their spin transition properties were investigated by (57)Fe Mossbauer spectroscopy, superconducting quantum interference device (SQUID) magnetometry, and differential scanning calorimetry (DSC). The temperature dependence of the high-spin molar fraction derived from (57)Fe Mössbauer spectroscopy in 1 reveals an abrupt single step transition between low-spin and high-spin states with a hysteresis loop of width 5 K (Tc(↑) = 296 K and Tc(↓) = 291 K). The properties drastically change with modification of anion and/or lattice solvent. The transition temperatures, deduced by SQUID magnetometry, shift to Tc(↑) = 273 K and Tc(↓) = 263 K for (2), Tc(↑) = 353 K and Tc(↓) = 333 K for (3), Tc(↑) = 338 K and Tc(↓) = 278 K for (4), T(↑) = 320 K and T(↓) = 305 K for (5), Tc(↑) = 106 K and Tc(↓) = 92 K for (6), and T(↑) = 325 K and T(↓) = 322 K for (7). Annealing experiments of 3 lead to a change of the morphology, texture, and magnetic properties of the sample. A dehydration/rehydration process associated with a spin state change was analyzed by a mean-field macroscopic master equation using a two-level Hamiltonian Ising-like model for 3. A new structural-property relationship was also identified for this series of materials [Fe(αEtGlytrz)3](anion)2·nSolvent based on Mössbauer and DSC measurements. The entropy gap associated with the spin transition and the volume of the inserted counteranion shows a linear trend, with decrease in entropy with increasing the size of the counteranion. The first materials of this substance class to display a complete spin transition in both spin states are also presented.

3.
Chemistry ; 21(15): 5843-55, 2015 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-25736846

RESUMO

A thermochromic 1D spin crossover coordination (SCO) polymer [Fe(ßAlatrz)3](BF4)2⋅2 H2O (1⋅2 H2O), whose precursor ßAlatrz, (1,2,4-triazol-4-yl-propionate) has been tailored from a ß-amino acid ester is investigated in detail by a set of superconducting quantum interference device (SQUID), (57)Fe Mössbauer, differential scanning calorimetry, infrared, and Raman measurements. An hysteretic abrupt two-step spin crossover (T1/2(↓) = 230 K and T1/2(↑) = 235 K, and T1/2(↓) = 172 K and T1/2(↑) = 188 K, respectively) is registered for the first time for a 1,2,4-triazole-based Fe(II) 1D coordination polymer. The two-step SCO configuration is observed in a 1:2 ratio of low-spin/high-spin in the intermediate phase for a 1D chain. The origin of the stepwise transition was attributed to a distribution of chains of different lengths in 1⋅2 H2O after First Order Reversal Curves (FORC) analyses. A detailed DFT analysis allowed us to propose the normal mode assignment of the Raman peaks in the low-spin and high-spin states of 1⋅2 H2O. Vibrational spectra of 1⋅2 H2O reveal that the BF4(-) anions and water molecules play no significant role on the vibrational properties of the [Fe(ßAlatrz)3](2+) polymeric chains, although non-coordinated water molecules have a dramatic influence on the emergence of a step in the spin transition curve. The dehydrated material [Fe(ßAlatrz)3](BF4)2 (1) reveals indeed a significantly different magnetic behavior with a one-step SCO which was also investigated.

4.
Chemistry ; 21(11): 4300-7, 2015 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-25601611

RESUMO

A conformationally flexible triazole-carboxylic acid ligand derived from an L-amino acid, namely, 4 H-1,2,4-triazol-4-yl-acetic acid (αHGlytrz), has been exploited to synthesize a structurally diverse and functionally intriguing metal-organic framework with CuSiF6. The crystal structure reveals a novel single-walled metal-organic nanotube (SWMONT), namely, {[Cu3(µ3-OH)(H2O)3(Glytrz)3]⋅SiF6⋅8 H2O⋅X}∞ (1), (where X = disordered lattice water molecules) having a pore size as large as zeolites. Compound 1 was synthesized as crystals, as powder, or as layers by precipitation/electrodeposition. Mercury intrusion porosimetry demonstrates the ability of this material to store metallic mercury, after a pressure treatment, contrary to previous literature examples.

5.
Inorg Chem ; 53(3): 1263-5, 2014 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-24417443

RESUMO

A mononuclear iron(II) neutral complex (1) is screened for sensing abilities for a wide spectrum of chemicals and to evaluate the response function toward physical perturbation like temperature and mechanical stress. Interestingly, 1 precisely detects methanol among an alcohol series. The sensing process is visually detectable, fatigue-resistant, highly selective, and reusable. The sensing ability is attributed to molecular sieving and subsequent spin-state change of iron centers, after a crystal-to-crystal transformation.


Assuntos
Compostos Ferrosos/química , Gases/análise , Metanol/análise , Álcoois/análise , Cristalografia por Raios X , Modelos Moleculares , Temperatura , Volatilização
6.
Chimia (Aarau) ; 67(6): 411-8, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23945101

RESUMO

The past decade has witnessed intense research activity in the area of Fe(II) spin crossover coordination polymers, which are structurally diverse and functionally intriguing materials. In this endeavor, a less exploited series of ligands have been selected among various N-donor triazole and tetrazole molecules. Developing conventions that allow the tailoring of such functional materials with predictable architecture and properties is an important objective and current interest in crystal engineering. However, detailed knowledge on the structure-property correlation is still scanty due to the small number of crystal structures of such compounds. The principal focus is to decipher the effect of various supramolecular factors such as intermolecular interactions, hydrogen bonding etc., on the resultant Fe(II) coordination polymers. This tutorial review aims at highlighting some of the developments of such structurally diverse and functionally intriguing 1D polymeric chains, 2D and 3D networks built from triazole or tetrazole ligands exhibiting fascinating spin crossover phenomena.


Assuntos
Compostos Ferrosos/química , Compostos Organometálicos/química , Polímeros/química , Tetrazóis/química , Triazóis/química , Cristalografia por Raios X , Magnetismo , Modelos Moleculares , Estrutura Molecular , Marcadores de Spin
7.
Am J Surg ; 225(4): 630-638, 2023 04.
Artigo em Inglês | MEDLINE | ID: mdl-36424200

RESUMO

INTRODUCTION: Mucinous cystic neoplasms (MCN) are mucin-producing epithelial cell tumors of pancreas. They consist of an ovarian-type stroma expressing estrogen and progesterone receptors. Pregnancy-associated MCNs are presumed to be larger in size and more aggressive without any concrete evidence. OBJECTIVE: and Data Sources: Systematic review of published literature using PubMed and Google Scholar databases. Original articles including case reports and series published between 1970&2021 were included wherein MCN was diagnosed during pregnancy/within one-year post-partum. Thirty-three publications having 36 cases, adding one of our own patient were analyzed in this review. RESULT: Median age at presentation was 32 years. Only three (9%) patients were asymptomatic. Mean size of MCN was 135 mm. Ten patients (27%) reported an increase in size during pregnancy. Most tumors involved body and tail of pancreas (60%). Distal pancreatectomy with splenectomy was the most common resection performed (57%). No foetal mortality was reported to date. CONCLUSION: Pregnancy may cause a rapid increase in size of MCN. Decision-making is more complex and needs a fine balance between optimal oncological and obstetric outcomes.


Assuntos
Cistadenocarcinoma Mucinoso , Neoplasias Císticas, Mucinosas e Serosas , Neoplasias Pancreáticas , Feminino , Gravidez , Humanos , Adulto , Neoplasias Pancreáticas/patologia , Neoplasias Císticas, Mucinosas e Serosas/cirurgia , Pâncreas/cirurgia , Pancreatectomia , Células Epiteliais/patologia , Cistadenocarcinoma Mucinoso/cirurgia
8.
Angew Chem Int Ed Engl ; 51(50): 12597-601, 2012 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-23129209

RESUMO

Mind the gap: A complete, cooperative spin transition for a mononuclear Mn(III) complex is reported with an 8 K hysteresis window. Raman spectra collected at a single temperature in warming and cooling modes confirm the electronic bistability within the hysteresis loop. The source of the cooperativity is a disconnection in the hydrogen-bonded 1D chains that connect adjacent cations owing to an order-disorder transition in the PF(6)(-) counterion.

9.
Ulus Travma Acil Cerrahi Derg ; 28(10): 1397-1403, 2022 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-36169463

RESUMO

BACKGROUND: Surgical site infection continues to be a major problem after laparotomy for perforation peritonitis, as it increases morbidity and hospital stay and decreases the quality of life. Intra-abdominal drain placement is a routine practice in perforation peri-tonitis. The aim of our study is to compare the incidence of surgical site infection in two groups of patients who were operated for perforation peritonitis: The first group received the intraperitoneal drain, while no drain was placed in the second group. METHODS: The present single-center, prospective, non-randomized study was conducted in the Department of General Surgery at the Postgraduate Institute of Medical Education and Research, India. A total of 122 patients underwent exploratory laparotomy for gastroduodenal and small bowel perforation peritonitis, of which 100 participants were included in this study, based on specified cri-teria for inclusion and exclusion. A total of 50 participants each were included in the drain group and the no drain group, respectively. A drain was placed in every alternate patient with perforation peritonitis who received primary closure or resection anastomosis. Patients with diabetes, renal failure, and hemodynamic instability and those who presented more than 72 h since symptom onset were excluded from the study. Peritoneal fluids were cultured. The primary endpoint was to identify the incidence of surgical site infections (SSIs) in the two groups. We also compared the time taken for the return of bowel movements, duration for which a nasogastric tube was inserted, whether any intervention was performed under local or general anesthesia within 30 days of surgery, the duration of hospital stay, and the ease of diagnosing repair leak in the post-operative period in both the groups. RESULTS: Demographics of participants in both the groups were matched. No significant difference was observed between the drain and no-drain groups with respect to the incidence of surgical site infection (p=0.779). The duration of surgery and length of hospital stay were significantly lower in the no drain group. A significant difference was observed between the two groups concerning the peritoneal culture growth, and increased bacterial growth was seen in the drain group. No significant difference in morbidity was noted between the two groups, which was classified according to the Clavien-Dindo classification. CONCLUSION: Routine use of intra-abdominal drains was not found to be effective in preventing SSIs, but a selection bias cannot be ruled out. Patients with no drains had a significantly shorter duration of hospital stay.


Assuntos
Peritonite , Infecção da Ferida Cirúrgica , Drenagem/efeitos adversos , Humanos , Peritonite/epidemiologia , Peritonite/etiologia , Peritonite/cirurgia , Complicações Pós-Operatórias/epidemiologia , Complicações Pós-Operatórias/etiologia , Complicações Pós-Operatórias/prevenção & controle , Estudos Prospectivos , Qualidade de Vida
10.
J Am Chem Soc ; 133(40): 15850-3, 2011 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-21936512

RESUMO

The first crystal structures of a dinuclear iron(II) complex with three N1,N2-1,2,4-triazole bridges in the high-spin and low-spin states are reported. Its sharp spin transition, which was probed using X-ray, calorimetric, magnetic, and (57)Fe Mossbauer analyses, is also delineated in the crystalline state by variable-temperature fluorimetry for the first time.

11.
Int J Mol Sci ; 12(8): 5339-51, 2011.
Artigo em Inglês | MEDLINE | ID: mdl-21954363

RESUMO

A ß-aminoacid ester was successfully derivatized to yield to 4H-1,2-4-triazol-4-yl-propionate (ßAlatrz) which served as a neutral bidentate ligand in the 1D coordination polymer [Fe(ßAlatrz)(3)](CF(3)SO(3))(2)·0.5H(2)O (1·0.5H(2)O). The temperature dependence of the high-spin molar fraction derived from (57)Fe Mossbauer spectroscopy recorded on cooling below room temperature reveals an exceptionally abrupt single step transition between high-spin and low-spin states with a hysteresis loop of width 4 K (T(c) (↑) = 232 K and T(c) (↓) = 228 K) in agreement with magnetic susceptibility measurements. The material presents striking reversible thermochromism from white, at room temperature, to pink on quench cooling to liquid nitrogen, and acts as an alert towards temperature variations. The phase transition is of first order, as determined by differential scanning calorimetry, with transition temperatures matching the ones determined by SQUID and Mössbauer spectroscopy. The freshly prepared sample of 1·0.5H(2)O, dried in air, was subjected to annealing at 390 K, and the obtained white compound [Fe(ßAlatrz)(3)](CF(3)SO(3))(2) (1) was found to exhibit a similar spin transition curve however much temperature was increased by (T(c) (↑) = 252 K and T(c) (↓) = 248 K). The removal of lattice water molecules from 1·0.5H(2)O is not accompanied by a change of the morphology and of the space group, and the chain character is preserved. However, an internal pressure effect stabilizing the low-spin state is evidenced.


Assuntos
Aminoácidos/química , Triazóis/química , Compostos Ferrosos/química , Estrutura Molecular , Polímeros/química , Temperatura , Termodinâmica
12.
BMJ Case Rep ; 14(6)2021 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-34088682

RESUMO

A 49-year-old woman presented to surgery outpatient clinic with the awareness of a right lower abdomen asymptomatic lump for one week. Contrast-enhanced CT of the abdomen demonstrated a 10×11×15 cm heterogeneous lesion anterior to the ileocecal junction with the possibility of leiomyosarcoma. The patient was prepared for laparotomy and intraoperative there was a large tumour arising from the medial wall of cecum. Right haemicolectomy was performed, and histopathology came as a desmoid tumour of the cecum. The patient had an uneventful postoperative course and is well on 1-year follow-up.


Assuntos
Neoplasias do Ceco , Fibromatose Agressiva , Leiomiossarcoma , Abdome , Neoplasias do Ceco/diagnóstico por imagem , Neoplasias do Ceco/cirurgia , Ceco/diagnóstico por imagem , Ceco/cirurgia , Feminino , Fibromatose Agressiva/diagnóstico por imagem , Fibromatose Agressiva/cirurgia , Humanos , Pessoa de Meia-Idade
13.
Pol Przegl Chir ; 93(4): 28-34, 2021 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-34515653

RESUMO

INTRODUCTION: Haemangiomas are the most common benign tumours of the liver. Most of them are asymptomatic. Giant hepatic haemangioma is defined as size greater than 5 cm in diameter. The surgical treatment for giant hepatic haemangioma is not very well defined and reported. Here we analysed the treatment outcome of giant hepatic haemangiomas and redefined the nomenclature according to the size and proposing an algorithm for management of all hepatic haemangiomas. MATERIAL AND METHODS: Retrospective analyses of 6 giant hepatic haemangioma more than 10 cm in size treated by a single surgeon were included. The clinical characteristics, diagnosis, managements and outcomes were recorded. Review of literature was done for definitions, management strategies and outcome of giant haemangiomas and an algorithm was proposed. RESULTS: Five patients were female and the mean age was 36.6 years (range 32 to 45). Pain abdomen was the most common symptoms (100%). Ultrasound abdomen was the initial diagnostic modality followed by contrast enhanced computed tomography. The mean size of haemangioma was 17.4cm (range 12cm to 32cm). Four patients had haemangioma in the left lobe and two had in the right lobe of liver. Formal hepatectomy was done in three patients and enucleation was done in three patients. The mean operating time was 3.66 hours (range 2.5 hours to 5 hours). The mean blood loss was 840ml (range 300ml to 1500ml). There was no surgical morbidity or mortality. On follow-up no haemangioma related complications are reported. CONCLUSIONS: Giant hepatic haemangioma is mostly symptomatic. Hepatectomy and enucleation can be done without significant morbidity and mortality. There is a need for redefining the nomenclature of giant hepatic haemangiomas according to the size.


Assuntos
Hemangioma , Neoplasias Hepáticas , Adulto , Feminino , Hemangioma/diagnóstico por imagem , Hemangioma/cirurgia , Hepatectomia , Humanos , Neoplasias Hepáticas/cirurgia , Pessoa de Meia-Idade , Estudos Retrospectivos
14.
Phlebology ; 36(5): 401-406, 2021 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-33251950

RESUMO

OBJECTIVE: External jugular vein (EJV) aneurysm is an extremely uncommon clinical condition. We have studied the clinical profile and need for surgery in this present seven case series of primary external jugular vein aneurysms. METHOD: Over the past three years, we have diagnosed and managed aneurysms of external jugular vein in seven patients, who presented with swelling in the posterior triangle of the neck. Venous duplex was obtained in all the patients, followed by computed tomography (CT) in three patients and one patient reported with magnetic resonance (MR) venography from another hospital. Three patients had symptoms ranging from mild intermittent discomfort to moderate pain underwent excision of aneurysm after ligation of both ends of EJV. Four patients had swelling on the lateral side of the neck due to EJV aneurysm, with no other associated symptoms. They were kept on six monthly follow-ups. RESULT: We operated three patients, as they were symptomatic, of which only two had thrombus in the aneurysmal sac. All three symptomatic patients had aneurysm of size >5 cm. Post-surgery and on subsequent follow-ups they were asymptomatic. The four asymptomatic patients kept on conservative management did not develop any thrombosis of aneurysm sac in follow up. CONCLUSION: Surgical excision is indicated for symptomatic patients with EJV aneurysm, preferably for size > 5 cm because of their higher association with thrombosis or symptoms. Asymptomatic patients can be managed non-operatively with regular surveillance by clinical examination and venous duplex or can be treated if patients insist due to cosmetic reasons.


Assuntos
Aneurisma , Veias Jugulares , Aneurisma/diagnóstico por imagem , Aneurisma/cirurgia , Humanos , Veias Jugulares/diagnóstico por imagem , Veias Jugulares/cirurgia , Pescoço , Flebografia , Veia Subclávia
15.
Cureus ; 13(8): e17372, 2021 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-34584782

RESUMO

Introduction Abdominal aortic aneurysms (AAA) are uncommon in young adults ≤55 years of age. There is a lack of literature on clinical characteristics, risk factors, and therapeutic outcomes so we present a case series of 11 patients of AAA aged ≤55 years. Methods We included single-center retrospective case series between 2013 to 2020. We reviewed 44 patients who were operated for AAA in a tertiary care center in India. We identified 13 patients who were ≤55 years; two patients with incomplete records were excluded. A patient information sheet was used to retrieve demographic data, clinical presentation, outcomes, and follow-up. Results Out of 11 patients, 10 were men. Nine patients (81.8%) had symptomatic AAA. The majority (45.4%) exhibited an infrarenal aneurysm and the median size of the aneurysm was 5.8 cm (IQR: 5.5-6.4 cm). Eight patients (72.7%) had a history of smoking. Hypertension was observed in six patients and one patient had associated coronary artery disease. Clamping time was > 45 minutes among three patients; all smokers. Blood loss was > 500 ml in five patients. The median length of hospital stay was 10 days (7-40); more among patients with metabolic equivalents (METS) score < 4, 14.5 (8-19) days. No grade III-IV complications and mortality were noted with a median follow-up of 15 months, with all patients living. Conclusion The aneurysm was symptomatic in the majority of participants. An association of smoking in increasing both the median clamping time and length of hospital stay was seen. No mortality and good disease-free follow-up suggested good outcomes.

16.
Inorg Chem ; 49(12): 5723-36, 2010 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-20507075

RESUMO

The thermally induced hysteretic spin transition (ST) that occurs in the polymeric chain compound [Fe(NH(2)trz)(3)](NO(3))(2) (1) above room temperature (T(c)(upward arrow) = 347 K, T(c)(downward arrow) = 314 K) has been tracked by (57)Fe Mössbauer spectroscopy, SQUID magnetometry, differential scanning calorimetry (DSC), and X-ray powder diffraction (XPRD) at variable temperatures. From the XRPD pattern indexation, an orthorhombic primitive cell was observed with the following cell parameters: a = 11.83(2) A, b = 9.72(1) A, c = 6.361(9) A at 298 K (low-spin state) and a = 14.37(2) A, b = 9.61(4) A, c = 6.76(4) A at 380 K (high-spin state). The enthalpy and entropy variation associated to the ST of 1, have been evaluated by DSC as DeltaH = 23(1) kJ mol(-1) and DeltaS = 69.6(1) J mol(-1) K(-1). These thermodynamic data were used within a two-level Ising like model for the statistical analysis of First Order Reversal Curve (FORC) diagram that was recorded for 1, in the cooling mode. Strong intramolecular cooperative effects are witnessed by the derived interaction parameter of J = 496 K. The crystal structure of [Cu(NH(2)trz)(3)](NO(3))(2).H(2)O (2) was obtained thanks to high quality single crystals prepared by slow evaporation after hydrothermal pretreatment. The catena poly[mu-tris(4-amino-1,2,4-triazole-N1,N2) copper(II)] dinitrate monohydrate (2) crystallizes in the monoclinic space group C2/c, with a = 16.635(6) A, b = 13.223(4) A, c = 7.805(3) A, beta = 102.56(3) degrees, Z = 4. Complex 2 is a 1D infinite chain containing triple N1,N2-1,2,4-triazole bridges with an intra-chain distance of Cu...Cu = 3.903(1) A. A dense H-bonding network with the nitrate counteranion involved in intra-chain and inter-chain interactions is observed. Such a supramolecular network could be at the origin of the unusually large hysteresis loop displayed by 1 (DeltaT approximately 33 K), as a result of an efficient propagation of elastic interactions through the network. This hypothesis is strengthened by the crystal structure of 2 and by the absence of crystallographic phase transition for 1 over the whole temperature range of investigation as shown by XRPD.

17.
Phys Chem Chem Phys ; 12(44): 14782-8, 2010 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-20931141

RESUMO

The vibrational properties of the trimeric iron complex [Fe(3)(4-(2'-hydroxy-ethyl)-1,2,4-triazole)(6)(H(2)O)(6)](CF(3)SO(3))(6) which serves as a model of the 1D iron coordination polymers based on 1,2,4-triazoles have been investigated by nuclear inelastic scattering of synchrotron radiation (NIS), as well as by Raman and infrared (IR) spectroscopy. The system reveals a soft spin crossover involving only the central iron atom with its FeN(6) core, while the terminal FeN(3)O(3) units show no spin transition. The NIS spectra of the central low-spin isomer exhibit a number of marker bands in the 350-450 cm(-1) region which have not been detected in the Raman spectra. The density functional theory (DFT) calculations allowed the assignment of these bands to Fe-N bending and stretching modes. A characteristic high-spin marker mode has been identified and discriminated from the iron-ligand modes of the terminal iron atoms. This characteristic central Fe-N mode has been observed experimentally at 245 cm(-1) and theoretically at 255 cm(-1). Contrary to mononuclear centrosymmetric Fe complexes, some of the symmetric vibrations of the trimeric complex involving iron movements are observed by NIS. Furthermore the DFT calculations displayed the importance of the coulombic repulsion between metal ions for the geometry and stability of a given spin isomer.

18.
Cureus ; 12(9): e10601, 2020 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-33123421

RESUMO

A 21-year-old unmarried and primigravida female indulged in criminal abortion at 18 weeks of gestation with the help of a village midwife. Instrumentation was done, and it led to uterine perforation with prolapse of 200 cm of small bowel through vagina. She was managed with resection of 160 cm of necrotic small bowel, repair of the uterine defect, and end jejunostomy, which was anastomosed with distal ileum three months later. This case highlights the risks of illegal abortion and the primitive societal mindset that forces unmarried women to resort to such means.

19.
Chemistry ; 15(17): 4327-42, 2009.
Artigo em Inglês | MEDLINE | ID: mdl-19291720

RESUMO

The relationships between the crystal structure and optical properties of switchable N-salicylideneanils have been revised and discussed on the basis of new experimental results and a computational approach. N-salicylidene-3-aminopyridine (L(3)) is a versatile thermo- and photochromic molecule. It also exhibits an infinitely slow thermal back relaxation (k = 9.9x10(-8) s(-1)) after photoswitching that is suitable for optical memories. Contrary to reports in the literature, N-salicylidene-4-aminopyridine (L(4)) is exclusively thermochromic. To explain these unexpected optical properties in the solid state, crystallography combined with UV-visible spectroscopic data was exploited. L(3) was also used as a ligand in new thermochromic coordination complexes [M(CH(3)OH)(2)(L(3))(2)(NCX)(2)], in which M(II) = Fe, Co, Ni, Cu or Mn and X = S or Se (1-6), which allowed the fine-tuning of the electron density in the photochromic moiety. The influence of the coordination through the nitrogen of the pyridine ring is also fully discussed.

20.
Sci Rep ; 9(1): 1872, 2019 02 12.
Artigo em Inglês | MEDLINE | ID: mdl-30755722

RESUMO

By limiting the heat spread during a fire hazard, intumescent coatings are important components of passive protection systems. They swell due to heat induced reactions of micro constituents and are transformed into carbonaceous porous-like media, known as intumescent chars. Their multiscale inner structures, key elements of performance, are costly to predict by recurrent and large scale fire testing while numerical simulations are challenging due to complex kinetics. Hence, we propose a novel approach using the fractal theory and the random nature of events to conceptualize the coating expansion. Experimental specimens were obtained from fire protective coatings exposed to bench scale hydrocarbon fire. Mass fractals were evidenced in the slices of 3D sample volumes reconstructed from X-ray microtomography. Consequently, geometrical building blocks were simulated by random walk, active walk, aggregation-like and site percolation: physical-chemical modes of action were inherent in the attribution of the randomness. It is a first demonstration to conceptualize different types of intumescent actions by a generalized approach with dimensionless parameters at multiscale, thus eliminating the simulation of complex kinetics to obtain a realistic morphology. Also, fractal results brought new evidence to former chemical analyses on fire test residues trying to explain the kinetics of expansion. Expected outcomes are to predict virtually the reaction of fire protective systems hence to speed-up the assessment of fire performance through computed properties of virtual volumes.

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