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1.
World J Urol ; 42(1): 249, 2024 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-38649544

RESUMO

PURPOSE: Prostate biopsy is central to the accurate histological diagnosis of prostate cancer. In current practice, the biopsy procedure can be performed using a transrectal or transperineal route with different technologies available for targeting of lesions within the prostate. Historically, the biopsy procedure was performed solely by urologists, but with the advent of image-guided techniques, the involvement of radiologists in prostate biopsy has become more common. Herein, we discuss the pros, cons and future considerations regarding their ongoing role. METHODS: A narrative review regarding the current evidence was completed. PubMed and Cochrane central register of controlled trials were search until January 2024. All study types were of consideration if published after 2000 and an English language translation was available. RESULTS: There are no published studies that directly compare outcomes of prostate biopsy when performed by a urologist or radiologist. In all published studies regarding the learning curve for prostate biopsy, the procedure was performed by urologists. These studies suggest that the learning curve for prostate biopsy is between 10 and 50 cases to reach proficiency in terms of prostate cancer detection and complications. It is recognised that many urologists are poorly able to accurately interpret multi parametric (mp)-MRI of the prostate. Collaboration between the specialities is of importance with urology offering the advantage of being involved in prior and future care of the patient while radiology has the advantage of being able to expertly interpret preprocedure MRI. CONCLUSION: There is no evidence to suggest that prostate biopsy should be solely performed by a specific specialty. The most important factor remains knowledge of the relevant anatomy and sufficient volume of cases to develop and maintain skills.


Assuntos
Previsões , Biópsia Guiada por Imagem , Próstata , Neoplasias da Próstata , Urologia , Masculino , Humanos , Biópsia Guiada por Imagem/métodos , Neoplasias da Próstata/patologia , Neoplasias da Próstata/diagnóstico por imagem , Próstata/patologia , Próstata/diagnóstico por imagem
2.
Clin Transplant ; 38(2): e15255, 2024 02.
Artigo em Inglês | MEDLINE | ID: mdl-38400672

RESUMO

INTRODUCTION: There is a lack of data regarding the peri-operative and long-term outcomes of kidney transplantation in cystic fibrosis (CF) patients. Herein, we report the peri-operative and long-term outcomes of kidney transplantation in CF patients. MATERIALS AND METHODS: All CF patients who received a kidney transplant at the national kidney transplant center between 1993 and 2022 were identified. Recipients of the contralateral donor kidney were selected as a control group. Primary outcomes included 1-, 5-, and 10- year death-censored graft survival and overall survival. Secondary outcomes included peri-operative morbidity, acute graft rejection, delayed graft function (DGF), and length of stay (LOS). RESULTS: Fourteen patients received a kidney transplant over the study period. Median age at transplantation was 35 (IQR 31, 40) years. The 1-, 5-, and 10-year death-censored graft survival was 92, 74, and 74% in the CF group compared to 100, 92, and 92% in the control group (p = .44). The 1-, 5-, and 10-year overall survival in the CF group was 85, 66, and 57% compared to 100, 92, and 82% in the control group (p = .036). There was no significant difference in peri-operative outcomes including LOS (10 vs. 11 days, p = .84), ICU admission (1 vs. 0 patients, p > .99), acute rejection episodes (2 vs. 1 patients, p > .99), and DGF (1 vs. 2 patients, p = .60). CONCLUSION: CF patients have good long-term graft survival, however, overall survival was worse compared to a matched cohort. These data provide important information for transplant surgeons when considering suitable donor allografts in this unique patient population.


Assuntos
Fibrose Cística , Transplante de Rim , Humanos , Transplante de Rim/efeitos adversos , Fibrose Cística/cirurgia , Rejeição de Enxerto , Sobrevivência de Enxerto , Doadores de Tecidos , Função Retardada do Enxerto/etiologia , Fatores de Risco , Estudos Retrospectivos
3.
Angew Chem Int Ed Engl ; : e202404532, 2024 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-38763910

RESUMO

The formation of phosphorus-rich alanes featuring butterfly-like geometries is achieved. The two-electron reduction products feature a unique P4 2- structure and can act as a source of P3-. The treatment of these phosphorus containing products with electrophiles under mild conditions results in the formation of different phosphines. This approach eliminates the need for high temperatures and/or high pressures, which are commonly required in industrial processes for the preparation of useful phosphines.The activation and further functionalization of white phosphorus (P4) by main group complexes has become an increasingly studied topic in recent times. Herein, we report the controlled formation of phosphorus-rich alanes featuring butterfly-like geometries from the selective reaction of P4 with dialumenes, ([L(IiPr)Al]2) (1: L=Tripp=2,4,6-iPr3C6H2; 2: L=tBu2MeSi; IiPr=[MeCN(iPr)]2C)). The two-electron-reduction product of P4 features a P4 2- structure and is shown to be able to act as a source of P3-. Treatments of different electrophiles (e.g., chlorotrimethylsilane (Me3SiCl), iodotrimethylsilane (Me3SiI), HCl, or acetyl chloride (CH3COCl)) with these alanes under mild conditions gave the corresponding phosphines (e.g., P(SiMe3)3, PH3, or P(COCH3)3).

4.
Angew Chem Int Ed Engl ; 63(6): e202315381, 2024 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-38059406

RESUMO

We show that countercations exert a remarkable influence on the ability of anionic cobaltate salts to catalyze challenging alkene hydrogenations. An evaluation of the catalytic properties of [Cat][Co(η4 -cod)2 ] (Cat=K (1), Na (2), Li (3), (Dep nacnac)Mg (4), and N(n Bu)4 (5); cod=1,5-cyclooctadiene, Dep nacnac={2,6-Et2 C6 H3 NC(CH3 )}2 CH)]) demonstrated that the lithium salt 3 and magnesium salt 4 drastically outperform the other catalysts. Complex 4 was the most active catalyst, which readily promotes the hydrogenation of highly congested alkenes under mild conditions. A plausible catalytic mechanism is proposed based on density functional theory (DFT) investigations. Furthermore, combined molecular dynamics (MD) simulation and DFT studies were used to examine the turnover-limiting migratory insertion step. The results of these studies suggest an active co-catalytic role of the counterion in the hydrogenation reaction through the coordination to cobalt hydride intermediates.

5.
Chemistry ; 29(2): e202202712, 2023 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-36195558

RESUMO

The reaction of the lithium aryl(silyl)amide Dipp(i Pr3 Si)NLi (Dipp=2,6-i Pr2 C6 H3 ) with one equivalent of SnCl2 in THF gave a novel stannylenoid Dipp(i Pr3 Si)NSnCl⋅LiCl(THF)2 . Heating the solution of amidostannylenoid in toluene to 80 °C resulted in dimeric amido(chloro)stannylene [Dipp(i Pr3 Si)NSnCl]2 , which can be converted to bis(amido)stannylene Sn[N(Dipp)(i Pr3 Si)]2 and amido(imino)stannylene Sn[N(Dipp)(i Pr3 Si)][IPrN] (IPrN=bis(2,6-diisopropylphenyl)imidazolin-2-imino). Treatment of bis(imino)stannylenoid [IPrN]2 Sn(Cl)Li with N2 O resulted in the dimeric complex [IPrNSn(Cl)OLi]2 . All compounds were characterized by NMR, elementary analysis, and X-ray structural determination.

6.
J Am Chem Soc ; 144(44): 20434-20441, 2022 Nov 09.
Artigo em Inglês | MEDLINE | ID: mdl-36315515

RESUMO

Phosphorus analogues of the ubiquitous cyclopentadienyl (Cp) are a rich and diverse family of compounds, which have found widespread use as ligands in organometallic complexes. By contrast, phospholes incorporating heavier group 14 elements (Si, Ge, Sn, and Pb) are hardly known. Here, we demonstrate the isolation of the first metal complexes featuring heavy cyclopentadienyl anions SnP42- and PbP42-. The complexes [(η4-tBu2C2P2)2Co2(µ,η5:η5-P4Tt)] [Tt = Sn (6), Pb (7)] are formed by reaction of white phosphorus (P4) with cyclooctadiene cobalt complexes [Ar'TtCo(η4-P2C2tBu2)(η4-COD)] [Tt = Sn (2), Pb (3), Ar' = C6H3-2,6{C6H3-2,6-iPr2}2, COD = cycloocta-1,5-diene] and Tt{Co(η4-P2C2tBu2)(COD)}2 [Tt = Sn (4), Pb (5)]. While the SnP42- complex 6 was isolated as a pure and stable compound, compound 7 eliminated Pb(0) below room temperature to afford [(η4-tBu2C2P2)2Co2(µ,η4:η4-P4) (8), which is a rare example of a tripledecker complex with a P42- middle deck. The electronic structures of 6-8 are analyzed using theoretical methods including an analysis of intrinsic bond orbitals and magnetic response theory. Thereby, the aromatic nature of P5- and SnP42- was confirmed, while for P42-, a specific type of symmetry-induced weak paramagnetism was found that is distinct from conventional antiaromatic species.

7.
Angew Chem Int Ed Engl ; 61(39): e202208930, 2022 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-35925668

RESUMO

The germanium iron carbonyl complex 3 was prepared by the reaction of dimeric chloro(imino)germylene [IPrNGeCl]2 (IPrN=bis(2,6-diisopropylphenyl)imidazolin-2-iminato) with one equivalent of Collman's reagent (Na2 Fe(CO)4 ) at room temperature. Similarly, the reaction of chloro(imino)stannylene [IPrNSnCl]2 with Na2 Fe(CO)4 (1 equiv) resulted in the Fe(CO)4 -bridged bis(stannylene) complex 4. We observed reversible formation of bis(tetrylene) and tetrylene-tetrylone character in complexes 3 vs. 5 and 4 vs. 6, which was supported by DFT calculations. Moreover, the Li/Sn/Fe trimetallic complex 12 has been isolated from the reaction of [IPrNSnCl]2 with cyclopentadienyl iron dicarbonyl anion. The computational analysis further rationalizes the reduction pathway from these chlorotetrylenes to the corresponding complexes.

8.
Chemistry ; 26(22): 4947-4951, 2020 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-32090377

RESUMO

This study details the isolation and characterisation of three novel silver(I) amides in solution and solid-state, [Ag(Cy3 P)(HMDS)] 2, [Ag(Cy3 P){N(TMS)(Dipp)}] 3 and [Ag(Cy3 P)2 (NPh2 )] 4. Their catalytic abilities have proved successful in hydroboration and hydrosilylation reactions with a full investigation performed with complex 2. Both protocols proceed under mild conditions, displaying exceptional functional-group tolerance and chemoselectivity, in excellent conversions at competitive reaction times. This work reveals the first catalytic hydroboration of aldehydes and ketones performed by a silver(I) catalyst.

9.
Clin Transplant ; 34(8): e13907, 2020 08.
Artigo em Inglês | MEDLINE | ID: mdl-32416641

RESUMO

INTRODUCTION: Few studies investigate significant perioperative predictors for long-term renal allograft survival after second kidney transplant (SKT). We compared long-term survival following SKT with primary kidney transplant and determined predictors of renal allograft failure after SKT. METHODS: Outcomes of all primary or second kidney transplant recipients at a national kidney transplant center between 1993 and 2017 were reviewed. The primary outcomes measurements were renal allograft survival for both first and second kidney transplants. Secondary outcome measurements were incidence of delayed graft function (DGF), incidence of acute rejection (AR), and predictors for renal allograft survival in SKT recipients. RESULTS: In total, there were 392 SKTs and 2748 primary kidney transplants performed between 1993 and 2017. The 1-, 5-, and 10-year death-censored graft survival for deceased-donor recipients was 95.3%, 88.7%, and 78.2% for primary kidney transplant and 94.9%, 87.1%, and 74.9% for SKT (P = .0288). Survival of primary renal allograft <6 years (HR 0.6, P = .017), AR episodes (HR 1.6, P = .031), DGF (HR 2.0, P = .005), and HLA-DR MM (HR 1.7, P = .018) was independent predictors of long-term renal allograft failure after SKT. CONCLUSION: These findings may provide important information on long-term survival outcomes after SKT and for identifying patients at risk for long-term renal allograft failure after SKT.


Assuntos
Transplante de Rim , Aloenxertos , Rejeição de Enxerto/etiologia , Sobrevivência de Enxerto , Humanos , Rim , Estudos Retrospectivos , Fatores de Risco
10.
Chemistry ; 25(11): 2773-2785, 2019 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-30370947

RESUMO

Three amide ligands of varying steric bulk and electronic properties were utilized to prepare a series of amido-germanium(II)/tin(II) halide compounds, (LEX)n , (L= -N{B(DipNCH)2 }(SiMe3 ), TBo L; -N{B(DipNCH)2 }(SiPh3 ), PhBo L; -N(Dip)(tBu), DBu L; Dip=C6 H3 iPr2 -2,6; E=Ge or Sn; X=Cl or Br; n=1 or 2). Reductions of these with a magnesium(I) dimer, {(Mes Nacnac)Mg}2 (Mes Nacnac=[(MesNCMe)2 CH]- , Mes=mesityl), afforded singly bonded amido-digermynes (TBo LGe-GeTBo L and PhBo LGe-GePhBo L), and an amido-distannyne (PhBo LSn-SnPhBo L), in addition to several low-valent, amido stabilized tetrel-tetrel bonded cluster compounds, (DBu LGe)4 , (DBu LSn)6 and Sn5 (TBo L)4 . The nature of the products resulting from these reactions was largely dependent on the steric bulk of the amide ligand employed. Cluster (DBu LGe)4 possessed an unusual folded butterfly structure, the bonding and electronic of which were examined using DFT calculations. Reactions of the amido-germanium(I) compounds with H2 were explored, and gave rise to the amido-digermene, TBo L(H)Ge=Ge(H)TBo L and the cyclotetragermane, {DBu L(H)Ge}4 . Reactions of (DBu LGe)4 with a series of unsaturated small molecule substrates yielded DBu LGeOGeDBu L, DBu LGe(µ-C2 H4 )2 GeDBu L and DBu LGe(µ-1,4-C6 H8 )(µ-1,2-C6 H8 )GeDBu L. The latter results imply that (DBu LGe)4 can act as a masked source of the digermyne DBu LGeGeDBu L in these reactions. All further reactivity studies indicated that the germanium(I) compounds exhibit a "transition-metal-like" behavior, which is closely related to that previously described for bulky digermynes and related compounds.

11.
Pediatr Blood Cancer ; 66(2): e27515, 2019 02.
Artigo em Inglês | MEDLINE | ID: mdl-30362242

RESUMO

PURPOSE: Obesity correlates with adverse events (AEs) in children with acute myelogenous leukemia and during maintenance therapy for acute lymphoblastic leukemia (ALL). Less is known about AEs in obese ALL patients during pre-maintenance chemotherapy. We evaluated the relationship between obesity (body mass index (BMI) ≥ 95th percentile) and AEs during pre-maintenance chemotherapy in pediatric patients with ALL. METHODS: One hundred fifty-five pediatric ALL patients diagnosed at a single institution between 2006 and 2012 were retrospectively evaluated for infections, treatment-requiring hypertension, insulin-requiring hyperglycemia, pancreatitis, pediatric intensive care unit admissions, sepsis, febrile neutropenia (FN) admissions, thrombosis, hepatotoxicity, and nephrotoxicity. Univariate and multivariable analyses compared proportions of obese versus nonobese patients experiencing AEs. RESULTS: AEs occurring significantly more frequently in obese patients by univariate analysis included treatment-requiring hypertension (17.5% vs 6.1%; OR, 3.27; 95% CI, 1.1-10.0, P = 0.0497) and insulin-requiring hyperglycemia (25.0% vs 11.3%; OR, 2.62; 95% CI, 1.04-6.56, P = 0.04). Obese patients had greater incidence rates for recurrent admission-requiring infections (incidence rate ratio (IRR) 1.64; 95% CI, 1.08-2.48, P = 0.02) and recurrent FN admissions (IRR, 1.53; 95% CI, 1.10-2.12, P = 0.01). Accounting for combined age and NCI risk status, obesity was a risk factor for treatment-requiring hypertension (OR, 3.90; 95% CI, 1.19-12.76, P = 0.02), insulin-requiring hyperglycemia (OR, 3.92; 95% CI, 1.39-11.05, P = 0.01), and FN admission (OR, 2.92; 95% CI, 1.27-6.73, P = 0.01). CONCLUSIONS: During pre-maintenance chemotherapy for ALL, obesity is a risk factor for the development of hypertension, hyperglycemia, and FN admissions. This research provides implications for augmented preventive and supportive care guidelines in obese ALL patients.


Assuntos
Antineoplásicos/efeitos adversos , Obesidade/complicações , Leucemia-Linfoma Linfoblástico de Células Precursoras/complicações , Leucemia-Linfoma Linfoblástico de Células Precursoras/tratamento farmacológico , Adolescente , Criança , Pré-Escolar , Feminino , Humanos , Masculino , Estudos Retrospectivos , Fatores de Risco , Adulto Jovem
12.
Chem Asian J ; 19(2): e202300941, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-37996985

RESUMO

A heteroleptic amino(imino)stannylene (TMS2 N)(It BuN)Sn: (TMS=trimethylsilyl, It Bu=C[(N-t Bu)CH]2 ) as well as two homoleptic NHI-stabilized tetrylenes, (It BuN)2 E: (NHI=N-heterocyclic imine, E=Ge, Sn) are presented. VT-NMR investigations of (It BuN)2 Sn: (2) reveal an equilibrium between the monomeric stannylene at room temperature and the dimeric form at -80 °C as well as in the solid state. Upon reaction of the homoleptic tetrylenes with CO2 , both compounds insert two equivalents of CO2 , however differing bonding modes can be observed. (It BuN)2 Sn: (2) inserts one equivalent of CO2 into each Sn-N bond, giving carbamato groups coordinated κ2 O,O' to the metal center. With (It BuN)2 Ge: (3), the Ge-N bonds stay intact upon activation, being bridged by one molecule of CO2 respectively, forming 4-membered rings. Furthermore, the reactivity of 2 towards N2 O was investigated, resulting in partial oxidation to form stannylene dimer [((It BuN)3 SnO)(It BuN)Sn:]2 (6).

13.
Ir J Med Sci ; 2024 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-38430412

RESUMO

INTRODUCTION: Clinicians frequently rely on patients to accurately tell them what prescription medications and doses they are taking in outpatient visits. This information is essential to monitor the efficacy of a medication and to determine any adverse interactions. This study aimed to assess urologist and urology trainee's visual recognition of common urology medications. METHODS: An online survey was distributed to urologists and urology trainees in Ireland. Images of 11 commonly prescribed urological medications were presented with free text options for answering. Information was gathered on respondent's role and experience. Data was analysed using STATA version 17. RESULTS: The survey had a 90% response rate from 50 distributions. Respondents' roles were consultant (31.1%), specialist registrar (33.3%), registrar (22.2%), senior house officer (11.1%) and intern (2.2%). Forty six percent had more than six years urology experience. Average rate of correct responses was 39.4% ± 23.9. The most accurate group were consultants (46.1% ± 22.1), followed by specialist registrars (41.2% ± 24.9), registrars (39.1% ± 26.8), senior house officers (21.8% ± 10.4) and interns (9.1% ± 0). The most and least recognised medications were sildenafil (Viagra©) (84.4%) and fesoterodine (Toviaz©) (11.1%), respectively. Just 28.9% of respondents had previously handled any of the medications listed. CONCLUSION: Patients often do not reliably know their own medications other than to describe them or show an unpackaged tablet. Prescribing safety is paramount to ensuring patient safety and reducing the risk of adverse drug reactions. This study shows that even experienced clinicians do not recognise the medications they regularly prescribe, and decisions should not be made without accurate medication reconciliation.

14.
Urol Oncol ; 41(7): 329.e11-329.e15, 2023 07.
Artigo em Inglês | MEDLINE | ID: mdl-37225633

RESUMO

INTRODUCTION: Penile cancer (PC) in men under 45 is very rare with an incidence of 0.1 to 0.8/100,000. There is little published data on disease characteristics and outcomes of PC in younger men. Herein, we evaluate the disease characteristics and outcomes of penile cancer in younger men compared to an older cohort. METHODS: This study included all men diagnosed with PC at our institution from 2016 to 2021. Primary outcomes included overall survival, cancer-specific survival, and disease-free survival. Secondary outcomes included disease characteristics and surgical management. Men aged ≤45 years (Group A) were compared with men aged >45 years (Group B) at diagnosis. RESULTS: There were 90 patients treated for invasive PC over the study period. The median age at diagnosis was 64 (26-88). The mean length of follow-up was 27 (±18) months. There were 12 (13%) in Group A, and 78 (87%) patients in Group B. Group A had a worse cancer-specific survival compared to Group B (39 months vs. not reached, HR 0.1 (95%CI 0.02-0.85, P = 0.03). There was no significant difference in overall or disease-free survival between both groups. More men in Group A had lymph node metastases at the time of diagnosis (58% vs. 19%, P < 0.001). There was no significant difference in histopathological features including tumor subtype, grade, T stage, p53 status or presence of lymphovascular or perineural invasion. CONCLUSION: In our study, younger men were more likely to have nodal involvement at time of diagnosis and had a worse cancer-specific survival.


Assuntos
Carcinoma de Células Escamosas , Neoplasias Penianas , Masculino , Humanos , Excisão de Linfonodo , Neoplasias Penianas/cirurgia , Carcinoma de Células Escamosas/patologia , Prognóstico , Metástase Linfática , Estudos Retrospectivos
15.
Int Immunol ; 23(10): 647-59, 2011 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-21937457

RESUMO

Increasing the pool of cells at early T-cell developmental stages enhances thymopoiesis and is especially beneficial when T-cell production is compromised by radiation or aging. Within the immature double-negative (DN; CD4(-)CD8(-)) thymocyte subpopulation, the DN1 subset contains the most primitive cells including the rare early T-cell progenitors (ETPs). In the present study, a human MCL1 transgene, under the control of its endogenous promoter, resulted in enlargement of an undistorted thymus in C57/BL6 mice. Enlargement occurred in females but not males, being seen at 1 month of age and maintained during progression into adulthood as the thymus underwent involution. The small DN1 subset was expanded disproportionally (ETPs increasing from ∼0.016 to 0.03% of thymocytes), while more mature thymocytes were increased proportionally (1.5-fold) along with the stroma. DN1 cells from transgenic females exhibited increased viability with maintained proliferation, and their survival in primary culture was extended. Exposure of transgenic females to γ-irradiation also revealed an expanded pool of radioresistant DN1 cells exhibiting increased viability. While the viability of DN1 cells from transgenic males was equivalent to that of their non-transgenic counterparts directly after harvest, it was enhanced in culture-suggesting that the effect of the transgene was suppressed in the in vivo environment of the male. Viability was increased in ETPs from transgenic females, but unchanged in more mature thymocytes, indicating that primitive cells were affected selectively. The MCL1 transgene thus increases the viability and pool size of primitive ETP/DN1 cells, promoting thymopoiesis and radioresistance in peripubescent females and into adulthood.


Assuntos
Proteínas Proto-Oncogênicas c-bcl-2/metabolismo , Timócitos/citologia , Timo/crescimento & desenvolvimento , Animais , Sobrevivência Celular , Feminino , Humanos , Masculino , Camundongos , Camundongos Congênicos , Camundongos Endogâmicos C57BL , Camundongos Transgênicos , Proteína de Sequência 1 de Leucemia de Células Mieloides , Proteínas Proto-Oncogênicas c-bcl-2/deficiência , Linfócitos T/citologia , Linfócitos T/imunologia , Timócitos/imunologia , Timo/citologia , Timo/imunologia , Irradiação Corporal Total
16.
Dalton Trans ; 50(39): 13985-13992, 2021 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-34542141

RESUMO

Magnesium cobaltates (Arnacnac)MgCo(COD)2 (1-3) were synthesised by reacting (Arnacnac)MgI(OEt2) with K[Co(η4-COD)2] (COD = 1,5-cyclooctadiene) [Arnacnac = CH(ArNCMe)2; Ar = 2,4,6-Me3-C6H2 (Mes), 2,6-Et2-C6H3 (Dep), 2,6-iPr2-C6H3Mes (Dipp)]. Compounds 1-3 form contact ion-pairs in toluene, while solvent separated ion-pairs are formed in THF. The effect of ion-pairing on the reactivity is illustrated by reaction of 2 with tert-butylphosphaalkyne, which affords distinct 1,3-diphosphacyclobutadiene complexes. The heteroleptic sandwich complex [(Depnacnac)MgCo(P2C2tBu2)]2 (4) is selectively formed in toluene, while the homoleptic bis(1,3-diphosphacyclobutadiene) complex [(Depnacnac)Mg(THF)3][Co(P2C2tBu2)2] (5) is obtained in THF. Complex 4 is a precursor to further unusual phosphaorganometallic compounds. Substitution of the labile COD ligand in 4 by white phosphorus (P4) enabled the synthesis of the phosphorus-rich sandwich compound [(Depnacnac)MgCoP4(P2C2tBu2)]2 (6). The heterobimetallic complex (Cp*NiP2C2tBu2)Co(COD) (7) was isolated after treatment of 4 with Cp*Ni(acac) (Cp* = C5Me5, acac = acetylacetonate).

17.
Organometallics ; 40(8): 1042-1052, 2021 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-34054182

RESUMO

The divalent iron complexes trans-[FeBr2(BINC)2], [Cp*FeCl(BINC)] (Cp* = Me5C5), and [FeBr2(CNAr3NC)2] with the chelating bis(isonitrile) ligands BINC (bis(2-isocyanophenyl)phenylphosphonate) and CNAr3NC (2,2″-diisocyano-3,5,3″,5"tetramethyl-1,1':3',1″-terphenyl) have been prepared and characterized. Their subsequent reduction yields the di- and trinuclear compounds [Fe3(BINC)6], [Cp*Fe(BINC)]2, [Fe(CNAr3NC)2]2, and [K(Et2O)]2[Fe(CNAr3NC)2]2. The molecular structures of all new species were determined by X-ray crystallography and compared to those of related iron carbonyl complexes, demonstrating that the bidentate isonitrile ligands are capable surrogates for two CO ligands with only minimal distortion of the tetrahedral or octahedral geometry of the parent complexes. The complexes were further characterized by NMR and IR spectroscopy, and the electrochemical properties of selected compounds were analyzed by UV-vis-NIR spectroelectrochemistry.

18.
J Exp Med ; 198(1): 79-89, 2003 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-12835478

RESUMO

Signal transducer and activator of transcription (STAT) proteins are latent transcription factors that mediate a wide range of actions induced by cytokines, interferons, and growth factors. We now report the development of thymic T cell lymphoblastic lymphomas in transgenic mice in which Stat5a or Stat5b is overexpressed within the lymphoid compartment. The rate of lymphoma induction was markedly enhanced by immunization or by the introduction of TCR transgenes. Remarkably, the Stat5 transgene potently induced development of CD8+ T cells, even in mice expressing a class II-restricted TCR transgene, with resulting CD8+ T cell lymphomas. These data demonstrate the oncogenic potential of dysregulated expression of a STAT protein that is not constitutively activated, and that TCR stimulation can contribute to this process.


Assuntos
Proteínas de Ligação a DNA/fisiologia , Proteínas do Leite , Leucemia-Linfoma Linfoblástico de Células Precursoras/etiologia , Receptores de Antígenos de Linfócitos T/fisiologia , Transativadores/fisiologia , Animais , Genes Codificadores da Cadeia beta de Receptores de Linfócitos T , Ativação Linfocitária , Camundongos , Camundongos Endogâmicos BALB C , Camundongos Endogâmicos C57BL , Camundongos Transgênicos , Análise de Sequência com Séries de Oligonucleotídeos , Fator de Transcrição STAT3 , Fator de Transcrição STAT5
19.
Chem Commun (Camb) ; 56(90): 14071-14074, 2020 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-33107502

RESUMO

[LSi(η2-P4)] (L = CH[C(Me)N(Dipp)][C(CH2)N(Dipp)], Dipp = 2,6-diisopropylphenyl) forms well-defined 1 : 1 and 2 : 1 complexes with N-heterocyclic carbene nickel fragments. The cluster compound [(IDipp)Ni2P8(SiL)2] (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) is selectively formed by thermolysis of the complex [(IDipp)Ni(µ-η2:2-P4)SiL].

20.
Ir J Med Sci ; 189(1): 289-293, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31418152

RESUMO

INTRODUCTION: Ureteric stents are frequently placed following endo-urological procedures. These stents cause significant morbidity for patients. Standard ureteric stents are removed by flexible cystoscopy. This procedure can be unpleasant for patients and requires additional resources. A newly designed magnetic stent allows removal in an outpatient setting. The aim of our study is to compare the magnetic stent and standard ureteric stents with regard to morbidity, pain on stent removal and cost-effectiveness. METHODS: This study was carried out across two sites between September 2016 and July 2017. In site A, a magnetic stent (Urotech, Black-Star®) is removed by magnetic retrieval device. Fifty consecutive patients completed the validated Ureteric Stent Symptom Questionnaire (USSQ) and visual analogue scale (VAS) at the time of stent removal. On site B, a soft polyurethane stent (Cook Universa) was removed by flexible cystoscopy. Fifty patients were identified retrospectively and completed questionnaires by post. Cost analysis was also performed. RESULTS: One hundred questionnaires were included for analysis. No significant difference in stent morbidity as assessed by the USSQ was shown between both groups. Median duration of stenting was significantly shorter in the magnetic stent group (5.5 versus 21.5 days, p < 0.001). Mean pain on stent removal was significantly less with magnetic retrieval (2.9 versus 3.9, p < 0.05). Complication rates were similar in both groups. Cost analysis showed a cost saving of €203 per patient with the magnetic stent group. CONCLUSION: Magnetic stents cause similar morbidity for patients compared with standard stents removed by flexible cystoscopy; they are associated with less pain at removal and are cost saving.


Assuntos
Remoção de Dispositivo/métodos , Fenômenos Magnéticos , Stents/efeitos adversos , Ureter/cirurgia , Feminino , Humanos , Masculino , Estudos Retrospectivos
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