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A solvothermal method to prepare PtNi alloys that have differing morphologies is described. By adjusting the feed ratio of Pt and Ni precursors in this process, PtNi alloys with different compositions (Pt : Ni atomic ratio from 1 : 3 to 3 : 1) and morphologies (evolution from nanobranches to nanoparticles) are generated. The prepared Pt48 Ni52 alloy, which has a composite morphology comprised of nanobranches and nanoparticles, exhibits superior activity and durability towards the hydrogen evolution reaction (HER) in seawater compared to those of commercial Pt/C catalyst and other PtNi alloys that have different compositions and morphologies. The excellent seawater HER performance of Pt48 Ni52 is ascribed to its nanobranch/nanoparticle morphology that optimally facilitates electron accumulation on Pt, which enhances resistance to chloride corrosion in seawater.
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Aleaciones , Cloruros , Corrosión , Halógenos , Hidrógeno , Agua de MarRESUMEN
Glycine max is easily infected with root rot in continuous cropping systems, which can severely affect crop yield. Arbuscular mycorrhizal fungi (AMF) can reduce the incidence of root rot and increase plant height and biomass indices. However, the molecular changes that occur during soybean symbiosis with AMF remain largely unknown. To better understand the molecular mechanism underlying soybean symbiosis with AMF, we performed transcriptomic and proteomic analyses to explore the changes in protein expression during a high-incidence period (79 days) in asymbiotic and symbiotic plants and to identify the key proteins that regulate the mechanism of soybean symbiosis with AMF. A total of 10â¯104 genes were identified in the CK-vs-F comparison, and 11â¯562 genes were significantly differentially expressed in the AF group compared with the F group. A total of 9488 proteins were identified, with 256 differentially expressed proteins (DEPs) in the CK-vs-F comparison and 651 DEPs in the F-vs-AF comparison. Key pathways and DEPs were found to be involved in processes associated with "phenylalanine metabolism", "plant hormone signal transduction", "plant-pathogen interaction", and "metabolic pathways". The expression of phenylalanine ammonia-lyase (PAL), calcium-dependent protein kinase (CPK), and other defense-related proteins was upregulated by Funneliformis mosseae, indicating that inoculation promotes the development of soybean and increases disease resistance. Our results suggest that symbiosis promotes the growth and development of soybean and increases disease resistance. This study provides new insight into the molecular basis of the mechanism by which AMF affect plant disease resistance.
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Glycine max , Micorrizas , Hongos , Raíces de Plantas/genética , Proteómica , Glycine max/genética , Simbiosis , TranscriptomaRESUMEN
The nutritional value of mutton chop rolls is gradually recognized by people, but it is easy to cause microbial contamination during storage, leading to spoilage and shortening of storage time. The bacterial diversity of mutton chop rolls in different cold preservation time was analyzed to explore the main pathogens of spoilage of mutton chop rolls. At the same time, the oxidative state of myoglobin and the change of mitochondrial Metmyoglobin (MMb) Reduction Ability (MRA) in different cold preservation were studied. It lays a foundation for further study on the mechanism of meat color stabilization of mutton chop rolls during cold preservation. A total of 10,123,180 effective Tags were obtained from three samples with different cold preservation time by high throughput sequencing. The relative abundance of Pseudomonas was the highest in the samples refrigerated for 8 days, Acinetobacter, Brochothrix and Lactobacillales showed the highest relative abundance in the samples refrigerated for 4 days, which were closely related to the deterioration of mutton chop rolls and color deterioration. With the increase of cold preservation time, Oxymyoglobin (OMb) content decreased and Metmyoglobin (MMb) content increased. MRA was negatively correlated with MMb. The content of NADH was extremely significant difference with OMb and MMb. At the same time, the content of NADH was a significant difference with MRA. This study provides theoretical basis for prolonging the shelf life, maintaining meat color stability, improving the quality of mutton chop rolls. And it also plays a certain role in promoting the production and consumption of chilled meat.
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Bacterias/clasificación , Frío , Microbiología de Alimentos , Microbiota , Mioglobina/metabolismo , Carne Roja/microbiología , Animales , Bacterias/aislamiento & purificación , Color , Almacenamiento de Alimentos , Mioglobina/análisis , Oxidación-Reducción , OvinosRESUMEN
Glycoprotein nonmetastatic melanoma protein B is a type 1 transmembrane protein that has been recently found to play a role in cancer cell proliferation, angiogenesis, and invasion. Due to its potential responsibility in cancer aggressiveness, the main objective of this work was to investigate its expression in bladder cancer and the biological functions in bladder cancer cells. Using immunohistochemistry, western blot, and reverse transcription polymerase chain reaction, we analyzed the expression of glycoprotein nonmetastatic melanoma protein B in bladder cancer tissues and bladder cancer cell lines. The effects of glycoprotein nonmetastatic melanoma protein B on proliferation, migration, and invasion were tested after knocking down the glycoprotein nonmetastatic melanoma protein B in bladder cancer cells with small interfering RNAs by CCK-8, Transwell, and Matrigel assays. Our results showed that glycoprotein nonmetastatic melanoma protein B protein was highly expressed in the bladder cancer tissues and cell lines. Downregulating glycoprotein nonmetastatic melanoma protein B could suppress the proliferation, migration, and invasion in bladder cancer cells. Glycoprotein nonmetastatic melanoma protein B expression was related to the poor differentiation and recurrence by immunohistochemistry analysis. The survival analysis also showed that glycoprotein nonmetastatic melanoma protein B was related to the patient prognosis. In conclusion, Glycoprotein nonmetastatic melanoma protein B protein was highly expressed in the bladder cancer, which was related to the poor prognosis in bladder cancer patients. Glycoprotein nonmetastatic melanoma protein B promoted the proliferation, migration, and invasion in bladder cancer cells.
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Proliferación Celular/genética , Glicoproteínas de Membrana/genética , Recurrencia Local de Neoplasia/genética , Neoplasias de la Vejiga Urinaria/genética , Adulto , Anciano , Apoptosis/genética , Línea Celular Tumoral , Supervivencia sin Enfermedad , Femenino , Regulación Neoplásica de la Expresión Génica , Técnicas de Silenciamiento del Gen , Humanos , Estimación de Kaplan-Meier , Masculino , Glicoproteínas de Membrana/antagonistas & inhibidores , Persona de Mediana Edad , Invasividad Neoplásica/genética , Recurrencia Local de Neoplasia/patología , Pronóstico , Neoplasias de la Vejiga Urinaria/patologíaRESUMEN
BACKGROUND: The aim of this study was to elucidate recurrent pregnancy loss (RPL)-associated psychosocial effects and sexual functions of Chinese men whose partners experience a history of RPL. METHODS: Questionnaire data from a total of 236 men whose partners experience RPL(RPL group) and another 236 non-RPL male volunteers(control group) were analyzed. The self-administered questionnaires included anxiety and depression measures (SAS & SDS), the Index of Sexual Satisfaction (ISS) and the International Index of Erectile Function (IIEF-5) for evaluating psychological burden, sexual satisfaction and erectile function, respectively. RESULTS: The mean age of the RPL group and control group was 29.8 ± 8.6 and 28.2 ± 7.3, respectively. The incidence of erectile dysfunction was significantly higher in the RPL group than in the control group (19.07 % vs. 7.63 %, P < 0.001). Anxiety and depression were also more prevalent in RPL group than in the control group (anxiety: 36.90 % vs. 19.08 %, P < 0.001; depression: 26.30 % vs. 7.63 %, P < 0.001). Furthermore, after adjusting for age in the RPL group, negative relationships were observed between the IIEF-5 score and anxiety and depression (P < 0.001), and a positive correlation was found between the ISS and anxiety and depression (P < 0.001). In addition, history of RPL, anxiety and depressive symptoms were significantly associated with a higher risk of ED. CONCLUSIONS: Psychological functioning, sexual satisfaction and erectile function are impaired in infertile men with RPL partners. These men should be targeted for psychological consultation.
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Aborto Habitual/psicología , Disfunción Eréctil/epidemiología , Hombres/psicología , Orgasmo , Adulto , Ansiedad/epidemiología , China/epidemiología , Estudios Transversales , Depresión/epidemiología , Humanos , MasculinoRESUMEN
Nickel-catalyzed cross-coupling of aryltrimethylammonium triflates and amines was carried out under mild conditions. The reaction has a broad scope of substrates and can be performed by a one-pot procedure from an aryldimethylamine.
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Background: Accumulated evidences indicate that dysbiosis of the urinary microbiota is associated with kidney stone formation. In the present study, we aimed to investigate the urinary microbiota composition and functionality of patients with calcium oxalate stones and compare it with those of healthy individuals. Method: We collected bladder urine samples from 68 adult patients with calcium oxalate stones and 54 age-matched healthy controls by transurethral catheterization. 16S rRNA gene and shotgun sequencing were utilized to characterize the urinary microbiota and functionality associated with calcium oxalate stones. Results: After further exclusion, a total of 100 subjects was finally included and analyzed. The diversity of the urinary microbiota in calcium oxalate stone patients was not significantly different from that of healthy controls. However, the urinary microbiota structure of calcium oxalate stone formers significantly differed from that of healthy controls (PERMANOVA, r = 0.026, P = 0.019). Differential representation of bacteria (e.g., Bifidobacterium) and several enriched functional pathways (e.g., threonine biosynthesis) were identified in the urine of calcium oxalate stone patients. Conclusion: Our results showed significantly different urinary microbiota structure and several enriched functional pathways in calcium oxalate stone patients, which provide new insight into the pathogenesis of calcium oxalate stones.
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Bacterias , Oxalato de Calcio , Microbiota , ARN Ribosómico 16S , Humanos , Oxalato de Calcio/orina , Oxalato de Calcio/metabolismo , Masculino , Femenino , ARN Ribosómico 16S/genética , Persona de Mediana Edad , Adulto , Bacterias/clasificación , Bacterias/genética , Bacterias/metabolismo , Bacterias/aislamiento & purificación , Cálculos Renales/orina , Cálculos Renales/microbiología , Orina/microbiología , Orina/química , Disbiosis/microbiología , Estudios de Casos y Controles , AncianoRESUMEN
d-π overlap, which represents overlap between metal-d and graphene-π orbitals to facilitate electron transfer, has rarely been reported. Ni/PtNi-G2 exhibits exceptional performance in seawater hydrogen evolution due to the electron-rich surface on Pt resulting from enhanced d-π overlap and subsequent electron transfer from graphene and Ni to Pt.
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The cross-coupling reaction of aryltrimethylammonium iodides with aryl- or heteroarylzinc chlorides catalyzed by amido pincer nickel complexes was performed. The reaction requires low catalyst loading and displays broad substrate scope.
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The aim of the present study was to assess the treatment outcomes in a cohort of adult patients with intratesticular rhabdomyosarcoma. Between 1999 and 2008, 296 patients underwent radical orchiectomy for intrascrotal mass. A retrospective chart review was carried out for adult patients diagnosed with intratesticular rhabdomyosarcoma. Overall, six patients (mean age 21 years, range 17-23) were included: five had embryonic rhabdomyosarcoma and one had pleomorphic rhabdomyosarcoma. Four patients underwent retroperitoneal lymph node dissection and five patients had postoperative chemotherapy. The mean length of follow up was 28 months (range 12-51 months). One patient was lost to follow up after 26 months, five cases remained alive at the end of the study. Surgical resection with chemotherapy was an effective way to achieve favorable outcomes and long-term survival in adult patients with metastases from intratesticular rhabdomyosarcoma.
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Rabdomiosarcoma/cirugía , Neoplasias Testiculares/cirugía , Adolescente , Protocolos de Quimioterapia Combinada Antineoplásica , Quimioterapia Adyuvante , Ciclofosfamida , Dactinomicina , Humanos , Masculino , Orquiectomía , Estudios Retrospectivos , Rabdomiosarcoma/tratamiento farmacológico , Neoplasias Testiculares/tratamiento farmacológico , Vincristina , Adulto JovenRESUMEN
We report an alternating-reduction approach by galvanic replacement and co-reduction to enable incorporation of Pd into Pt shell, and the obtained PtPd hollow nanocubes with an enhanced alloy effect and highly active {100} facets show high catalytic activity and superior durability in the methanol oxidation reaction.
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OBJECTIVE: To analyze the incidence of benign lesions in Chinese patients undergoing nephrectomies for renal masses identified as localized renal cell carcinoma (RCC) in preoperative imaging. METHODS: Between 1999 and 2007, 303 patients (112 female, 191 male) with presumed localized RCC underwent nephrectomy (234 radical nephrectomies and 69 partial nephrectomies). Preoperative computed tomography images and pathological findings were reviewed and analyzed. RESULTS: Pathological examinations revealed 31 (10.2%) benign lesions in the 303 patients. Among these 31 benign lesions, 15 (5.0%) were angiomyolipomas (AML) and only four (1.3%) were oncocytomas. Significantly, 20 (17.9%) of the 112 female patients had benign lesions compared with 11 (5.8%; P = 0.001) male patients. Benign renal lesions were found in five (25.0%) of the 20 patients with renal masses smaller than 2 cm, 13 (13.0%) of the 100 patients with renal masses 2-4 cm in size and 13 (7.1%) of the 183 patients with renal masses larger than 4 cm. CONCLUSIONS: Patients in the present study population show a low incidence of benign renal lesions, approximately half of them being AML. Female patients and patients with renal masses smaller than 4 cm are more likely to have benign renal lesions.
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Carcinoma de Células Renales/epidemiología , Carcinoma de Células Renales/patología , Neoplasias Renales/epidemiología , Neoplasias Renales/patología , Adolescente , Adulto , Anciano , Anciano de 80 o más Años , Carcinoma de Células Renales/cirugía , Niño , Preescolar , China , Femenino , Humanos , Incidencia , Neoplasias Renales/cirugía , Masculino , Persona de Mediana Edad , Nefrectomía , Estudios Retrospectivos , Adulto JovenRESUMEN
BACKGROUND AND OBJECTIVE: Patients with clinical stage I seminoma accounts for 70%-80% of patients with this disease. This study was to analyze the relationship between different therapeutic methods and the prognosis of this disease. METHODS: The data of all patients with clinical Stage I seminoma treated by multi-disciplinary approach from 1999 to 2008 in Sun Yat-sen University Cancer Center were analyzed. The patients were divided into 3 groups based on the treatment they received after orchiectomy: 30 patients treated with chemotherapy, 8 with radiotherapy, and 20 under surveillance. The prognosis of different treatment groups was evaluated. RESULTS: Among the 58 patients with stage I seminoma, 57 were followed up successfully. The median follow-up time was 50 months (range, 8-115 months). No relapse or metastasis was seen in the chemotherapy group. One patient relapsed in the radiotherapy group. Four patients had metastasis of retroperitoneal lymph node in the surveillance group. The disease-free survival was higher in the chemotherapy group than that in the surveillance group (P=0.005). There was no significant difference in the relapse-free survival between the surveillance group and the radiotherapy group (P=0.364). CONCLUSIONS: Chemotherapy is a safe and effective treatment for patients with Stage-1 seminoma after radical orchidectomy.
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Protocolos de Quimioterapia Combinada Antineoplásica/uso terapéutico , Orquiectomía , Seminoma , Neoplasias Testiculares , Adolescente , Adulto , Bleomicina/uso terapéutico , Cisplatino/uso terapéutico , Terapia Combinada , Supervivencia sin Enfermedad , Etopósido/uso terapéutico , Estudios de Seguimiento , Humanos , Metástasis Linfática , Masculino , Persona de Mediana Edad , Recurrencia Local de Neoplasia , Estadificación de Neoplasias , Orquiectomía/métodos , Estudios Retrospectivos , Seminoma/tratamiento farmacológico , Seminoma/patología , Seminoma/radioterapia , Seminoma/cirugía , Neoplasias Testiculares/tratamiento farmacológico , Neoplasias Testiculares/patología , Neoplasias Testiculares/radioterapia , Neoplasias Testiculares/cirugía , Resultado del Tratamiento , Adulto JovenRESUMEN
In this paper the poly-dopamine (PDA)/hyaluronic acid (HA) coatings with different HA molecular weight (MW, 4 × 103, 1 × 105, 5 × 105 and 1 × 106 Da) were prepared onto the NaOH passivated Mg-Zn-Y-Nd alloy aiming at potential application of cardiovascular implants. The characterization of weight loss, polarization curves and surface morphology indicated that the coatings with HA MW of 1 × 105 (PDA/HA-2) and 1 × 106 Da (PDA/HA-4) significantly enhanced the corrosion resistance of Mg-Zn-Y-Nd. In vitro biological test also suggested better hemocompatibility, pro-endothelialization, anti-hyperplasia and anti-inflammation functions of the PDA/HA-2- and PDA/HA-4-coated Mg-Zn-Y-Nd alloy. Nevertheless, the in vivo implantation of SD rats' celiac artery demonstrated that the PDA/HA-2 had preferable corrosion resistance and biocompatibility.
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Aleaciones , Materiales Biocompatibles Revestidos , Aleaciones/química , Aleaciones/farmacología , Animales , Materiales Biocompatibles Revestidos/química , Materiales Biocompatibles Revestidos/farmacología , Corrosión , Células Endoteliales de la Vena Umbilical Humana , Humanos , Ácido Hialurónico/química , Ácido Hialurónico/farmacología , Indoles/química , Indoles/farmacología , Magnesio/química , Magnesio/farmacología , Ensayo de Materiales , Neodimio/química , Neodimio/farmacología , Polímeros/química , Polímeros/farmacología , Ratas , Ratas Sprague-Dawley , Itrio/química , Itrio/farmacología , Zinc/química , Zinc/farmacologíaRESUMEN
Nitric oxide (NO) released by vascular endothelial cells (VECs), as a functional factor and signal pathway molecule, plays an important role in regulating vasodilation, inhibiting thrombosis, proliferation and inflammation. Therefore, numerous researches have reported the relationship between the NO level in VECs and the cardiovascular biomaterials' structure/functions. In recent years, biomedical magnesium (Mg) alloys have been widely studied and rapidly developed in the cardiovascular stent field for their biodegradable absorption property. However, influence of the Mg alloys' degradation products on VEC NO release is still unclear. In this work, Mg-Zn-Y-Nd, an Mg alloy widely applied on the biodegradable stent research, was investigated on the influence of the degradation time, the concentration and reaction time of degradation products on VEC NO release. The data showed that the degradation product concentration and the reaction time of degradation products had positive correlation with NO release, and the degradation time had negative correlation with NO release. All these influencing factors were controlled by the Mg alloy degradation behaviors. It was anticipated that it might make sense for the cardiovascular Mg alloy design aiming at VEC NO release and therapy.
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Aleaciones/química , Células Endoteliales/efectos de los fármacos , Células Endoteliales/metabolismo , Magnesio/química , Magnesio/farmacología , Óxido Nítrico/metabolismo , Proliferación Celular/efectos de los fármacos , Supervivencia Celular/efectos de los fármacos , Células Endoteliales/citología , CinéticaRESUMEN
MicroRNA (miRNA)145 has been demonstrated to serve a role in several types of tumors, however, the potential molecular mechanism of action of miRNA145 in bladder cancer metastasis remains to be elucidated. This study aimed to investigate the potential modulation of miRNA145 in bladder carcinoma and elucidate the underlying molecular mechanism. The expression of miRNA145 in bladder adenocarcinoma tissues and bladder cancer cells was measured by reverse transcriptionquantitative polymerase chain reaction. miRNA145 mimics and inhibitor were transfected into bladder cancer (BC) cells to determine the role of miRNA145 on cell motility and invasion measured by wound healing and transwell assays. Luciferase assay was performed to confirm whether Ncadherin was the direct target of miRNA145. Subsequently, expression of Ncadherin and matrix metalloproteinase9 (MMP9) in BC cells were detected by western blot analysis. miRNA145 was significantly downregulated cells and tissues from patients with BC, compared with healthy controls. miRNA145 markedly inhibited the ability of BC cells to migrate and invade. Furthermore, Ncadherin was identified as a target of miRNA145 in BC cells. MMP9, acting downstream of Ncadherin, was downregulated in BC cells by miRNA145. In the present study, miRNA145 suppressed the migration and invasion of BC cells by regulating Ncadherin. The results of the present study indicated that miRNA145 may function as a tumor suppressor and may have a potential to be a diagnostic and predictive biomarker, and a therapeutic target for treatment of BC.
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Cadherinas/genética , Regulación Neoplásica de la Expresión Génica , MicroARNs/genética , Interferencia de ARN , Neoplasias de la Vejiga Urinaria/genética , Regiones no Traducidas 3' , Adulto , Anciano , Línea Celular Tumoral , Movimiento Celular/genética , Proliferación Celular , Femenino , Humanos , Masculino , Persona de Mediana Edad , Estadificación de Neoplasias , Neoplasias de la Vejiga Urinaria/patologíaRESUMEN
As a main treatment of prostate cancer, castration therapy has been widely applied in the clinic. However, the therapeutic strategy for hormone-independent prostate cancer (HIPC) was not satisfied. Gemcitabine is an important chemotherapeutic agent that has been approved for the treatment of numerous human solid tumors, including HIPC, whereas the gemcitabine resistance has become a serious problem in clinical chemotherapy. In the present study, the mechanisms of resistance to gemcitabine were investigated in HIPC cell lines. The results demonstrated that the autophagy markers were induced significantly in HIPC cells subsequent to gemcitabine treatment. Meanwhile, administration of gemcitabine to HIPC cells increased the expression of high mobility group box1 (HMGB1). Furthermore, the gemcitabine-induced autophagy response was attenuated in stable HIPC cells harboring HMGB1 shRNA. Notably, the HIPC cells stably transfected with HMGB1 shRNA or treated with autophagy inhibitors were more sensitive to gemcitabine compared with the control group. These data suggested that inhibition of HMGB1 increased the sensitivity to gemcitabine by decreasing autophagy response in HIPC cells. Overall, the present findings demonstrate a new mechanism for the resistance to gemcitabine in HIPC cell lines.
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OBJECTIVE: To summarize the technical measures in achieving the elimination of lymphatic filariasis in Tengzhou city. METHODS: To collect and analyze the materials on research and control of lymphatic filariasis in Tengzhou city during the disease elimination program over the 40 years. RESULTS: Following to the national criteria for the control and elimination of filariasis, efforts were made for epidemiological investigation, mass blood examination, and mass drug administration by taking diethylcarbamazine (DEC) medicated salt for the whole population. After the criteria of transmission interruption (basic elimination) of filariasis were met in 1974, re-examination and treatment for the cases with microfilaremia, and parasitological and entomological surveillance were conducted. In 1995, filariasis elimination in the whole city was declared. CONCLUSION: Comprehensive measures focusing on the elimination of source of infection were proved effective for interrupting the transmission of filariasis. Unremitting surveillance was necessary for achieving the goal of elimination of filariasis.
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Dietilcarbamazina/uso terapéutico , Filariasis Linfática/prevención & control , Filaricidas/uso terapéutico , Animales , China/epidemiología , Filariasis Linfática/epidemiología , Humanos , Microfilarias/aislamiento & purificación , PrevalenciaRESUMEN
BACKGROUND: This analysis was conducted to evaluate the efficacy and safety of cisplatin based chemotherapy for treating patients with cutaneous squamous cell carcinoma. METHODS: Clinical studies evaluating the efficacy and safety of cisplatin based regimens on response and safety for patients with cutaneous squamous cell carcinoma were identified using a predefined search strategy. Pooled response rates (RR) of treatment were calculated. RESULTS: In cisplatin based regimens, 4 clinical studies which including 50 patients with advanced cutaneous squamous cell carcinoma were considered eligible for inclusion. Regimens included cisplatin, doxorubicin, or vindesine. Pooled analysis suggested that, in all patients, the pooled RR was 60% (30/50) in cisplatin based regimens. Nausea and vomiting were the main side effects. No grade III or IV renal or liver toxicity were observed. No treatment related death occurred with the cisplatin based treatments. CONCLUSION: Evidence based analysis suggests that cisplatin based regimens are associated with a good response rate and acceptable toxicity for treating patients with cutaneous squamous cell carcinoma.
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Protocolos de Quimioterapia Combinada Antineoplásica/uso terapéutico , Carcinoma de Células Escamosas/tratamiento farmacológico , Resistencia a Antineoplásicos/efectos de los fármacos , Recurrencia Local de Neoplasia/tratamiento farmacológico , Terapia Recuperativa , Neoplasias Cutáneas/tratamiento farmacológico , Carcinoma de Células Escamosas/mortalidad , Carcinoma de Células Escamosas/patología , Cisplatino/administración & dosificación , Doxorrubicina/administración & dosificación , Humanos , Metaanálisis como Asunto , Recurrencia Local de Neoplasia/mortalidad , Recurrencia Local de Neoplasia/patología , Estadificación de Neoplasias , Pronóstico , Neoplasias Cutáneas/mortalidad , Neoplasias Cutáneas/patología , Tasa de Supervivencia , Vindesina/administración & dosificaciónRESUMEN
Lithium and nickel complexes bearing quinoline-based ligands have been synthesized and characterized. Reaction of 8-azidoquinoline with Ph(2)PNHR (R = p-MeC(6)H(4), Bu(t)) affords N-(8-quinolyl)iminophosphoranes RNHP(Ph(2))=N(8-C(9)H(6)N) (1a, R = p-MeC(6)H(4); 1b, R = Bu(t). C(9)H(6)N = quinolyl)). Reaction of 1a with (DME)NiCl(2) generates a nickel complex [NiCl(2){N(8-C(9)H(6)N)=P(Ph(2))NH(p-MeC(6)H(4))}] (2a). Treatment of 1b with (DME)NiCl(2) and following with NaH produces [NiCl{(1,2-C(6)H(4))P(Ph)(NHBu(t))=N(8-C(9)H(6)N)}] (4). Complex 4 was also obtained by reaction of (DME)NiCl(2) with [Li{(1,2-C(6)H(4))P(Ph)(NHBu(t))=N(8-C(9)H(6)N)}] (5) prepared through lithiation of 1b. Reaction of 2-PyCH(2)P(Ph(2))=N(8-C(9)H(6)N) (6, Py = pyridyl) and PhN=C(Ph)CH(2)P(Ph(2))=N(8-C(9)H(6)N) (8), respectively, with (DME)NiCl(2) yields two five-coordinate N,N,N-chelate nickel complexes, [NiCl(2){2-PyCH(2)P(Ph(2))=N(8-C(9)H(6)N)}] (7) and [NiCl(2){PhN=C(Ph)CH(2)P(Ph(2))=N(8-C(9)H(6)N)}] (9). Similar reaction between Ph(2)PCH(2)P(Ph(2))=N(8-C(9)H(6)N) (10) and (DME)NiCl(2) results in five-coordinate N,N,P-chelate nickel complex [NiCl(2){Ph(2)PCH(2)P(Ph(2))=N(8-C(9)H(6)N)}] (11). Treatment of [(8-C(9)H(6)N)N=P(Ph(2))](2)CH(2) (12) [prepared from (Ph(2)P)(2)CH(2) and 2 equiv. of 8-azidoquinoline] with LiBu(n) and (DME)NiCl(2) successively affords [NiCl{(8-C(9)H(6)N)NP(Ph(2))}(2)CH] (13). The new compounds were characterized by (1)H, (13)C and (31)P NMR spectroscopy (for the diamagnetic compounds), IR spectroscopy (for the nickel complexes) and elemental analysis. Complexes 2a, 4, 7, 9, 11 and 13 were also characterized by single-crystal X-ray diffraction techniques. The nickel complexes were evaluated for the catalysis in the cross-coupling reactions of arylzinc reagents with aryl chlorides and aryltrimethylammonium salts. Complex 7 exhibits the highest activity among the complexes in catalyzing the reactions of arylzinc reagents with either aryl chlorides or aryltrimethylammonium bromides.