This review was devoted to outlining the use and potential increasing application of the Design of Experiment (DoE) approach to the rational and planned synthesis of inorganic nanomaterials, with a ...particular focus on polycrystalline nanostructures (metal and alloys, oxides, chalcogenides, halogenides, etc.) produced by sustainable wet chemistry routes based on a multi-parameter experimental landscape. After having contextualised the stringent need for a rational approach to inorganic materials’ synthesis, a concise theoretical background on DoE is provided, focusing on its statistical basis, shortly describing the different sub-methodologies, and outlining the pros and cons of each. In the second part of the review, a wider section is dedicated to the application of DoE to the rational synthesis of different kinds of chemical systems, with a specific focus on inorganic materials.
The possibility to precisely control reaction outcomes for pursuing materials with well-defined features is a main endeavor in the development of inorganic materials. Confining reactions within a ...confined space, such as nanoreactors, is an extremely promising methodology which allows to ensure control over the final properties of the material. An effective room temperature inverse miniemulsion approach for the controlled synthesis of undoped and Eu3+-doped calcium molybdate crystalline nanophosphors was developed. The advantages and the efficiency of confined space in terms of controlling nanoparticle features like size, shape, and functional properties are highlighted by systematically comparing miniemulsion products with calcium molybdate particles obtained without confinement from a typical batch synthesis. A relevant beneficial impact of space confinement by miniemulsion nanodroplets is observed on the control of size and shape of the final nanoparticles, resulting in 12 nm spherical nanoparticles with a narrow size distribution, as compared to the 58 nm irregularly shaped and aggregated particles from the batch approach (assessed by TEM analysis). Further considerable effects of the confined space for the miniemulsion samples are found on the doping effectiveness, leading to a more homogeneous distribution of the Eu3+ ions into the molybdate host matrix, without segregation (assessed by PXRD, XAS, and ICP-MS). These findings are finally related to the photoluminescence properties, which are evidenced to be closely dependent on the Eu3+ content for the miniemulsion samples, as an increase of the relative intensity of the direct f–f excitation and a shortening of the lifetime (from 0.901 ms for 1 at. % to 0.625 ms for 7 at. % samples) with increasing Eu3+ content are observed, whereas no relationship between these parameters and the Eu3+ content is evidenced for the batch samples. All these results are ascribed to the uniform and controlled crystallization occurring inside each miniemulsion nanodroplet, as opposed to the less controlled nucleation and growth for a classic nonconfined approach.
Background -2proPSA seems to outperform free/total prostate-specific antigen (PSA) ratio in prostate cancer diagnosis. However, -2proPSA stability remains an underestimated issue. We examined ...-2proPSA stability over time in whole blood before separation of serum and plasma and its implications for prostate health index (Phi) determination. Total PSA (tPSA) and free PSA (fPSA) stabilities were also assessed. Methods Blood was drawn from 26 patients and separated in two tubes for plasma (K2EDTA and K2EDTA plus protease inhibitors - P100) and one for serum (clot activator plus gel separator). Tubes were stored at room temperature before centrifugation 1, 3 and 5 h for serum and EDTA plasma or 1 and 5 h for P100 plasma. To investigate the influence of gel separator on markers' stability, blood was collected from 10 patients in three types of tubes to obtain serum: tubes with clot activator plus gel separator, with silica particles or glass tubes. Biomarkers were assayed with chemiluminescent immunoassays. Results -2proPSA and Phi levels significantly and progressively increased over time in serum (+4.81% and +8.2% at 3 h; +12.03% and +14.91% at 5 h, respectively, vs. 1 h; p<0.001). Conversely, -2proPSA levels did not change in plasma (EDTA or P100). tPSA levels did not change over time in serum or plasma, whereas fPSA decreased in serum. All markers were higher in plasma than in serum at any time point. This difference did not seem to be attributable to the use of gel for serum preparation. Conclusions EDTA prevented spurious in vitro modifications in PSA-related isoforms, confirming that a stabilized blood sample is a prerequisite for -2proPSA measurement and Phi determination.
The goal of the study was to define treatment rules for the uncommon, rarely (10%) malignant and chemorefractory Leydig cell tumors (LCT) of the testis.
The main clinical data of patients treated in ...centers affiliated to the GUONE (North-Eastern Uro-Oncological Group, Italy) were reviewed. We considered 52 patients (54 tumors, 2 bilateral) whose ages ranged from 13 to 70 years (mean 36). Of the treatments performed, 52 were orchiectomies and 2 were enucleations (unfavorable pathology in only 2 tumors). There were 5 lymphadenectomies (retroperitoneal lymph node dissections): 2 for suspected stage II disease and 1 each for unfavorable pathology, bilateral disease and associated Sertoli tumor (pathology: pN0 in all cases). The length of follow-up ranged from 15 to 249 months (mean 81).
There was no relapse in 51 patients and 1 died as a result of metastatic disease (orchiectomy at the age of 70; unremarkable pathology).
Malignant LCT seems to be, in our experience, less frequent than previously reported. Age and pathology are useful prognostic factors, but their predictive value should never be considered absolute. Enucleation seems justified in young patients with favorable pathology. In clinical stage I LCT, retroperitoneal lymph node dissection should be offered to older patients and/or to patients with unfavorable pathology. A prolonged follow-up is mandatory.
The diagnosis and follow-up of bladder cancer are mainly based on cystoscopy, an invasive method which could be negative in case of flat malignancies such as carcinoma in situ. Other noninvasive ...diagnostic methods have not yet given satisfactory results. There is a need for a reliable yet noninvasive method for the detection of bladder cancer. Our aim was to investigate whether cell-free DNA quantified in urine (ucf-DNA) could be a useful marker for the diagnosis of bladder cancer. A standard urine test was performed in 150 naturally voided morning urine samples that were processed to obtain a quantitative evaluation of ucf-DNA. Leukocyturia and/or bacteriuria were found in 18 subjects, who were excluded from the study. Statistical analysis was performed on 45 bladder cancer patients and 87 healthy subjects. Ucf-DNA was extracted from urine samples by a spin column-based method and quantified using four different methods: GeneQuant Pro (Amersham Biosciences, Pittsburg, PA, USA), Quant-iT DNA high-sensitivity assay kit (Invitrogen, Carlsbad, CA, USA), Real-Time PCR (Applied Biosystems, Foster City, CA, USA), and NanoDrop 1000 (NanoDrop Technologies, Houston, TX, USA). Median free DNA quantification did not differ statistically between bladder cancer patients and healthy subjects. A receiver-operating characteristic (ROC) curve was developed to evaluate the diagnostic performance of ucf-DNA quantification for each method. The area under the ROC curve was 0.578 for GeneQuant Pro, 0.573 for the Quant-iT DNA high-sensitivity assay kit, 0.507 for Real-Time PCR, and 0.551 for NanoDrop 1000, which indicated that ucf-DNA quantification by these methods is not able to discriminate between the presence and absence of bladder cancer. No association was found between ucf-DNA quantification and tumor size or tumor focality. In conclusion, ucf-DNA isolated by a spin column-based method and quantified by GeneQuant Pro, Quant-iT DNA high-sensitivity assay kit, Real-Time PCR or NanoDrop 1000 does not seem to be a reliable marker for the diagnosis of bladder cancer.
Our experience with laser treatment of urethral strictures with a 980-nm diode laser is reported.
45 consecutive patients with relapsing urethral strictures (mean age 65, range 25-85 years) were ...treated between February 1995 and February 1998. The fibrous and scar tissue was cut and vaporized at the 6 o'clock position with the laser beam.
44/45 patients were available for follow-up at 1 year and 32/43 at 2 years. At 12 months the average peak flow rates of the patients was 18 ml/s, and at the second year assessment it was 15.5 ml/s. Of the patients 21/44 (47.7%) were extremely satisfied (0-1 of the quality-of-life, QoL, assessment index) with the procedure, 14/44 (31.8%) were satisfied (2 of the QoL assessment index), and 9/44 (20.4%) were not satisfied (> or = 3 of the QoL assessment index) due to the low flow rate or the recurrence of the stricture. (The sum of the first two categories is 79.5%.) At the second year assessment the percentage of satisfied patients reached 78%, with 71% of the patients stable without any dilatation.
Usually in recurrent strictures of the urethra open surgery is suggested, but we believe that there is still a place for endoscopy. With the laser we can make an incision at the 6 o'clock position without significant bleeding, very easily opening the urethra. We had 79.5 and 71% good results at the 1- and 2-year assessments (mean peak flow rate of 18 and 15.5 ml/min), respectively. To date, no definitive conclusions can be drawn, but we believe that laser treatment is indicated for recurrent strictures in high risk or elderly patients and in those who demand a minimally invasive procedure.
A patient treated with prophylactic infradiaphragmatic radiation therapy for clinical stage I left testicular pure seminoma developed a large mass of the chest wall 12 years after primary treatment. ...An incisional biopsy confirmed pure seminoma. After chemotherapy, surgical removal of the residual mass and second-line chemoradiation therapy for persistent seminoma, the patient had a vertebral relapse. He died of progression 24 months after the first relapse despite further therapy.
The involvement of vena cava by residual masses after cytoreductive chemotherapy for bulky metastatic germ cell tumors is a rare but possible event. It could ensue by tumor invasion of the inferior ...vena cava (IVC), venous or neoplastic thrombosis, or by close adherence and encasement of IVC by scar tissue containing fibrosis or cancer; it usually occurs in right testicular neoplasms. In this study we evaluated a group of nine over 86 patients who underwent IVC (and possibly aortic) surgery for post-chemotherapy residual masses and we assessed long term oncological and functional efficacy of the procedure.
Between 1980 and 1997, 86 patients underwent retroperitoneal lymphadenectomy (RPLND) after induction or additional salvage chemotherapy. A subgroup of nine patients, all with primary tumors of the right testis in stage II C to III, showed evidence of caval involvement, four had caval thrombosis, seven exhibited caval invasion; in one case the IVC was displaced and compressed with no clear evidence of infiltration. Surgical management was: three en-bloc and four restricted vena caval resection and two thrombectomy.
Of nine patients who underwent IVC surgery, six are alive and have no evidence of disease (follow-up 43-207 months), while three patients deceased for early progression (6-10 months). There were no major surgical complications: only one patient exhibited a significant lymphedema as a result of the primary vascular involvement or of following IVC surgery.
IVC resection is sometimes necessary to complete RPLND of residual masses: it might be crucial to gain oncological clearance, with moderate long term morbidity even for extensive vena cava resections. Among patients eligible for postchemotherapy RPLND, caval involvement selects a higher risk subgroup that should be addressed to medical centers experienced in IVC neoplastic involvement.
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