Layered Silicates Exhibiting MOF-Like Gate-Opening Behaviors in Liquid-Phase Adsorptions: Experimental and Theoretical Investigations.

Layered silicates, including clay minerals, can be used as liquid-phase adsorbents in many important applications. However, because their two-dimensional interlayer space is narrow and not entirely opened due to the presence of interlayer species, guest species are forced to penetrate while expanding the interlayer space, which limits their adsorption performances compared with microporous materials such as MOFs and zeolites. Herein, as reported for the adsorption of gaseous species on flexible MOFs, we report a layered silicate that exhibits gate-opening adsorption in liquid phases. This layered silicate, synthesized via dilute acid treatment of the parent sodium-type, exhibits an abrupt increase in the basal spacing (layer thickness + interlayer space) to reach a plateau even at an earlier stage of benzoic acid adsorption from acetonitrile, whereas a typical layered silicate, magadiite, exhibits a gradual increase in the basal spacing as adsorption progress under identical conditions. The layered silicate shows an excellent adsorption capacity and rate for benzoic acid uptake from acetonitrile, which is considerably higher than that of magadiite. With comprehensive adsorption tests using different adsorbates and solvents, we propose that the layered silicate has zeolite-like but distorted, flexible open microchannels within each layer, and the intralayer microchannels can effectively and rapidly accommodate the solvent (acetonitrile) molecules, which are capable of expanding the framework to initiate the adsorption of aromatic compounds. The density function theory calculation revealed the adsorption mechanism, where the layered silicate accommodates acetonitrile in the intralayer microchannel followed by the interlayer space, and the former selectively plays a role as the adsorption site of aromatic compounds via exchange with acetonitrile.

Clinical efficacy of mini-percutaneous nephrolithotomy versus retrograde intrarenal surgery for the management of upper urinary tract calculus (1-2.5 cm) in children ≤10 years of age.

BACKGROUND: With improvements in endoscopic surgery, open surgical procedures for urinary system stones have cleared the path for the use of less invasive treatment modalities in patients with pediatric kidney stone disease. Extracorporeal shock wave lithotripsy (ESWL), percutaneous nephrolithotomy (PCNL), and retrograde intrarenal surgery (RIRS) are among the treatment options available. OBJECTIVE: To prospectively evaluate the outcomes of mini-percutaneous nephrolithotomy and retrograde intrarenal surgery (RIRS) for children ≤10 years of age with upper urinary tract calculus (1-2.5 cm). STUDY DESIGN: Sixty pediatric patients with single or multiple renal stones (1-2.5 cm in diameter) were collected prospectively and equally divided into two groups to undergo RIRS or mini-PCNL. The operative and postoperative outcomes of both groups were analyzed. RESULTS: The groups' mean ages and genders were comparable. The mean stone size for the RIRS group was 1.86 cm and 1.69 cm for the PCNL group (P = 0.449). The PCNL group had statistically longer mean fluoroscopy and hospitalization times. The stone-free rates (SFRs) after a single procedure were 27 (90%) in the PCNL group and 25 (83.33%) in the RIRS group (P = 0.706). The UAS was placed in 13 (43.33%) patients in the RIRS group. In the RIRS group, 14 (46.67%) children required preoperative DJ stent application to passively dilate the ureteric orifice. As regard post DJ stenting, 13 (46%) cases applied DJ in the mini PCNL group. major complications were observed in either group. Minor complication (Clavien 1-3) rates were 16.66% and 13.33% for the PCNL and RIRS groups, respectively. There were no differences found between the RIRS and mini-PCNL groups regarding operative time. The mean cost of RIRS was $703.96 and $537.03 for the mini-PCNL. CONCLUSION: According to the results of this study, mini-PCNL and RIRS are effective procedures for treating renal stones in children up to 2.5 cm with comparable success and complication rates. Hospital stay, radiation exposure, and fluoroscopy time are significantly lower in RIRS than in the mini PCNL technique. Although RIRS is effective, a major disadvantage is the greater requirement for JJ stent insertion either before or after the procedure and the consequent need for a second procedure for removal.

Integrated geochemical and magnetic potentially toxic elements assessment: a statistical solution discriminating anthropogenic and lithogenic magnetic signals in a complex area of the southeast Nile Delta.

Magnetic proxy approaches proved to be efficient for potentially toxic elements (PTEs) pollution assessment when targeting forests or areas with a homogenous background where anthropogenic magnetic signals could be easily distinguished. Here, we present a multidisciplinary approach for magnetic susceptibility ([Formula: see text]) and HM assessment in a complex area in the Nile Delta, where geogenic input, land use, and various industries with different fly ash and surface water emissions interfere. Statistical analysis discriminates between the effects of lithologic elements and the concentrations of toxic anthropogenic elements. The studied elements are classified into lithogenic and anthropogenic-related (HMs, Au industry, and fertilizers industry) groups with maximum contamination levels of eight anthropogenic-related and highly toxic PTEs (Cu, Zn, Mo, Cd, Sb, Pb, Hg, and As) in the Akrasha industrial area (pollution load index = 15.84). Considering the whole data set, the numerical correlation of [Formula: see text] with most PTE concentrations and the pollution load index (PLI) is weak, while it is moderate to strong with lithogenic elements. However, a comparison of lithogenic elements and PTE concentrations along with x-values in two separate clusters supports the correspondence of lithology with elevated x-values in silt and clay-rich soil samples as well as HM concentration in industrial sandy soils. Correspondence between magnetic maps and chemistry data with land use reflects the potential of magnetic proxy methods for qualitative PTE pollution pre-delineation of the polluted spots, provided that lithological conditions are carefully considered.

Ultrasonically-assisted synthesis of CeO2 within WS2 interlayers forming type II heterojunction for a VOC photocatalytic oxidation.

Here, we investigate the band structure, density of states, photocatalytic activity, and heterojunction mechanism of WS2 with CeO2 (CeO2@WS2) as a photoactive heterostructure. In this heterostructure, CeO2's growth within WS2 layers is achieved through ultrasonicating WS2 and intercalating CeO2's precursor within the WS2 interlayers, followed by hydrothermal treatment. Through a set of density functional calculations, we demonstrate that CeO2 and WS2 form an interface through a covalent bonding that can be highly stable. The electrochemical impedance spectroscopy (EIS) found that the CeO2@WS2 heterostructure exhibits a remarkably higher conductivity (22.23 mS cm-2) compared to either WS2 and CeO2, assignable to the interface in CeO2@WS2. Furthermore, in a physically mixed CeO2-WS2 where the interaction between particles is noncovalent, the resistance was significantly higher (0.67 mS cm-2), confirming that the heterostructure in the interface is covalently bonded. In addition, Mott-Schottky and the bandgap measurements through Tauc plots demonstrate that the heterojunction in CeO2 and WS2 is type II. Eventually, the CeO2@WS2 heterostructure indicated 446.7 µmol g -1 CO2 generation from photocatalytic oxidation of a volatile organic compound (VOC), formic acid, compared to WS2 and CeO2 alone.

MOF-derived nanocrystalline ZnO with controlled orientation and photocatalytic activity.

We show here that MOF-5, a sample Zn-based MOF, can uniquely transform into distinct zinc oxide nanostructures. Inspired by the interconversion synthesis of zeolites, we converted MOF-5 into nanocrystalline ZnO. We found the conversion of MOF-5 into ZnO to be tunable and straightforward simply by controlling the treatment temperature and choosing an appropriate structure-directing agent (SDA). Refined X-ray diffraction (XRD) patterns showed that a synthesis temperature of 180 °C (sample ZnO-180) was optimal for achieving high crystallinity. We examined ZnO-180 with high-resolution transmission electron microscopy (HRTEM), which confirmed that the samples were made of individual crystallites grown along the c-axis, or the (001) direction, thus exposing lower energy surfaces and corroborating the XRD pattern and the molecular dynamics calculations. Further investigations revealed that the obtained ZnO at 180 °C has a superior photocatalytic activity in degrading methylene blue to other ZnO nanostructures obtained at lower temperatures.

Correlation Between Preoperative Gastric Volume and Weight Loss After Laparoscopic Sleeve Gastrectomy.

PURPOSE: Long-term studies reported inadequate weight loss or weight regain after laparoscopic sleeve gastrectomy (LSG). This study investigated a possible relationship between preoperative gastric volume (GV) measured by CT volumetry and weight loss one year after LSG. METHODS: This prospective study included 120 patients scheduled for LSG. 3D CT gastric volumetry was done before surgery. The weight loss in the first year was serially recorded. The primary outcome measure was the correlation between preoperative GV and postoperative weight loss after one year. The secondary outcomes were the correlation between preoperative GV and other patients' characteristics as age and body mass index (BMI). RESULTS: Weight and BMI decreased significantly up to 12 months. The percentage of excess weight loss (%EWL) at 6 and 12 months was significantly higher than at three months. Preoperative GV was 1021 ± 253, ranging from 397 to 1543 mL. GV was not related to sex, age, weight, height, postoperative weight, and BMI. CONCLUSION: Preoperative gastric volume cannot predict weight loss one year after LSG. It is not correlated with age, sex, or preoperative weight, and BMI.

Phenyl-Modified Carbon Nitride Quantum Nanoflakes for Ultra-Highly Selective Sensing of Formic Acid: A Combined Experimental by QCM and Density Functional Theory Study.

Formic acid (HCOOH) is an important intermediate in chemical synthesis, pharmaceuticals, the food industry, and leather tanning and is considered to be an effective hydrogen storage molecule. Direct contact with its vapor and its inhalation lead to burns, nerve injury, and dermatosis. Thus, it is critical to establish efficient sensing materials and devices for the rapid detection of HCOOH. In the present study, we introduce a chemical sensor based on a quartz crystal microbalance (QCM) sensor capable of detecting trace amounts of HCOOH. This sensor is composed of colloidal phenyl-terminated carbon nitride (Ph-g-C3N4) quantum nanoflakes prepared using a facile solid-state method involving the supramolecular preorganization technology. In contrast to other synthetic methods of modified carbon nitride materials, this approach requires no hard templates, hazardous chemicals, or hydrothermal treatments. Comprehensive characterization and density functional theory (DFT) calculations revealed that the QCM sensor designed and prepared here exhibits enhanced detection sensitivity and selectivity for volatile HCOOH, which originates from chemical and hydrogen-bonding interactions between HCOOH and the surface of Ph-g-C3N4. According to DFT results, HCOOH is located close to the cavity of the Ph-g-C3N4 unit, with bonding to graphitic carbon and pyridinic nitrogen atoms of the nanoflake. The sensitivity of the Ph-g-C3N4-nanoflake-based QCM sensor was found to be the highest (128.99 Hz ppm-1) of the substances studied, with a limit of detection (LOD) of HCOOH down to a sub-ppm level of 80 ppb. This sensing technology based on phenyl-terminated attached-g-C3N4 nanoflakes establishes a simple, low-cost solution to improve the performance of QCM sensors for the effective discrimination of HCOOH, HCHO, and CH3COOH vapors using smart electronic noses.

Template-oriented synthesis of hydroxyapatite nanoplates for 3D bone printing.

The design of hydroxyapatite (HA) nanoarchitecture is critical for fabricating artificial bone tissues as it dictates the biochemical and the mechanical properties of the final product. Herein, we incorporated a simple hard-template approach to synthesise single crystal nanoplates of HA. We used the 2D graphitic nitride (g-C3N4) material to prepare an HA sol-gel under hydrothermal conditions. A new HA nanostructure was then formed during the calcination and removal of g-C3N4 at a higher temperature, which finally led to the production of nanoplates (thickness of ∼100 nm) while in lateral dimension the average size was in the micrometre scale. We characterised the synthesised HA nanoplates with XRD, TEM, and HRTEM. The theoretically predicted nanostructure construction based on Wulff's method is in full agreement with the experimental observations. We then prepared different weight ratios of HA and polylactic acid (PLA) composites for artificial 3D bone fabrication. The strong interaction between PLA and HA's (110) facet, which was the second most prevalent, resulted in the composite's mechanical robustness. After mechanical testing, an optimum ratio was selected for biological studies and 3D printing. Biological experiments demonstrated that the synthesised composite had excellent viability in vitro.

Conversion of a 2D Lepidocrocite-Type Layered Titanate into Its 1D Nanowire Form with Enhancement of Cation Exchange and Photocatalytic Performance.

Layered titanates with one-dimensional (1D) shapes have been an important class of nanomaterials due to their combination of 1D and 2D fascinating properties. Among many layered titanates, lepidocrocite-type layered titanates have significant advantages such as superior intercalation and exfoliation properties, while the synthesis of the 1D-shape forms is still challenging. Here, we report on a facile one-pot hydrothermal conversion of a lepidocrocite-type layered titanate into the corresponding nanowire-shape form. The reaction mechanism involves the decomposition of the starting layered titanate into 1D small segments which assemble into the nanowire. This new nanowire shows properties resulting from the combination of 1D and 2D nanostructural features, excellent cation exchange ability, and high photoinduced charge separation and photocatalytic efficiency. As a demonstration, we evaluate the nanowire as a sequestrating material capable of collecting toxic cations, like Cd2+, from water and photoreducing them (immobilizing them tightly). We find that the nanowire shows an efficient and ultrafast photoimmobilization activity, whereas the starting layered titanate and a benchmark TiO2 photocatalyst (P25) show no activity under the identical conditions. The photoimmobilization rate (within 1 min) is considerably faster than the cation exchange rates reported for state-of-the-art cation exchangers (with no photoimmobilization ability). The nanowire used for photoimmobilization reactions is easily recovered from water by decantation, showing the possible practical use for safe disposal of toxic cations in the environment.

Differential Expression of RAGE, EGFR and Ki-67 in Primary Tumors and Lymph Node Deposits of Breast Carcinoma

Background: Breast cancer is a complex disease that results from the inheritance of a number of susceptible genes. Intensive search wok was conducted world-wide on molecular bases of breast cancer in order to achieve the best therapeutic modalities; however, breast cancer still remains a challengeable task. It is very important to determine if the biological parameters in metastatic regional lymph nodes are similar to that in the primary breast cancer because therapy is indicated for patients with synchronous metastatic regional lymph nodes of breast cancer. Difference in therapeutic response in cases of breast cancer may be assumed partially to variability in the biological behavior of tumor tissue in primary breast cancer and lymph node metastasis. Aim: Our aim is to evaluate any variability in the expression of three types of tissue markers in both the primary breast tumors and corresponding axillary lymph nodes in order to expect the targeted therapeutic effect on both sites. Material and Methods: Three markers from different categories; RAGE, EGFR and Ki-67 were immunohistochemicalyl studied for their expression in biopsy specimens from primary breast tumors and their corresponding axillary lymph nodes. Results: There was a statistically significant difference in the expression of these markers between benign and malignant breast lesions.Although we found some differences in the expression of the three studied markers between primary breast cancer and corresponding axillary lymph nodes, yet these variations were mostly not statistically significant. Conclusion: Our findings support the validity of anti-RAGE and anti-EGFR therapy for treatment of both primary and nodal metastatic breast cancer in immunopositive cases.

Alginate-based nanocomposites for efficient removal of heavy metal ions.

Cobalt ferrite nanoparticles (CF), titanate nanotubes (T), alginate (G) and their nanocomposite microparticles (CF/G and T/G) were prepared and used for efficient removal of Cu2+, Fe3+ and As3+ ions from water. The nanocomposites were characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), FTIR and vibrating sample magnetometer (VSM). In addition, the effects of pH, contact time, adsorbent weight and heavy metal ion concentration on the removal efficiency were investigated. Our results revealed a successful preparation of the nanocomposite particles. The optimized batch experiment conditions were found to be pH of 6.5, contact time of 2h and adsorbent weight of 0.15g. The removal efficiencies for Cu2+ using G, CF, T, CF/G and T/G were found to be 91%, 100%, 99.9%, 95% and 98%, respectively. While that of Fe3+ removal was 60%, 100%, 100%, 60% and 82%, respectively. Efficient removal of As3+ ions was also attained (98% upon using T nanoadsorbents). The current study demonstrated that the developed nanomaterials (CF and T) and their corresponding alginate-based nanocomposite microparticles could be further tailored and used as efficient adsorbents for the uptake of different heavy metal ions from wastewater.

The value of combined use of survivin mRNA and matrix metalloproteinase 2 and 9 for bladder cancer detection in voided urine.

OBJECTIVE: In a trial to improve the diagnostic efficacy of conventional urine cytology we determine survivin RNA and matrix metalloproteinase 2 and 9 in urine of bladder cancer cases. METHOD: Voided urine specimens were collected from patients with histologically confirmed bladder urothelial carcinoma (Group 1; n=46), urological patients without urothelial carcinoma (Group 2; n=20), and healthy volunteers (Group 3; n=20). Urine cytology, survivin RNA was estimated by qualitative nested RT-PCR and MMP-2, MMP-9 activity were detected by gelatin zymography. The expression of survivin RNA and matrix metalloproteinase 2 and 9 in bladder cancer was compared with benign and normal cases. RESULTS: Positivity rates of survivin RNA and MMPs zymography were significantly different among the 3 groups. Urine survivin detection by qualitative nested RT-PCR showed 76.1% sensitivity and 95% specificity. The overall sensitivity, specificity of urinary MMP zymography was 67.3%, 90% respectively. The combined use of urine cytology with urine survivin or MMPs zymography increased sensitivity of urine cytology from 50% to 84.7%. The highest sensitivity (95.6%) was obtained on combining the three markers. CONCLUSION: Survivin RNA and MMPS zymography can be considered as promising noninvasive markers for bladder cancer early detection. Combined use of the three markers improved the sensitivity for detecting bladder cancer.

Detection of hyaluronidase RNA and activity in urine of schistosomal and non-schistosomal bladder cancer.

Diagnosis of bladder cancer is done by cystoscopy and cytology. In the last decade, many urine-based tests for bladder cancer have been developed and tested in different populations. Hence, it was relevant to assess the diagnostic significance of urinary hyaluronidase RNA and its enzyme activity in bladder cancer. Seventy patients with bladder cancer, 56 patients with benign bladder lesions, and 49 healthy controls were enrolled in this study. Voided urine samples from all subjects were used for estimation of urinary HAase RNA by semi-quantitative reverse transcription polymerase chain reaction (RT-PCR) and determination of its enzymatic activity by zymography. There was a significant difference in the mean ranks and positivity rates of HAase RNA expression (P < 0.01) and its enzymatic activity among the three investigated groups: malignant, benign, and normal (P < 0.01). In detecting bladder cancer, the sensitivity of urine cytology (42.83 %) was improved to 100 % when combined with urinary Hyal RNA or Hyal enzyme activity. Detection of urinary Hyal RNA and its enzyme activity is promising noninvasive tests with high sensitivities and specificities for detection of bladder cancer.

Urinary retinoic acid receptor-ß2 gene promoter methylation and hyaluronidase activity as noninvasive tests for diagnosis of bladder cancer.

OBJECTIVES: We evaluated the significance of urinary retinoic acid receptor-ß2 (RAR-ß2) gene promoter methylation and hyaluronidase activity in comparison with voided urine cytology (VUC) in diagnosis of bladder cancer. DESIGN AND METHODS: This study included 100 patients diagnosed with bladder cancer, 65 patients with benign urological disorders and 51 healthy volunteers. Urine supernatant was used for determining hyaluronidase activity by zymography while urine sediment was used for cytology and detection of methylated RAR-ß2 gene promoter by methylation specific nested PCR. RESULTS: The sensitivity and specificity were 53% and 90.5% for VUC, 65% and 89.7% for percent methylation fraction of RAR-ß2 gene promoter, and 89% and 90.5% for hyaluronidase activity; combination of the three parameters increased sensitivity to 95%. A significant association was observed between investigated markers and advanced grade tumor. CONCLUSIONS: Combined use of RAR-ß2 gene promoter methylation, hyaluronidase activity and VUC is promising non-invasive tool for bladder cancer detection.

Aberrant methylation of RARbeta2 and APC genes in voided urine as molecular markers for early detection of bilharzial and nonbilharzial bladder cancer.

BACKGROUND: Bladder cancer cells illustrate major disruptions in their DNA methylation patterns as compared with normal ones. Authors aimed to identify epigenetic molecular markers in urine for early detection of bladder cancer. MATERIALS AND METHODS: We retrospectively analyzed the methylation status of RARß(2) and APC genes in urine samples from 210 bladder cancer patients, 61 patients with benign urological diseases, and 49 healthy volunteers by using methylation-specific PCR. RESULTS: Methylated RARß(2) and APC were significantly higher in bladder cancer patients (62.8%, 59.5%) than benign (16.4%, 5%) but not detected in healthy volunteers (0%) at (P < 0.0001). Both methylated genes showed no significant difference among clinicopathologic factors; however, they were detected in all grades and stages. Among the 128 patients with bilharzial bladder cancer, 94 (73.4%) showed methylated RARß(2) and 86 (67.2%) showed methylated APC. Homoplasmic methylation pattern of both genes were only detected in bilharzial bladder cancer cases. Both sensitivities and specificities of the methylated genes for bladder cancer detection were superior to urine cytology and when altogether combined, the sensitivities improved to (91.8%), (93.5%), (91.9%), and (80.9%) in detection of: bladder cancer, non-muscle invasive bladder cancer, low-grade tumors, and bilharzial associated bladder cancer, respectively. CONCLUSION: Thus, methylated RARß(2) and APC genes might be valuable urinary molecular markers for early detection of bilharzial and nonbilharzial bladder cancer.