Turkish Journal of Chemistry最新文献

{"title":"Transdermal delivery system to release phthalocyanine photosensitizers for the potential treatment of skin cancer with PDT.","authors":"Meryem Çamur Demir, Fatma Kurşun Baysak, Caner Yahya Boyar, Alihan Toksoy, Fatih Algi","doi":"10.55730/1300-0527.3665","DOIUrl":"https://doi.org/10.55730/1300-0527.3665","url":null,"abstract":"<p><p>This research aims to examine the transdermal release of water-soluble indium and zinc metallo phthalocyanine (InPc and ZnPc) compounds from the poly(vinyl alcohol) (PVA) membrane and the cytotoxicity effect of these Pcs on normal mouse fibroblasts (L929 fibroblast) and human melanoma (SK-MEL-30) cells. For this purpose, the effects of temperature, pH, drug concentration and membrane thickness on transdermal release were investigated in order to obtain the optimum transdermal release profile by preparing PVA membranes with different thicknesses and crosslinked by heat treatment. Optimum drug release was found to be 85.36% using 6 μm thick PVA membrane at 37 ± 0.5 °C, when upper cell pH 1.2 and lower cell pH 5.5, for 3 mg/mL InPc drug concentration. Under the same conditions, the drug release value for ZnPc was found to be 69.78%. In addition, in vitro studies were performed on L929 and SK-MEL-30 cells. under optimized drug (InPc and ZnPc) and membrane conditions. It was found that no significant cytotoxic effect was observed in L929 and SK-MEL-30 cells in the dark. Photodynamic tests were also carried out with InPc and ZnPc. The results show that cell viability decreases in SK-MEL-30 cells at concentrations of 10 μg/mL and above. In addition, while the InPc IC50 value was determined as 4.058 μg/mL, this value was determined as 11.574 μg/mL for ZnPc.</p>","PeriodicalId":23367,"journal":{"name":"Turkish Journal of Chemistry","volume":"48 2","pages":"376-386"},"PeriodicalIF":1.3,"publicationDate":"2024-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11265854/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141761201","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the efficiency of nitrogenated carbon quantum dots/TiO₂ S-scheme heterojunction in the photodegredation of ciprofloxacin in aqueous environments.","authors":"Yılmaz Ateş, Zafer Eroğlu, Özkan Açişli, Önder Metin, Semra Karaca","doi":"10.55730/1300-0527.3679","DOIUrl":"https://doi.org/10.55730/1300-0527.3679","url":null,"abstract":"<p><p>In this study, we developed a heterojunction photocatalyst, namely nitrogen-doped carbon quantum dots/titanium dioxide (<i>N-</i>CQDs/TiO₂), for the effective and sustainable treatment of ciprofloxacin (CIP) antibiotic in aqueous solution. First, <i>N-</i>CQDs were prepared from a chitosan biopolymer with a green, facile, and effective hydrothermal carbonization technique and then anchored on the TiO₂ surface via a hydrothermal process. The morphological, structural, and optical properties of the as-prepared materials were characterized by using advanced analytical techniques. The impacts of the mass percentage of <i>N</i>-CQDs, catalyst and CIP concentration, and pH on photocatalytic CIP degradation were investigated in depth. Comparative analyses were performed to evaluate different processes including adsorption, photolysis, and photocatalysis for the removal of CIP with TiO₂ and <i>N-</i>CQDs/TiO₂. The results revealed that <i>N</i>-CQDs/TiO₂ exhibited the highest CIP removal efficiency of up to 83.91% within 120 min using UVA irradiation under optimized conditions (10 mg/L CIP, 0.4 g/L catalyst, and pH 5). Moreover, the carbon source used in the fabrication of <i>N</i>-CQDs was also considered, and lower removal efficiency was obtained when glucose was used as a carbon source instead of chitosan. This excellent improvement in CIP degradation was attributed to the ideal separation and migration of photogenerated carriers, strong redox capability, and high generation of reactive oxygen species provided by the successful construction of the <i>N-</i>CQDs/TiO₂ S-scheme heterojunction. Scavenger experiments indicated that h⁺ and •OH reactive oxygen species were the predominant factors for CIP elimination in water. Overall, this study presents a green synthesis approach for <i>N</i>-CQDs/TiO₂ heterojunction photocatalysts using natural materials, demonstrating potential as a cost-effective and efficient method for pharmaceutical degradation in water treatment applications.</p>","PeriodicalId":23367,"journal":{"name":"Turkish Journal of Chemistry","volume":"48 4","pages":"550-567"},"PeriodicalIF":1.3,"publicationDate":"2024-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11407339/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142296502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Antiviral and cytotoxic activities and chemical profiles of two species of <i>Abies nordmanniana</i> from Türkiye.","authors":"Nazlı Sarikahya, Gaye Sümer Okkali, Furkan O Çöven, Sevda Zeinali, Gülce Gucur, A Dila Çağlar, Ece Uyar, Ahmet C Gören, Ayşe Nalbantsoy","doi":"10.55730/1300-0527.3670","DOIUrl":"https://doi.org/10.55730/1300-0527.3670","url":null,"abstract":"<p><p><i>Abies</i> is an important genus of the family Pinaceae, with about 50 species found in the highlands of Asia, Europe, North Africa, and North and Central America. The principal aim of the present work was to investigate the chemical content and biological potential of the resin and cone from <i>Abies nordmanniana</i> subsp. <i>bornmulleriana</i> and <i>Abies nordmanniana</i> subsp. <i>equi-trojani</i>, respectively. The flavonoid and phenolic contents of the resin and cones were evaluated using liquid chromatography-high resolution mass spectrometry (LC-HRMS). Additionally, the essential oil and fatty acid compositions were analyzed using gas chromatography-mass spectrometry (GC-MS) and gas chromatography-flame ionization detector (GC-FID), respectively. Cytotoxicity of the extracts and essential oils were screened against certain cancer cell lines, namely, human prostate adenocarcinoma cell line (PC3), human lung adenocarcinoma cell line (A549), human pancreatic cancer cell line (PANC-1), human hepatocellular carcinoma cell line (HepG2), human breast cancer cell line (MDA-MB231), and normal human lung fibroblast cell line (CCD-34-LU), with MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide] assay. According to the MTT results, hexane extracts of both cone (CH) and resin (RH), ethanol-water (CEW), dichloromethane (CD), and acetone (CA) extracts of the cone mostly inflict cytotoxicity in HepG2 cell line. Antiviral activities of <i>Abies nordmanniana</i> subsp. extracts at doses of 5 μg/g and 10 μg/g were also evaluated in ovo for their virucidal activity against avian coronavirus. <i>Abies nordmanniana</i> subsp. extracts exhibited concentration-dependent antiviral activity on specific pathogen-free embryonated chicken eggs. Significantly, cone acetone extract (CA), cone ethanol extract (CE), and cone dichloromethane extract (CD) of <i>Abies nordmanniana</i> subsp. exhibited strong inhibition of the virus at a concentration of 10 μg/g. The most potent virucidal activity was observed with ethanol-water extract of conifer form (CEW). According to these results, it was proved that <i>Abies nordmanniana</i> species could be a potential, sustainable, and renewable drug source, especially considering the impressive antiviral and significant cytotoxic activity potentials.</p>","PeriodicalId":23367,"journal":{"name":"Turkish Journal of Chemistry","volume":"48 3","pages":"436-447"},"PeriodicalIF":1.3,"publicationDate":"2024-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11265925/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141761202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rapid synthesis of azoindolizine derivatives via aryldiazonium salts.","authors":"Ferruh Lafzi","doi":"10.55730/1300-0527.3675","DOIUrl":"https://doi.org/10.55730/1300-0527.3675","url":null,"abstract":"<p><p>A practical, rapid, and efficient method for the synthesis of azoindolizine derivatives via aryldiazonium salts with excellent yields was reported. Firstly, the corresponding aniline derivatives were synthesized via a simple and rapid method. Then, the optimal reaction conditions were investigated using a variety of protic and aprotic solvents that demonstrating the robustness of the approach. Finally, the applicability of this method to various sources of indolizine and phenyldiazonium tetrafluoroborate salts was expanded.</p>","PeriodicalId":23367,"journal":{"name":"Turkish Journal of Chemistry","volume":"48 3","pages":"506-511"},"PeriodicalIF":1.3,"publicationDate":"2024-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11265887/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141763993","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sensitive and accurate determination of oil-soluble and water-soluble organosulfur compounds in garlic matrix using reversed phase-high performance liquid chromatography.","authors":"Ümmügülsüm Polat Korkunç, Buse Tuğba Zaman, Sezgin Bakirdere, Emine Karakuş","doi":"10.55730/1300-0527.3658","DOIUrl":"https://doi.org/10.55730/1300-0527.3658","url":null,"abstract":"<p><p>Garlic is in the family Liliaceae and has many different constituents such as organic sulfur compounds, amino acids, carbohydrates, minerals, and vitamins. In this work, a simple, sensitive, and accurate analytical method was developed for the determination of selected organosulfur compounds (OSCs) in garlic bulbs using reversed phase-high performance liquid chromatography (RP-HPLC). Oil-soluble and water-soluble OSCs were extracted from the garlic samples via acetonitrile and deionized water, respectively. The OSCs were separated on a Phenomenex C18 (250 mm, 4 mm, 5mm) column and the monitoring was performed with a UV detector at 220 nm. An isocratic mobile phase comprising of 0.10 M trifluoroacetic acid (TFA) in 85% acetonitrile (ACN) and 0.10 M TFA in distilled water (DW) (90: 10% v/v) was used to elute the analytes. Under optimum experimental conditions, the limits of detection (LOD) for the analytes were calculated in the range of 0.09 to 0.17 mg/kg. For the garlic sample extracts analyzed under optimal instrumental conditions, DAS (diallyl sulfide), DADS (diallyl disulfide), and DATS (diallyl trisulfide) were detected in the ranges of 8.0 to 32.5 mg/kg, 20.4 to 67.3 mg/kg, and 60.7 to 356.6 mg/kg, respectively. Spiked recovery experiments were conducted on the garlic samples to confirm the method's applicability and accuracy. The recovery results ranged between 39.0% and 90.9% for the garlic samples extracted with deionized water. The developed method is simple, precise, accurate, reliable, and time-effective for the determination of OSCs. Additionally, the green profile of the developed method was investigated by using AGREEprep software and the greenness score was recorded as 0.65, indicating that the method developed is environmentally friendly.</p>","PeriodicalId":23367,"journal":{"name":"Turkish Journal of Chemistry","volume":"48 2","pages":"281-288"},"PeriodicalIF":1.3,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11265896/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141761199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hummers' method-assisted liquid-phase exfoliation enables the fabrication of few-layer borophene from bulk boron.","authors":"Mehmet Semih Bingöl, Mehmet Yilmaz, Ahmet Emre Kasapoğlu","doi":"10.55730/1300-0527.3659","DOIUrl":"https://doi.org/10.55730/1300-0527.3659","url":null,"abstract":"<p><p>The fabrication of few-layer borophene (BP) from bulk boron (b-B) is of great importance and still a scientific challenge due to the complex structure and crystallinity of b-B. Herein, we propose a novel technique to prepare a few-layer BP on a large scale with a large lateral size in a well-controlled manner. For this, we employed the Hummers' method-assisted liquid-phase exfoliation. In the first step, the chemical exfoliation of the b-B as a precursor was performed by the modified Hummers' method. After chemical exfoliation, mechanical delamination was employed by using an immersion sonicator. Finally, BP sheets were collected with dimensions ranging from several hundred nanometers to a few micrometers and an average thickness of 4.2 nm. We envision that the proposed low-cost, flexible, and large-scale production method will provide unique advantages for the application of few-layer BP in the realization of high-performance electronics, optoelectronics, flexible devices, sensing systems, energy conversion, and storage devices.</p>","PeriodicalId":23367,"journal":{"name":"Turkish Journal of Chemistry","volume":"48 2","pages":"289-298"},"PeriodicalIF":1.3,"publicationDate":"2024-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11265855/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141761178","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Construction of hyperbranched imprinted nanomaterials for selective adsorption of cadmium (II).","authors":"Sheng Nan Hu, Xinyu Zhang, Ming Guo, Shengchun Wu, Wenjun Lu","doi":"10.55730/1300-0527.3664","DOIUrl":"https://doi.org/10.55730/1300-0527.3664","url":null,"abstract":"<p><p>A hyperbranched ion-imprinted polymer (IIP) material containing multiple selective adsorption sites was synthesized using halloysite nanotubes, methyl acrylate, and ethylenediamine in the presence of a template ion [i.e. Cd (II) heavy metal]. The successful preparation of the Cd-IIP composition was confirmed by FT-IR, XRD, TEM, TGA, and elemental analysis. The polymers exhibited good adsorption of Cd (II) with a maximum adsorption capacity of 64.37 mg·g^-1. The imprinting factor (α) for Cd (II) was 2.62 and the selection factor (β) was 1.78, indicating a specific adsorption of Cd (II) ion. The selection coefficients of Cd-IIP for Cd (II)/Pb (II), Cd (II)/Cu (II), Cd (II)/Ni (II), Cd (II)/Cr (III), and Cd (II)/Na (I) also indicated an excellent selectivity of the hyperbranched polymers for Cd (II) in the presence of competitive ions. The removal efficiency remained more than 75% after five cycles of desorption/adsorption. We envision that the HNTs based Cd-IIP has promising applications in the removal of Cd (II) from wastewater.</p>","PeriodicalId":23367,"journal":{"name":"Turkish Journal of Chemistry","volume":"48 2","pages":"364-375"},"PeriodicalIF":1.3,"publicationDate":"2024-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11265921/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141761161","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Improving the water solubility of cannabidiol using a peptide carrier.","authors":"Melek Parlak Khalily","doi":"10.55730/1300-0527.3655","DOIUrl":"https://doi.org/10.55730/1300-0527.3655","url":null,"abstract":"<p><p>Cannabidiol (CBD), nonpsychotropic cannabinoid found in <i>Cannabis sativa</i>, is a very promising drug candidate offering many differential effects such as sedative, antiinflammatory, antioxidant, and neuroprotective properties. Nevertheless, the therapeutic use of CBD is hindered by its lack of water solubility and relatively low bioavailability. Various carriers have been used to address the solubility issues of CBD and other highly lipophilic drugs so far. However, self-assembled peptide nanostructures as carrier have not been used to improve the water solubility of CBD yet. In this study, a self-assembling peptide micelle was demonstrated to be an effective vehicle for encapsulation of CBD and increased its aqueous solubility up to 2000-fold compared to CBD itself.</p>","PeriodicalId":23367,"journal":{"name":"Turkish Journal of Chemistry","volume":"48 2","pages":"229-236"},"PeriodicalIF":1.3,"publicationDate":"2024-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11265886/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141761179","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Graphene aerogels: part 1 - derived from graphene oxide and thermally reduced graphene oxide via supercritical carbon dioxide drying.","authors":"Meryem Samanci, Ayşe Bayrakçeken","doi":"10.55730/1300-0527.3657","DOIUrl":"https://doi.org/10.55730/1300-0527.3657","url":null,"abstract":"<p><p>Graphene aerogels have become promising materials in many areas of industry, especially in energy applications due to their superior physical and electrochemical properties. Generally, graphene oxide (GO)-derived aerogels (A) are synthesized by using the hydrothermal method. In this study, both GO and reduced graphene oxide (RGO)-derived aerogels were synthesized by using the sol-gel method coupled with the supercritical carbon dioxide (SCCO₂) drying process. It aims to examine the changes in the structure of the final aerogel by changing the amount (0.25-0.5-1% wt.) and type of graphene-based precursor materials used in the synthesis. Physical characterizations of graphene aerogels were conducted using Brunauer-Emmett-Teller (BET) analysis, scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis, transmission electron microscopy (TEM), micro-Raman spectroscopy, X-ray diffractometer (XRD) to highlight their structural properties. Additionally, X-ray photoelectron spectroscopy (XPS) analyses were performed to determine the oxidation levels on the surface of the RGO-1 aerogel. The cyclic voltammetry (CV) method was used to examine the electrochemical behavior of the graphene aerogels against corrosion. Specific capacitance values of the synthesized materials were calculated before and after corrosion. Furthermore, the surface charge changes that occur after corrosion were examined. GOAs displayed the highest specific capacitance value among graphene aerogels. Notably, the RGOA-1 aerogel exhibited the highest corrosion resistance. The pseudo-capacitive charge ratio of RGOA-1 after corrosion was measured at 0.5 mC cm^-2.</p>","PeriodicalId":23367,"journal":{"name":"Turkish Journal of Chemistry","volume":"48 2","pages":"251-280"},"PeriodicalIF":1.3,"publicationDate":"2024-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11265928/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141761176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Graphene aerogels: part 2 - derived from commercial graphene and chemically reduced graphene oxide via supercritical carbon dioxide drying.","authors":"Meryem Samanci, Ayşe Bayrakçeken","doi":"10.55730/1300-0527.3660","DOIUrl":"https://doi.org/10.55730/1300-0527.3660","url":null,"abstract":"<p><p>Graphene aerogels (GAs), the most important class of carbonaceous aerogels, have attracted attention of many researchers due to their superior physical and chemical properties. In this study, commercial graphene (GR) and chemically reduced graphene oxide (RGO) were used as graphene-based precursor materials, unlike graphene oxide (GO), which is widely used in the literature in GA synthesis. GAs were synthesized using the sol-gel technique and dried with supercritical carbon dioxide (SCCO₂). In addition, graphene-based materials were used in different ratios and their distribution in the aerogel matrix and its effect on surface properties were investigated. In addition, the synthesized GAs were structurally compared with GR, RGO, and carbon aerogel (CA) without graphene-based materials. Physical characterizations (Brunauer, Emmett, and Teller (BET) analysis, scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis, micro-Raman spectroscopy, X-ray diffractometer (XRD) were made to examine the structural properties of GAs. In order to analyze the behavior of the surfaces of the synthesized materials against electrochemical corrosion, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) analyses were performed. As a result of the electrochemical corrosion process of the synthesized materials, the change in their specific capacitance and the formation of pseudocapacitive charge on the surfaces were examined.</p>","PeriodicalId":23367,"journal":{"name":"Turkish Journal of Chemistry","volume":"48 2","pages":"299-328"},"PeriodicalIF":1.3,"publicationDate":"2024-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11265932/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141761177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}