bluuebunny/crossref_metadata_2025 huggingface dataset:
Through the Maze: Cross‐Coupling Pathways to a Helical Hexaphenyl “Geländer” Molecule
Authors: Rickhaus Michel , Bannwart Linda Maria , Unke Oliver , Gsellinger Heiko , Häussinger Daniel , Mayor Marcel
Published: December 2014

This paper highlights a new concept on how to induce chirality in a hexaphenyl Geländer‐type system. Bridging a terphenyl backbone with a considerably longer benzyl ether oligomer enforces a continuous twist of the molecule, while preventing an achiral meso form. By highlighting cross‐coupling strategies and explored synthetic pathways, this report aims to serve as an Ariadne's thread for the synthesis of precisely functionalized, complex polyaromatic systems. The synthetic challenges and considerations required to access the designed target are outlined and solutions to each step of the assembly are presented. Encountered isomerizations are discussed as much as synthetic tools to access highly functionalized intermediates with multiorthogonal moieties. A strong focus is made on the employment of Suzuki–Miyaura protocols for the targeted connection of polyaromatic fragments and ultimately the desired oligomeric structure.
Algae as production systems of bioactive compounds
Authors: Michalak Izabela , Chojnacka Katarzyna
Published: December 2014

Algal extracts are gaining increasing interest due to their unique composition and possibilities of wide industrial applications. Various extraction techniques are used for conversion of algal biomass into extracts. Recently, attention of scientists has been paid to novel methods, such as enzyme‐assisted extraction, microwave‐assisted extraction, pressurized liquid extraction, supercritical fluid extraction, and ultrasound‐assisted extraction, which enable the extraction of biologically active compounds without their degradation. In this review, the properties of biologically active compounds extracted from the biomass of algae reported in the literature are presented in a structured way. Algal extracts contain compounds such as carbohydrates, proteins, minerals, oil, fats, polyunsaturated fatty acids as well as bioactive compounds such as antioxidants (polyphenols, tocopherols [vitamin E], vitamin C, mycosporine‐like amino acids), and pigments, such as carotenoids (carotene xanthophyll), chlorophylls, and phycobilins (phycocyanin, phycoerythrin), which possess antibacterial, antiviral, antifungal, antioxidative, anti‐inflammatory, and antitumor properties. Finally, we assemble a list of applications of algal extracts in different developing branches of agriculture (biostimulants, bioregulators, feed additives) and in pharmaceutical industry.
Application of species sensitivity distribution in aquatic probabilistic ecological risk assessment of cypermethrin: A case study in an urban stream in South China
Authors: Li Huizhen , You Jing
Published: December 2014

A tiered ecological risk assessment was applied to quantitatively refine the overall probabilistic risk of cypermethrin, a pyrethroid insecticide, to aquatic organisms. These results were then validated through the bioassays using field water from an urban stream, Chebei Creek in Guangzhou, South China. Seventeen water samples were collected along Chebei Creek for evaluation. In total, 71% of the field waters were acutely toxic to Hyallela azteca and 24% of the waters caused 100% mortality. Toxic unit evaluation suggested that cypermethrin was one of the main contributors to toxicity. The tiered ecological risk assessment approach (deterministic quotient method and probabilistic methods, including joint probability curve and Monte Carlo Simulation) suggested that cypermethrin posed significant threats to aquatic ecology in this stream. The overall probabilistic risk of cypermethrin to aquatic species in Chebei Creek reached 66% when acute-to-chronic ratios were set at 125. An exceedance probability of cypermethrin in Chebei Creek that affected H. azteca as modeled using the joint probability curve method was 88%, suggesting that most sites were at risk due to cypermethrin exposure. This value was similar to the results obtained from acute toxicity tests (71% of field water samples were acutely toxic to H. azteca), indicating the effectiveness of the tiered approach to assess risk of cypermethrin in urban waterways. To the authors' knowledge, the present study is the first to provide a focused probabilistic evaluation of ecological risk for cypermethrin in a complex urban waterway environment. Despite uncertainties existing in the ecological risk assessment procedure, this approach provides a comprehensive assessment of ecological risk of cypermethrin, and subsequently, a foundation for further risk diagnosis and management in urban waterways. Environ Toxicol Chem 2015;34:640–648. © 2014 SETAC
Fate of flame retardants and the antimicrobial agent triclosan in planted and unplanted biosolid-amended soils
Authors: Davis Elizabeth F. , Gunsch Claudia K. , Stapleton Heather M.
Published: December 2014

A comprehensive understanding of the fate of contaminant-laden biosolids is needed to fully evaluate the environmental impacts of biosolid land application. The present study examined the fate of several flame retardants and triclosan in biosolid-amended soil in a 90-d greenhouse experiment. Objectives included evaluating the persistence of these compounds in soil, their phytoaccumulation potential by alfalfa (Medicago sativa), and potential degradation reactions. Concentrations of the polybrominated diphenyl ether (PBDE) congeners BDE-47 and BDE-209 and the antimicrobial triclosan declined significantly over time in biosolid-amended soil planted with alfalfa and then reached a steady state by day 28. In contrast, no significant losses of those analytes were observed from soil in nonvegetated pots. The amount of an analyte lost from vegetated soil ranged from 43% for the flame retardant di(2-ethylhexyl)-2,3,4,5-tetrabromophthalate to 61% for triclosan and was significantly and negatively related to the log octanol–water partition coefficient. Alfalfa roots and shoots were monitored for the compounds, but no clear evidence of phytoaccumulation was observed. Methyl triclosan formation was observed in the biosolid-amended soils during the study period, indicating in situ biotransformation of triclosan. The present study demonstrates that, although they are highly recalcitrant, PBDEs, selected alternate brominated flame retardants, and triclosan are capable of undergoing dissipation from biosolid-amended soils in the presence of plants. Environ Toxicol Chem 2015;34:968–976. © 2014 SETAC
The influence of natural organic matter and aging on suspension stability in guideline toxicity testing of silver, zinc oxide, and titanium dioxide nanoparticles with Daphnia magna
Authors: Cupi Denisa , Hartmann Nanna B. , Baun Anders
Published: December 2014

The present study investigated changes in suspension stability and ecotoxicity of engineered nanoparticles (ENPs) by addition of Suwannee River natural organic matter and aging of stock and test suspensions prior to testing. Acute toxicity tests of silver (Ag), zinc oxide (ZnO), and titanium dioxide (TiO2) ENPs with Daphnia magna were carried out following Organisation for Economic Co-operation and Development test guidelines. Daphnia magna was found to be very sensitive to Ag ENPs (48-h 50% effective concentration 33 μg L−1), and aging of the test suspensions in M7 medium (up to 48 h) did not decrease toxicity significantly. Conversely, the presence of Suwannee River natural organic matter (NOM; 20 mg L−1) completely alleviated Ag ENP toxicity in all testing scenarios and did not aid in stabilizing suspensions. In contrast, addition of Suwannee River NOM stabilized ZnO ENP suspensions and did not decrease toxicity. Aging for 48 h generated monotonous concentration–response curves in the presence and absence of Suwannee River NOM. At concentrations up to 100 mg L−1 TiO2 ENPs did not cause immobilization of D. magna under any of the tested conditions. Presence of Suwannee River NOM caused agglomeration in stock suspensions. The authors' results suggest that aging and presence of Suwannee River NOM are important parameters in standard toxicity testing of ENPs, which in some cases may aid in gaining better control over the exposure conditions but in other cases might contribute to agglomeration or elimination of ENP toxicity. Therefore, modifications to the current guidelines for testing ENPs should be evaluated on a case-by-case basis. Environ Toxicol Chem 2015;34:497–506. © 2014 SETAC
The Effect of 6 versus 9 Years of Zoledronic Acid Treatment in Osteoporosis: A Randomized Second Extension to the HORIZON-Pivotal Fracture Trial (PFT)
Authors: Black Dennis M. , Reid Ian R. , Cauley Jane A. , Cosman Felicia , Leung Ping Chung , Lakatos Peter , Lippuner Kurt , Cummings Steven R. , Hue Trisha F. , Mukhopadhyay Amitava , Tan Monique , Aftring R. Paul , Eastell Richard
Published: December 2014

While bisphosphonates reduce fracture risk over 3 to 5 years, the optimal duration of treatment is uncertain. In a randomized extension study (E1) of the Health Outcomes and Reduced Incidence with Zoledronic Acid Once Yearly−Pivotal Fracture Trial (HORIZON−PFT), zoledronic acid (ZOL) 5 mg annually for 6 years showed maintenance of bone mineral density (BMD), decrease in morphometric vertebral fractures, and a modest reduction in bone turnover markers (BTMs) compared with discontinuation after 3 years. To investigate the longer-term efficacy and safety of ZOL, a second extension (E2) was conducted to 9 years in which women on ZOL for 6 years in E1 were randomized to either ZOL (Z9) or placebo (Z6P3) for 3 additional years. In this multicenter, randomized, double-blind study, 190 women were randomized to Z9 (n = 95) and Z6P3 (n = 95). The primary endpoint was change in total hip BMD at year 9 vs. year 6 in Z9 compared with Z6P3. Other secondary endpoints included fractures, BTMs, and safety. From year 6 to 9, the mean change in total hip BMD was −0.54% in Z9 vs. −1.31% in Z6P3 (difference 0.78%; 95% confidence interval [CI]: −0.37%, 1.93%; p = 0.183). BTMs showed small, non-significant increases in those who discontinued after 6 years compared with those who continued for 9 years. The number of fractures was low and did not significantly differ by treatment. While generally safe, there was a small increase in cardiac arrhythmias (combined serious and non-serious) in the Z9 group but no significant imbalance in other safety parameters. The results suggest almost all patients who have received six annual ZOL infusions can stop medication for up to 3 years with apparent maintenance of benefits. © 2015 American Society for Bone and Mineral Research.
Benefits of fresh‐frozen plasma as a replacement fluid to neutralize ABO antibodies
Authors: Won Dong Il , Ham Ji Yeon , Kim Chan Duck , Suh Jang Soo , Kim Byung Chang
Published: December 2014

Background

ABO‐incompatible organ transplantation requires pre‐transplant conditioning to reduce ABO antibody levels in the recipients. With respect to replacement fluids used in plasma exchange, we intended to verify whether fresh‐frozen plasma (FFP) containing soluble ABO substance (SAS) is more effective than albumin solution in reducing ABO IgG antibody levels.

Methods

Apheresis data were retrospectively studied for in vivo effects, and in vitro plasma mixing studies were prospectively performed. The amount of ABO IgG antibodies bound to red cells was measured as the mean fluorescence intensity (MFI) using flow cytometry. Neutralization of ABO antibodies in the recipientst plasma by an ABO‐incompatible donornc plasma was measured using the inhibition assay principle. The MFI value of the unneutralized control tube was divided by that of the neutralized test tube (neutralizing‐capacity index, NCI).

Results

The plasma exchange procedures replaced with group AB FFP showed a significantly greater decreased titer than those replaced with albumin (P = 0.010). The in vitro plasma mixing study simulating plasma exchange also produced consistent results. When the pooled group O plasma was neutralized for anti‐A by individual group AB plasmas (AB‐to‐O, N = 30), the NCI was 12.8 ± 5.4 (6.5–29.5). When this group O plasma was neutralized by pooled group AB or A plasma, the repeatedly measured NCI (N = 5) of A‐to‐O (11.4 ± 1.4) was not significantly different from that of AB‐to‐O (9.7 ± 1.3, P = 0.074).

Conclusions

ABO antibody levels are reduced more effectively by group AB FFP than by albumin. Either group AB or donor type (group A or B) FFP can be infused to group O recipients. FFP units with higher SAS levels can be selected from multiple available candidate units using our protocol for measuring the neutralizing‐capacity. J. Clin. Apheresis 30:288–296, 2015. © 2014 Wiley Periodicals, Inc.
Role of Wnt/β‐Catenin Signaling in Epithelial Differentiation of Lung Resident Mesenchymal Stem Cells
Authors: Shi Chaowen , Lv Tengfei , Xiang Zou , Sun Zhaorui , Qian Weiping , Han Xiaodong
Published: December 2014

Accumulating evidence has demonstrated that stem cells have the ability to repair the lung tissue injuries following either injection of cultured cells or bone marrow transplantation. As a result, increasing attention has focused on the lung resident mesenchymal stem cells (LR‐MSCs) for repairing damaged lung tissues. Meanwhile, some studies have revealed that Wnt/β‐catenin signaling plays an important role in the epithelial differentiation of mesenchymal stem cells (MSCs). In the current study, our aim was to explore the roles of Wnt/β‐catenin signaling on cell proliferation and epithelial differentiation of LR‐MSCs. We have successfully isolated the stem cell antigen (Sca)‐1+CD45−CD31− cells which were proposed to be LR‐MSCs by magnetic‐activated cell sorting (MACS). Furthermore, we demonstrated the expression of epithelial markers on LR‐MSCs following indirect co‐culture of these cells with alveolar epithelial type II (ATII) cells, confirming the epithelial phenotype of LR‐MSCs following co‐culture. In order to clarify the regulatory mechanisms of Wnt/β‐catenin signaling in epithelial differentiation of LR‐MSCs, we measured the protein levels of several important members involved in Wnt/β‐catenin signaling in the presence or absence of some canonical activators and inhibitors of the β‐catenin pathways. In conclusion, our study demonstrated that Wnt/β‐catenin signaling may be an essential mechanism underlying the regulation of epithelial differentiation of LR‐MSCs. J. Cell. Biochem. 116: 1532–1539, 2015. © 2015 Wiley Periodicals, Inc.
Internalization of Near‐Infrared Fluorescently Labeled Activatable Cell‐Penetrating Peptide and of Proteins into Human Fibrosarcoma Cell Line HT‐1080
Authors: Tansi Felista , Kallweit Eric , Kaether Christoph , Kappe Katarina , Schumann Christina , Hilger Ingrid , Reissmann Siegmund
Published: December 2014

The internalization of near‐infrared fluorescently labeled cargos into living cells and tissues allows a highly sensitive detection without interference from skin, porphins or other fluorescent cell and tissue compounds. In this study, the uptake of labeled bovine serum albumin and an antibody, into fibrosarcoma (HT‐1080) cells was triggered by the formation of non‐covalent complexes with different cell‐penetrating peptides; uptake efficiency and intracellular localization were determined. To improve selectivity of internalization into tumor cells, a fluorescent activatable cell‐penetrating peptide (ACPP) was synthesized and functionally characterized. This 25‐mer peptide was designed to be activatable by Matrix‐Metallo‐Proteases (MMPs). Its uptake selectivity was estimated using cells with different MMP activities. J. Cell. Biochem. 116: 1222–1231, 2015. © 2014 Wiley Periodicals, Inc.
HIF‐1 Alpha and Placental Growth Factor in Pregnancies Complicated With Preeclampsia: A Qualitative and Quantitative Analysis
Authors: Rath Gayatri , Aggarwal Ruby , Jawanjal Poonam , Tripathi Richa , Batra Aruna
Published: December 2014

Background

The pathophysiology of preeclampsia is not clearly understood worldwide. Hypoxia inducible factor 1α (HIF‐1α) is thought to be the preliminary factor for the hypoxic conditions prevailing in preeclampsia, which causes imbalance in the expression of angiogenic proteins. A proangiogenic protein, placental growth factor (PIGF), is reported to be dysregulated in preeclampsia. Therefore, this study focuses on the investigation of HIF‐1α and PIGF in preeclamptic conditions and a possible molecular association between them.

Methods

Placental tissue (n = 45 + 45) and serum samples (n = 80 + 80) of preeclamptic patients and healthy control were collected and processed for the analysis of HIF‐1α and PIGF by immunohistochemistry and enzyme‐linked immunosorbent assay (ELISA).

Results

In preeclamptic group, the significant nuclear and cytoplasmic expression of HIF‐1α was noticed in syncytiotrophoblast (P = 0.0001) but in control placenta, it was localized to cytoplasm (P = 0.0001). The intensity of PIGF expression was lower in syncytiotrophoblast cytoplasm (P = 0.0001) in preeclamptic cases as compared with control. Also, the significant upregulated concentration of HIF‐1α and downregulated PIGF was observed in serum samples of preeclamptic woman (P = 0.0001). Thus, there was a significant direct negative correlation between HIF‐1α and PIGF both at tissue and serum level (P < 0.01).

Conclusion

The direct inverse association between HIF‐1α and PIGF in serum and placental tissues may be responsible for the low oxidative stress and endothelial dysfunction, leading to the pathogenesis of preeclampsia.
Development of Pyrosequencing Method for Detection of UGT1A1 Polymorphisms in Thai Colorectal Cancers
Authors: Sukasem Chonlaphat , Atasilp Chalirmporn , Chansriwong Pichai , Chamnanphon Montri , Puangpetch Apichaya , Sirachainan Ekapob
Published: December 2014

Background

UGT1A1 is a polymorphic enzyme that has been associated with irinotecan drug metabolisms. We developed a pyrosequencing method to detect allele frequency and genotype of UGT1A1 polymorphisms (UGT1A1*28 and UGT1A1*6) in Thai colorectal cancer patients.

Method

A pyrosequencing method was designed to determine UGT1A1 genetic polymorphisms including UGT1A1*28 (A[TA]7TAA) and UGT1A1*6 (211G>A) in 91 Thai colorectal cancers.

Result

Genotyping by the pyrosequencing technique was 100% concordant with capillary electrophoresis sequencing. The allele frequencies for UGT1A1 genetic polymorphisms were *1/*1 (54.95%), *1/*6 (13.19%), *1/*28 (25.27%), *28/*6 (4.40%), and *28/*28 (2.20%). No homozygous mutation UGT1A1*6 was found in our population.

Conclusions

We developed a rapid, reliable, more cost‐effective, and simple assay to detect UGT1A1 genetic polymorphisms in routine practice before initiating irinotecan therapy. The UGT1A1*28 and UGT1A1*6 alleles were found to be similar in the Asian populations.
Development of a Sol Particle Homogeneous Immunoassay for Measuring Full‐Length Selenoprotein P in Human Serum
Authors: Tanaka Mutsumi , Saito Yoshiro , Misu Hirofumi , Kato Seiji , Kita Yuki , Takeshita Yumie , Kanamori Takehiro , Nagano Toru , Nakagen Masatoshi , Urabe Takeshi , Takamura Toshinari , Kaneko Shuichi , Takahashi Kazuhiko , Matsuyama Naoto
Published: December 2014

Background

Selenoprotein P (SeP), a selenium‐rich extracellular glycoprotein, is the primary selenoprotein in the plasma. SeP plays an important role in the maintenance of selenium levels in the peripheral tissues. We developed a new sol particle homogeneous immunoassay (SPIA) for measuring full‐length SeP (FL‐SeP) levels in the human serum.

Methods

We used colloidal gold particles coated with two types of anti‐SeP monoclonal antibodies, one recognizing the N‐terminal side domain of SeP and the other recognizing the C‐terminal side domain.

Results

The assay range was 0.2–9 mg/l, and the linearity was excellent. The within‐day and between‐day coefficients of variation ranged from 0.73% to 2.24% and 0.45% to 1.11%, respectively. Serum samples (n = 200) were examined using the newly developed assay system (employing a Model 7070 Hitachi automatic clinical analyzer) and the conventional enzyme‐linked immunosorbent assay. These two methods were compared using the Passing–Bablok regression analysis; the resulting regression equation and correlation coefficient were y = 0.940x + 0.165 and r = 0.954, respectively.

Conclusions

Our new SPIA assay is a fully automated homogeneous immunoassay that can be used in conjunction with various commercial analyzers. The assay was sensitive, precise, and suitable for clinical measurement of the FL‐SeP in the human serum.
Diagnostic Algorithm for the Diagnosis of Pediatric Parasitic Gastroenteritis
Authors: Beal Stacy G. , Couturier Marc Roger , Gander Rita M. , Doern Christopher D.
Published: December 2014

Background

Current practices for ordering stool studies in patients with abdominal and gastrointestinal symptoms are not standardized. We hypothesized that an algorithm involving first‐line use of a Cryptosporidium/Giardia combination antigen test and stricter use of ova and parasite (O&P) examinations would be clinically and cost effective.

Methods

In this study, stool O&P test results for pediatric patients in Dallas, Texas, were reviewed. All results obtained between 2009 and 2012 were included. Patient charts were reviewed to determine test results, symptoms, treatment, travel, and past medical history. Using these data, a retrospective modeling study was done to evaluate the utility of a diagnostic algorithm that limits O&P testing to those patients who are immunocompromised or have travelled outside the United States.

Results

Over the 3‐year period of this study, we found that the prevalence of gastrointestinal parasitic disease in children was 1.9%. Analysis of the diagnostic algorithm for the judicious use of stool O&P showed that as much as 65% of testing may be unnecessary and could be eliminated.

Conclusions

Our findings show that the prevalence of pediatric gastrointestinal parasitic disease in Texas may be lower than expected. In addition, these data show that a diagnostic algorithm limiting O&P testing may be both clinically and cost effective in low‐prevalence settings. However, such an algorithm would miss a significant number of infections due to Dientamoeba fragilis and Blastocystis hominis.
A Mutagenic Primer Assay for Genotyping of the CRHR1 Gene Rare Variant rs1876828 (A/G) in Asians: A Cost‐Effective SNP Typing
Authors: Sharma Neeraj , Awasthi Shally , Phadke Shubha R
Published: December 2014

Background

Today, the genetic and genomic research entered in a new era of high‐throughput genotyping technology. However, mutagenic polymerase chain reaction–restriction fragment length polymorphism (PCR‐RFLP) is still a choice of genotyping method in molecular epidemiological research. It has been extensively used for the detection of risk alleles, if the target SNP has no natural discriminating restriction site. We undertook this study to develop a mutagenic primer assay for a CRHR1 rare gene variant: rs1876828 (A/G) and to determine their allele frequency in north Indian children.

Methods

The mutagenic primers were designed and assay conditions were optimized to perform mutagenic PCR‐RFLP in 550 subjects. The efficiency of assay and results were validated by sequencing.

Results

This study demonstrated that the mutagenic primer assay is feasible and applicable to discriminate CRHR1 gene rare variant rs1876828 (A/G) and the “frequency of allele “G” was 100% in north Indian asthmatics as well as normal subjects.

Conclusion

This method can be used for both large‐ and small‐scale study of complex genetic, where CRHR1 gene plays the pivotal roles.
Expression of Phosphodiesterase 4B cAMP‐Specific Gene in Subjects With Cryptorchidism and Down's Syndrome
Authors: Salemi Michele , Condorelli Rosita A. , La Vignera Sandro , Castiglione Roberto , Salluzzo Maria Grazia , Bonaccorso Carmela M. , Vinci Mirella , Bosco Paolo , Romano Carmelo , Campagna Cristina , Romano Corrado , Calogero Aldo E.
Published: December 2014

Cryptorchidism represents a risk factor for infertility and germ cell testicular neoplasia. An increased rate of cryptorchidism has been reported in subjects with Down's syndrome. Cyclic nucleotide phosphodiesterases (PDEs) are important messengers that regulate and mediate a number of cellular responses to extracellular signals, such as neurotransmitters and hormones. PDE4B, cAMP‐specific (PDE4B) gene which maps to chromosome 1p31.3 appears to be involved in schizophrenia, chronic psychiatric illness, learning, memory, and mood disturbances. Expression of PDE4 enzymes have been studied in testes of cryptorchid rats. Expression of PDE4B protein examination showed marked degenerative changes in the epithelial lining of the seminiferous tubules. These findings led us to evaluate PDE4 mRNA expression in leukocytes of peripheral blood of five men with DS and cryptorchidism and eleven subjects with DS without cryptorchidism compared with healthy men (controls) by quantitative Real Time PCR (qRT‐PCR).

This study showed that the PDE4B gene was downexpressed in men with DS and cryptorchidism compared to normal controls and DS without cryptorchidism. A lower expression of the PDE4B gene may be involved in the neurological abnormalities in subjects with Down's syndrome. Moreover, PDE4B gene may be involved in the testicular abnormalities of men with DS and cryptorchidism.
Coated nickel foam electrode for the implementation of continuous electro‐Fenton treatment
Authors: Bocos Elvira , Pérez‐Álvarez David , Pazos Marta , Rodríguez‐Argüelles Maria Carmen , Sanromán Maria Ángeles
Published: December 2014

BACKGROUND

Electro‐Fenton technology has already demonstrated its ability to degrade organic pollutants. In this treatment hydroxyl radicals are formed due to the reaction of the iron catalyst along with in situ electrogenerated H2O2. However, one of the main limitations of this system is the iron released in the treated effluent. Therefore, retention of iron is required, and in this study, the use of a new cathode in which the iron is fixed on nickel foam is proposed as a solution to the electro‐Fenton treatment in continuous processes.

RESULTS

The retention of iron was ensured by its fixation on nickel foam using chitosan, an eco‐friendly polymer, as coating agent. Different chitosan coatings were tested to optimize the manufacturing process of the new cathode. It was concluded that the best electrode for the electro‐Fenton treatment of different dyes (Poly R‐478 and Lissamine Green B) was obtained using a half‐coating electrode cover with iron–chitosan of medium molecular weight. Furthermore, its reusability was positively evaluated in successive cycles. Finally, a continuous treatment using a fluidized bed reactor was successfully performed for the treatment of dye Lissamine Green B.

CONCLUSION

Summarizing, this new cathode is a suitable alternative for the treatment of coloured wastewater by continuous electro‐Fenton treatment. © 2014 Society of Chemical Industry
Assessment of percutaneous transhepatic portal vein embolization with portal vein stenting for perihilar cholangiocarcinoma with severe portal vein stenosis
Authors: Hyodo Ryota , Suzuki Kojiro , Ebata Tomoki , Komada Tomohiro , Mori Yoshine , Yokoyama Yukihiro , Igami Tsuyoshi , Sugawara Gen , Naganawa Shinji , Nagino Masato
Published: December 2014

Background

The aim of the present study was to assess the clinical efficiency of portal vein (PV) stenting when performed with preoperative percutaneous transhepatic portal vein embolization (PTPVE) in patients with severe PV stenosis due to tumor invasion.

Methods

Between 2007 and 2013, four consecutive patients (one male, three females; mean age, 52 years; age range, 25–73 years) with perihilar cholangiocarcinoma and PV stenosis underwent PTPVE and PV stenting. Patients were analyzed with regard to the procedure, hypertrophy of the future remnant liver (FRL), and plasma clearance rate of indocyanine green by the FRL (ICGK‐F). Further, the %FRL volume increase in PTPVE was compared between the stenting group and the usual PTPVE group who have perihilar cholangiocarcinomas without PV stenosis.

Results

Preoperative PTPVE with PV stenting was successfully performed and portal flow to the FRL improved after stenting in all four patients. The %FRL volume increase was 18–60% (mean, 34%) in the stenting group and was 12–51% (mean, 21%) in the usual PTPVE group. The ICGK‐F value after PTPVE exceeded 0.05 in all four patients. All patients achieved R0 resection.

Conclusions

Preoperative PTPVE with PV stenting appears to be feasible in cases of severe PV tumor invasion and stenosis. This procedure may allow a broader indication for surgery.
Optimization and determination of polycyclic aromatic hydrocarbons in biochar‐based fertilizers
Authors: Chen Ping , Zhou Hui , Gan Jay , Sun Mingxing , Shang Guofeng , Liu Liang , Shen Guoqing
Published: December 2014

The agronomic benefit of biochar has attracted widespread attention to biochar‐based fertilizers. However, the inevitable presence of polycyclic aromatic hydrocarbons in biochar is a matter of concern because of the health and ecological risks of these compounds. The strong adsorption of polycyclic aromatic hydrocarbons to biochar complicates their analysis and extraction from biochar‐based fertilizers. In this study, we optimized and validated a method for determining the 16 priority polycyclic aromatic hydrocarbons in biochar‐based fertilizers. Results showed that accelerated solvent extraction exhibited high extraction efficiency. Based on a Box–Behnken design with a triplicate central point, accelerated solvent extraction was used under the following optimal operational conditions: extraction temperature of 78°C, extraction time of 17 min, and two static cycles. The optimized method was validated by assessing the linearity of analysis, limit of detection, limit of quantification, recovery, and application to real samples. The results showed that the 16 polycyclic aromatic hydrocarbons exhibited good linearity, with a correlation coefficient of 0.996. The limits of detection varied between 0.001 (phenanthrene) and 0.021 mg/g (benzo[ghi]perylene), and the limits of quantification varied between 0.004 (phenanthrene) and 0.069 mg/g (benzo[ghi]perylene). The relative recoveries of the 16 polycyclic aromatic hydrocarbons were 70.26–102.99%.
Simultaneous determination of amino acids and neurotransmitters in plasma samples from schizophrenic patients by hydrophilic interaction liquid chromatography with tandem mass spectrometry
Authors: Domingues Diego Soares , Crevelin Eduardo José , de Moraes Luiz Alberto Beraldo , Cecilio Hallak Jaime Eduardo , de Souza Crippa José Alexandre , Costa Queiroz Maria Eugênia
Published: December 2014

A sensitive, reproducible, and rapid method was developed for the simultaneous determination of underivatized amino acids (aspartate, serine, glycine, alanine, methionine, leucine, tyrosine, and tryptophan) and neurotransmitters (glutamate and γ‐aminobutyric acid) in plasma samples using hydrophilic interaction liquid chromatography coupled to triple quadrupole tandem mass spectrometry. The plasma concentrations of amino acids and neurotransmitters obtained from 35 schizophrenic patients in treatment with clozapine (27 patients) and olanzapine (eight patients) were compared with those obtained from 38 healthy volunteers to monitor the effectiveness of treatment. The chromatographic conditions separated ten target compounds within 3 min. This method presented linear ranges that varied from (lower limit of quantification: 9.7–13.3 nmol/mL) to (upper limit of quantification: 19.4–800 nmol/mL), intra‐ and interassay precision with coefficients of variation lower than 10%, and relative standard error values of the accuracy ranged from –2.1 to 9.9%. The proposed method appropriately determines amino acids and neurotransmitters in plasma from schizophrenic patients. Compared with the control group (healthy volunteers), the plasma levels of methionine in schizophrenic patients treated with olanzapine are statistically significantly higher. Moreover, schizophrenic patients treated with clozapine tend to have increased plasma levels of glutamate.
Rapid and sensitive analysis of multiple bioactive constituents in tripterygium glycosides tablets using liquid chromatography coupled with time‐of‐flight mass spectrometry
Authors: Su Meng‐xiang , Zhou Wen‐di , Lan Juan , Di Bin , Hang Tai‐jun
Published: December 2014

A simultaneous determination method based on liquid chromatography coupled with time‐of‐flight mass spectrometry was developed for the analysis of 11 bioactive constituents in tripterygium glycosides tablets, an immune and inflammatory prescription used in China. The analysis was fully optimized on a 1.8 μm particle size C18 column with linear gradient elution, permitting good separation of the 11 analytes and two internal standards in 21 min. The quantitation of each target constituent was carried out using the narrow window extracted ion chromatograms with a ±l0 ppm extraction window, yielding good linearity (r2 > 0.996) with a linear range of 10–1000 ng/mL. The limits of quantitation were low ranging from 0.25 to 5.02 ng/mL for the 11 analytes, and the precisions and repeatability were better than 1.6 and 5.3%, respectively. The acceptable recoveries obtained were in the range of 93.4–107.4%. This proposed method was successfully applied to quantify the 11 bioactive constituents in commercial samples produced by nine pharmaceutical manufacturers to profile the quality of these preparations. The overall results demonstrate that the contents of the 11 bioactive constituents in different samples were in great diversity, therefore, the quality, clinical safety, and efficacy of this drug needs further research and evaluation.
Graphene‐coated cotton fibers as a sorbent for the extraction of multiclass pesticide residues from water and their determination by gas chromatography with mass spectrometry
Authors: Montesinos Isabel , Sfakianaki Afroditi , Gallego Mercedes , Stalikas Constantine D
Published: December 2014

A straightforward functionalization procedure is proposed for synthesizing a cotton‐supported graphene as an extraction material, which is effectively employed for the extraction of multiclass pesticides from environmental waters prior to their determination by gas chromatography with mass spectrometry. Different experimental parameters that affect the extraction efficiency, including pH of the extraction, stirring rate, extraction time, ionic strength, presence of humic acid, sample volume, amount of sorbent, and elution conditions, were investigated and properly established. The advantages of the present extraction method are the simplicity of implementation, rapidity, and low consumption of sorbent per extraction. Moreover, the pesticides on the adsorbent are stable, under certain storage conditions, rendering the cotton‐supported graphene suitable for environmental field studies. The applicability of the cotton–graphene‐based procedure for routine analysis was demonstrated by the determination of pesticides in a lake water sample. The recoveries ranged from 83 to 107%, the limits of quantitation were in the range of 0.02–0.09 μg/L, and the calculated relative standard deviations varied from 3 to 8% (data obtained with the same batch of sorbent). Because of the acceptable analytical characteristics, the developed method shows great prospects in determining certain classes of pesticides in water.
Application of packed porous nanofibers—Solid‐phase extraction for the detection of sulfonamide residues from environmental water samples by ultra high performance liquid chromatography with mass spectrometry
Authors: Chen Rong , Yang Yingying , Wang Na , Hao Lijun , Li Li , Guo Xinyan , Zhang Junchi , Hu Yuzhu , Shen Weiyang
Published: December 2014

Porous electrospun nanofibers, as new materials for solid‐phase extraction, were synthesized by electrospinning and coupled with ultra high performance liquid chromatography and mass spectrometry to determine sulfonamide residues in environmental water. Aligned porous polystyrene electrospun nanofibers were fabricated under the mechanism of phase separation. The high‐specific surface of these nanofibers (70 m2/g) could improve recoveries of the target sulfonamides 4–10 times compared with that of polystyrene nonporous material (3.8 m2/g). Under the optimized conditions, 13 sulfonamide residues showed an excellent linear relationship in the range of 0.125–12.5 ng/mL with a linear correlation coefficient (r2) greater than 0.99, and the detection limits of sulfonamides were as low as 0.80–5.0 ng/L. Compared to the commercial C18and HLB columns, the homemade porous nanofibers columns had some merits including simple fabrication and extraction process, short process time and environmental friendliness. The optimized method was applied to eight water samples collected from different livestock farms (Xuzhou, China). The results showed that polystyrene porous nanofibers were promising to preconcentrate sulfonamides of different polarities in the waste water.
Preparation of a weak anion exchange/hydrophobic interaction dual‐function mixed‐mode chromatography stationary phase for protein separation using click chemistry
Authors: Zhao Kailou , Yang Fan , Xia Hongjun , Wang Fei , Song Qingguo , Bai Quan
Published: December 2014

In this study, 3‐diethylamino‐1‐propyne was covalently bonded to the azide‐silica by a click reaction to obtain a novel dual‐function mixed‐mode chromatography stationary phase for protein separation with a ligand containing tertiary amine and two ethyl groups capable of electrostatic and hydrophobic interaction functionalities, which can display hydrophobic interaction chromatography character in a high‐salt‐concentration mobile phase and weak anion exchange character in a low‐salt‐concentration mobile phase employed for protein separation. As a result, it can be employed to separate proteins with weak anion exchange and hydrophobic interaction modes, respectively. The resolution and selectivity of the stationary phase were evaluated in both hydrophobic interaction and ion exchange modes with standard proteins, respectively, which can be comparable to that of conventional weak anion exchange and hydrophobic interaction chromatography columns. Therefore, the synthesized weak anion exchange/hydrophobic interaction dual‐function mixed‐mode chromatography column can be used to replace two corresponding conventional weak anion exchange and hydrophobic interaction chromatography columns to separate proteins. Based on this mixed‐mode chromatography stationary phase, a new off‐line two‐dimensional liquid chromatography technology using only a single dual‐function mixed‐mode chromatography column was developed. Nine kinds of tested proteins can be separated completely using the developed method within 2.0 h.
Analysis of a new drug of abuse: Cathinone derivative 1‐(3,4‐dimethoxyphenyl)‐2‐(ethylamino)pentan‐1‐one
Authors: Weiß Jennifer A. , Taschwer Magdalena , Kunert Olaf , Schmid Martin G.
Published: December 2014

Recently, novel psychoactive drugs for human abuse such as amphetamines, phenethylamines, benzofuries, and tryptamines, cathinones have gained high popularity. These designer drugs are mainly sold via online stores as “bath salts” and are labeled “not for human consumption.” Due to the novelty of the compounds, only a little information about pharmacology, toxicology, and the long‐term damage they may cause is available. Moreover, there are only few analytical methods for their identification and analysis.

Among new cathinone derivatives, 1‐(3,4‐dimethoxyphenyl)‐2‐(ethylamino)pentan‐1‐one (DL‐4662), became available via an internet shop. A sample of this compound was purchased and investigated.

The first aim of our study was an identity check by NMR spectroscopy and gas chromatography with mass spectrometry. As many of the recreational drugs are chiral and are mainly sold as racemates, a further goal of our research was enantioseparation by gas chromatography with mass spectrometry and high‐performance liquid chromatography with UV detection, to prove whether DL‐4662 was traded enantiomerically pure or as racemic mixture. Both chiral separation methods showed the presence of a racemate.
On‐line determination of sarcosine in biological fluids utilizing dummy molecularly imprinted polymers in microextraction by packed sorbent
Authors: Moein Mohammad Mahdi , Abdel‐Rehim Abbi , Abdel‐Rehim Mohamed
Published: December 2014

Several years ago, sarcosine received attention as a prostate‐cancer marker. Prostate cancer is one of the most widespread types of tumor diseases in men. The prostate‐specific antigen is normally used as a marker, and it can only be detected in blood with a sensitivity of approximately 80%. In the present study, dummy molecularly imprinted polymers in microextraction by packed sorbent with on‐line liquid chromatography coupled to tandem mass spectrometry was used for the determination of sarcosine in human plasma and urine samples. The polymer network glycine was used for the dummy molecularly imprinted polymers. The selectivity of the method was evaluated using similar prostate‐cancer biomarkers. In addition, various parameters affecting the extraction performance were investigated. The method limits of detection and quantification in the plasma and urine were 1.0 and 3.0 ng/mL, respectively. The values of the coefficient of determination were over 0.99 for all runs in the studied concentration range (3.0–10 000 ng/mL). The method recovery was 87 and 89% in plasma and urine, respectively. The intraday and interday precisions of sarcosine in the plasma and urine samples were in the ranges of 4.0–7.1, 3.0–6.3, 2.9–4.7, and 5.0–6.7, respectively.
Validated green high‐performance liquid chromatographic methods for the determination of coformulated pharmaceuticals: A comparison with reported conventional methods
Authors: Elzanfaly Eman S. , Hegazy Maha A. , Saad Samah S. , Salem Maissa Y. , Abd El Fattah Laila E.
Published: December 2014

The introduction of sustainable development concepts to analytical laboratories has recently gained interest, however, most conventional high‐performance liquid chromatography methods do not consider either the effect of the used chemicals or the amount of produced waste on the environment. The aim of this work was to prove that conventional methods can be replaced by greener ones with the same analytical parameters. The suggested methods were designed so that they neither use nor produce harmful chemicals and produce minimum waste to be used in routine analysis without harming the environment. This was achieved by using green mobile phases and short run times. Four mixtures were chosen as models for this study; clidinium bromide/chlordiazepoxide hydrochloride, phenobarbitone/pipenzolate bromide, mebeverine hydrochloride/sulpiride, and chlorphenoxamine hydrochloride/caffeine/8‐chlorotheophylline either in their bulk powder or in their dosage forms. The methods were validated with respect to linearity, precision, accuracy, system suitability, and robustness. The developed methods were compared to the reported conventional high‐performance liquid chromatography methods regarding their greenness profile. The suggested methods were found to be greener and more time‐ and solvent‐saving than the reported ones; hence they can be used for routine analysis of the studied mixtures without harming the environment.
Poly(l‐lactic acid)‐modified silica stationary phase for reversed‐phase and hydrophilic interaction liquid chromatography
Authors: Ohyama Kaname , Takasago Shizuka , Kishikawa Naoya , Kuroda Naotaka
Published: December 2014

Poly(l‐lactic acid) is a linear aliphatic thermoplastic polyester that can be produced from renewable resources. A poly(l‐lactic acid)‐modified silica stationary phase was newly prepared by amide bond reaction between amino groups on aminopropyl silica and carboxylic acid groups at the end of the poly(l‐lactic acid) chain. The poly(l‐lactic acid)‐silica column was characterized in reversed‐phase liquid chromatography and hydrophilic interaction liquid chromatography with the use of different mobile phase compositions. The poly(l‐lactic acid)‐silica column was found to work in both modes, and the retention of test compounds depending on acetonitrile content exhibited “U‐shaped” curves, which was an indicator of reversed‐phase liquid chromatography/hydrophilic interaction liquid chromatography mixed‐mode retention behavior. In addition, carbonyl groups included into the poly(l‐lactic acid) backbone work as an electron‐accepting group toward a polycyclic aromatic hydrocarbon and provide π–π interactions.
Determination of tetrakis(hydroxymethyl)phosphonium sulfate in commercial formulations and cooling water by capillary electrophoresis with contactless conductivity detection
Authors: Marques Thaís Tamye , Shiroma Letícia Sayuri , de Jesus Dosil Pereira
Published: December 2014

A novel capillary electrophoresis method using capacitively coupled contactless conductivity detection is proposed for the determination of the biocide tetrakis(hydroxymethyl)phosphonium sulfate. The feasibility of the electrophoretic separation of this biocide was attributed to the formation of an anionic complex between the biocide and borate ions in the background electrolyte. Evidence of this complex formation was provided by 11B NMR spectroscopy. A linear relationship (R2 = 0.9990) between the peak area of the complex and the biocide concentration (50–900 μmol/L) was found. The limit of detection and limit of quantification were 15.0 and 50.1 μmol/L, respectively. The proposed method was applied to the determination of tetrakis(hydroxymethyl)phosphonium sulfate in commercial formulations, and the results were in good agreement with those obtained by the standard iodometric titration method. The method was also evaluated for the analysis of tap water and cooling water samples treated with the biocide. The results of the recovery tests at three concentration levels (300, 400, and 600 μmol/L) varied from 75 to 99%, with a relative standard deviation no higher than 9%.
True metabolizable energy of American black duck foods
Authors: Coluccy John M. , Castelli Michael V. , Castelli Paul M. , Simpson John W. , Mcwilliams Scott R. , Armstrong Llwellyn
Published: December 2014

Understanding the true metabolizable energy (TME) of foods is critical to estimating the energetic carrying capacity of landscapes for migrating and wintering waterfowl. We estimated gross energy, nutrient composition, and TMEN (TME corrected for zero nitrogen balance) for 7 foods that are commonly found in the diet of American black duck (Anas rubripes) and other waterfowl wintering along the Atlantic Coast. TMEN values ( ± SE) were 3.66 ± 0.12 kcal/g for mummichog (Fundulus heteroclitus), 2.02 ± 0.12 kcal/g for grass shrimp (Palaemonetes intermedius, P. pugio, and P. vulgaris), 1.57 ± 0.11 kcal/g for fiddler crabs (Uca minax, U. pugilator, and U. pugnax), 1.42 ± 0.13 kcal/g for sea lettuce (Ulva lactuca), 1.39 ± 0.12 kcal/g for saltmarsh cordgrass seeds (Spartina alterniflora), 1.10 ± 0.14 kcal/g for widgeon grass vegetation (Ruppia maritima), and 0.77 ± 0.16 kcal/g for saltmarsh snails (Melampus bidentatus). TMEN estimated for foods in this study will assist conservation planners in carrying out bioenergetics modeling along the Atlantic Coast. © 2014 The Wildlife Society.