Journals
2018 EN
Bystron Tomas · Horbenko Anastasiia · Syslova Kamila
+3 more
For the first time, the electrochemical synthesis of 2‐iodoxybenzoic acid (IBX), a benign, well‐established, popular and highly selective oxidising agent, is described. The objective of the work was to investigate the possibility of generating IBX electrochemically in aqueous solutions by using boron‐doped diamond anodes. In 0.2 M H 2 SO 4 aqueous solution, 2‐iodobenzoic acid (IBA) was found to be oxidised at potentials >1.6 V vs. SCE, initially to 2‐iodosobenzoic acid (IsBA), which was oxidised to IBX at potentials >1.8 V vs. SCE. Reductions of IBX to IsBA and IsBA to IBA occurred at similar potentials of ca. −0.7 V vs. SCE. The voltammetry results were confirmed by performing a series of batch electrolyses at different electrode potentials. Thus, depending on the electrode potential chosen, IBA can be oxidised anodically either to IsBA or IBX with 100 % overall selectivity. The only side‐reaction was O 2 generation, but charge yields did not decrease below 55 % even at conversions >95 %.
Journals
2018 EN
Bystron Tomas · Horbenko Anastasiia · Syslova Kamila
+3 more
The Cover Feature illustrates the electrochemical oxidation of 2‐iodobenzoic acid to 2‐iodoxybenzoic acid (IBX) through a 2‐iodosobenzoic acid intermediate at a boron‐doped diamond electrode. The process takes place with high selectivity and high charge yield. More information can be found in the Communication by T. Bystron et al. on page 1002 in Issue 7, 2018 (DOI: 10.1002/celc.201800027).
Journals
2018 EN
Bladek Kamila J. · Reid Margaret E. · Nishihara Hirotomo
+3 more
By complexing a bent phosphonate monoester ligand with cobalt(II), coupled with in situ ester hydrolysis, coordination microspheres (CALS=CALgary Sphere) are formed whereas the use of the phosphonic acid directly resulted in a sheet‐like structure. Manipulation of the synthetic conditions gave spheres with different sizes, mechanical stabilities, and porosities. Time‐dependent studies determined that the sphere formation likely occurred through the formation of a Co 2+ and ligand chain that propagates in three dimensions through different sets of interactions. The relative rates of these assembly processes versus annealing by ester hydrolysis and metal dehydration determine the growth of the microspheres. Hardness testing by nanoindentation is carried out on the spheres and sheets. Notably, no templates or capping agents are employed, the growth of the spheres is intrinsic to the ligand geometry and the coordination chemistry of cobalt(II) and the phosphonate monoester.
Journals
2018 EN
Habartová Lucie · Bunganič Bohuš · Tatarkovič Michal
+4 more
To enable the early diagnosis of pancreatic cancer, the search for and definition of reliable biomarkers remain a subject of great interest, with the specificity and sensitivity of the currently used biomarkers being below the required values. We tested a novel diagnostic approach for pancreatic cancer based on the specific molecular signature of blood plasma components. To acquire more detailed structural information, structure‐sensitive chiroptical methods (electronic circular dichroism and Raman optical activity) were supplemented by conventional Raman and infrared spectroscopies. The obtained spectra were subsequently processed by linear discriminant analysis yielding high values of specificity and sensitivity. In addition, to monitor not only large biomolecules as potential biomarkers but also those of low molecular weight, we conducted an analysis of blood plasma samples by using metabolomics. The achieved results suggest a panel of promising biomarkers for a reliable detection of pancreatic cancer.
Journals
2018 EN
Guziejewski Dariusz · Morawska Kamila · Popławski Tomasz
+3 more
The electrochemical reduction of lactofen (LCT) at the glassy carbon (GCE) and silver amalgam film electrode (AMFE) is investigatedin detail by the means of square wave voltammetry (SWV), square wave stripping voltammetry (SWSV) and cyclic voltammetry. The influence of various factors such as supporting electrolyte composition and SW parameters were studied. The AMFE electrode showed an excellent electrochemical activity toward the electro‐reduction of LCT, leading to a significant improvement in sensitivity as compared to the glassy carbon electrode.The SWSV detection limits for GCE and AMFE were 285.0 nM and 2.0 nM, respectively. The applicability of the developed voltammetric method for analysis of tap water and river water is illustrated with spiked samples analysis. Moreover, as lactofen is highly toxic to fish and other aquatic organisms, its interaction with dsDNA isolated from salmon sperm was tested. The intercalative mode of LCT binding to dsDNA was estimated. The heterogeneous rate constants were calculated for the free LCT and the LCT‐dsDNA complex. Moreover, LCT‐dsDNA complex binding ratio and equilibrium constant were determined. The decrease in the SWV peak current of LCT in the presence of dsDNA was used for the determination of dsDNA.
Journals
2018 EN
Oyefiade Adeoye A. · Ameis Stephanie · Lerch Jason P.
+7 more
Neural communication is facilitated by intricate networks of white matter (WM) comprised of both long and short range connections. The maturation of long range WM connections has been extensively characterized, with projection, commissural, and association tracts showing unique trajectories with age. There, however, remains a limited understanding of age‐related changes occurring within short range WM connections, or U‐fibers . These connections are important for local connectivity within lobes and facilitate regional cortical function and greater network economy. Recent studies have explored the maturation of U‐fibers primarily using cross‐sectional study designs. Here, we analyzed diffusion tensor imaging (DTI) data for healthy children and adolescents in both a cross‐sectional ( n = 78; mean age = 13.04 ± 3.27 years) and a primarily longitudinal ( n = 26; mean age = 10.78 ± 2.69 years) cohort. We found significant age‐related differences in fractional anisotropy (FA), mean diffusivity (MD), axial diffusivity (AD) and radial diffusivity (RD) across the frontal, parietal, and temporal lobes of participants within the cross‐sectional cohort. By contrast, we report significant age‐related differences in only FA for participants within the longitudinal cohort. Specifically, larger FA values were observed with age in frontal, parietal, and temporal lobes of the left hemisphere. Our results extend previous findings restricted to long range WM to demonstrate regional changes in the microstructure of short range WM during childhood and adolescence. These changes possibly reflect continued myelination and axonal organization of short range WM with increasing age in more anterior regions of the left hemisphere. Hum Brain Mapp 39:204–217, 2018 . © 2017 Wiley Periodicals, Inc.
Journals
2018 EN
Colombo Mara · LòpezPerolio Irene · Meeks Huong D.
+111 more
Although the spliceogenic nature of the BRCA2 c.68‐7T > A variant has been demonstrated, its association with cancer risk remains controversial. In this study, we accurately quantified by real‐time PCR and digital PCR (dPCR), the BRCA2 isoforms retaining or missing exon 3. In addition, the combined odds ratio for causality of the variant was estimated using genetic and clinical data, and its associated cancer risk was estimated by case‐control analysis in 83,636 individuals. Co‐occurrence in trans with pathogenic BRCA2 variants was assessed in 5,382 families. Exon 3 exclusion rate was 4.5‐fold higher in variant carriers (13%) than controls (3%), indicating an exclusion rate for the c.68‐7T > A allele of approximately 20%. The posterior probability of pathogenicity was 7.44 × 10 −115 . There was neither evidence for increased risk of breast cancer (OR 1.03; 95% CI 0.86–1.24) nor for a deleterious effect of the variant when co‐occurring with pathogenic variants. Our data provide for the first time robust evidence of the nonpathogenicity of the BRCA2 c.68‐7T > A. Genetic and quantitative transcript analyses together inform the threshold for the ratio between functional and altered BRCA2 isoforms compatible with normal cell function. These findings might be exploited to assess the relevance for cancer risk of other BRCA2 spliceogenic variants.
Journals
2018 EN
Eriksson Louise · Bergh Jonas · Humphreys Keith
+3 more
Theoretically, time from breast cancer diagnosis to therapeutic surgery should affect survival. However, it is unclear whether this holds true in a modern healthcare setting in which breast cancer surgery is carried out within weeks to months of diagnosis. This is a population‐ and register‐based study of all women diagnosed with invasive breast cancer in the Stockholm‐Gotland healthcare region in Sweden, 2001–2008, and who were initially operated. Follow‐up of vital status ended 2014. 7,017 women were included in analysis. Our main outcome was overall survival. Main analyses were carried out using Cox proportional hazards models. We adjusted for likely confounders and stratified on mode of detection, tumor size and lymph node metastasis. We found that a longer interval between date of morphological diagnosis and therapeutic surgery was associated with a poorer prognosis. Assuming a linear association, the hazard rate of death from all causes increased by 1.011 (95% CI 1.006–1.017) per day. Comparing, for example, surgery 6 weeks after diagnosis to surgery 3 weeks after diagnosis, thereby confers a 1.26‐fold increased hazard rate. The increase in hazard rate associated with surgical delay was strongest in women with largest tumors. Whilst there was a clear association between delays and survival in women without lymph node metastasis, the association may be attenuated in subgroups with increasing number of lymph node metastases. We found no evidence of an interaction between time to surgery and mode of detection. In conclusion, unwarranted delays to primary treatment of breast cancer should be avoided.
Journals
2018 EN
Li Jingmei · Wen Wei Xiong · Eklund Martin
+18 more
Breast cancer patients with BRCA1/2 ‐driven tumors may benefit from targeted therapy. It is not clear whether current BRCA screening guidelines are effective at identifying these patients. The purpose of our study was to evaluate the prevalence of inherited BRCA1/2 pathogenic variants in a large, clinically representative breast cancer cohort and to estimate the proportion of BRCA1/2 carriers not detected by selectively screening individuals with the highest probability of being carriers according to current clinical guidelines. The study included 5,122 unselected Swedish breast cancer patients diagnosed from 2001 to 2008. Target sequence enrichment (48.48 Fluidigm Access Arrays) and sequencing were performed (Illumina Hi‐Seq 2,500 instrument, v4 chemistry). Differences in patient and tumor characteristics of BRCA1/2 carriers who were already identified as part of clinical BRCA1/2 testing routines and additional BRCA1/2 carriers found by sequencing the entire study population were compared using logistic regression models. Ninety‐two of 5,099 patients with valid variant calls were identified as BRCA1/2 carriers by screening all study participants (1.8%). Only 416 study participants (8.2%) were screened as part of clinical practice, but this identified 35 out of 92 carriers (38.0%). Clinically identified carriers were younger, less likely postmenopausal and more likely to be associated with familiar ovarian cancer compared to the additional carriers identified by screening all patients. More BRCA2 (34/42, 81.0%) than BRCA1 carriers (23/50, 46%) were missed by clinical screening. In conclusion, BRCA1/2 mutation prevalence in unselected breast cancer patients was 1.8%. Six in ten BRCA carriers were not detected by selective clinical screening of individuals.
Journals
2018 EN
Urbanek Kinga Anna · HabrowskaGórczyńska Dominika Ewa · Kowalska Karolina
+3 more
Deoxynivalenol (DON) is a type B trichothecene, produced by the Fusarium species. Exposure to DON might cause disruptive effects such as reduced weight gain, neuroendocrine changes and immune modulation in animals (rats, dogs, pigs). There is huge concern that similar effects can be observed in humans. DON is a potential regulator of intracellular steroidogenesis. It is also possible that DON will be involved in the regulation of miRNAs connected with steroidogenesis. This review summarizes the latest knowledge about the influence of DON on steroidogenesis and human hormonal balance.