Multivariate process trajectories for molecular description of MF thermal curing and correlation with hydrolytic stability

During curing of thermosetting resins the technologically relevant properties of binders and coatings develop. However, curing is difficult to monitor due to the multitude of chemical and physical processes taking place. Precise prediction of specific technological properties based on molecular properties is very difficult. In this study, the potential of principal component analysis (PCA) and principal component regression (PCR) in the analysis of Fourier transform infrared (FTIR) spectra is demonstrated using the example of melamine-formaldehyde (MF) resin curing in solid state. FTIR/PCA-based reaction trajectories are used to visualize the influence of temperature on isothermal cure. An FTIR/PCR model for predicting the hydrolysis resistance of cured MF resin from their spectral fingerprints is presented which illustrates the advantages of FTIR/PCR compared to the combination differential scanning calorimetry/isoconversional kinetic analysis. The presented methodology is transferable to the curing reactions of any thermosetting resin and can be applied to model other technologically relevant final properties as well.     

Metabolic Glycoengineering in hMSC-TERT as a Model for Skeletal Precursors by Using Modified Azide/Alkyne Monosaccharides

Metabolic glycoengineering enables a directed modification of cell surfaces by introducing target molecules to surface proteins displaying new features. Biochemical pathways involving glycans differ in dependence on the cell type; therefore, this technique should be tailored for the best results. We characterized metabolic glycoengineering in telomerase-immortalized human mesenchymal stromal cells (hMSC-TERT) as a model for primary hMSC, to investigate its applicability in TERT-modified cell lines. The metabolic incorporation of N-azidoacetylmannosamine (Ac₄ManNAz) and N-alkyneacetylmannosamine (Ac₄ManNAl) into the glycocalyx as a first step in the glycoengineering process revealed no adverse effects on cell viability or gene expression, and the in vitro multipotency (osteogenic and adipogenic differentiation potential) was maintained under these adapted culture conditions. In the second step, glycoengineered cells were modified with fluorescent dyes using Cu-mediated click chemistry. In these analyses, the two mannose derivatives showed superior incorporation efficiencies compared to glucose and galactose isomers. In time-dependent experiments, the incorporation of Ac₄ManNAz was detectable for up to six days while Ac₄ManNAl-derived metabolites were absent after two days. Taken together, these findings demonstrate the successful metabolic glycoengineering of immortalized hMSC resulting in transient cell surface modifications, and thus present a useful model to address different scientific questions regarding glycosylation processes in skeletal precursors.     

Peracetic acid as a single endodontic irrigant: effects on microhardness,roughness and erosion of root canal dentin

The aim was to assess the effects of 1% peracetic acid (PAA) as a single endodontic irrigant on microhardness, roughness, and erosion of root canal dentin, compared with 2.5% sodium hypochlorite (NaOCl) and with 2.5% NaOCl combined with 17% EDTA. Forty human, single‐rooted tooth hemisections were submitted to Knoop microhardness test, before and after the following irrigation protocols: PAA = 1% PAA; NaOCl = 2.5% NaOCl; NaOCl‐EDTA‐NaOCl = 2.5% NaOCl +17% EDTA +2.5% NaOCl; and SS = saline. Another 40 roots were instrumented, irrigated with the same protocols, and sectioned longitudinally. The roughness analysis was performed on the mesial section using a confocal laser scanning microscope, whereas erosion was analyzed on each third of the distal section, using a scanning electron microscope. The data were analyzed using ANOVA and Tukey post‐tests, and Kruskal‐Wallis and Dunn post‐tests (α = .05). The PAA and NaOCl‐EDTA‐NaOCl groups showed no significant differences (p > .05); both promoted reduction in microhardness and increase in roughness, compared with the NaOCl and SS groups (p < .05). NaOCl‐EDTA‐NaOCl promoted higher erosion in the cervical and middle thirds than the other groups (p < .05); there was no difference among PAA, NaOCl, and SS (p > .05). There was also no difference among the groups regarding the apical third (p > .05). PAA used as a single endodontic irrigant caused reduction in root canal dentin microhardness and increase in roughness in a similar way to NaOCl‐EDTA‐NaOCl; however, PAA caused less erosion than NaOCl‐EDTA‐NaOCl.     

On‐the‐Spot Immobilization of Quantum Dots,Graphene Oxide,and Proteins via Hydrophobins

Class I hydrophobin Vmh2, a peculiar surface active and versatile fungal protein, is known to self‐assemble into chemically stable amphiphilic films, to be able to change wettability of surfaces, and to strongly adsorb other proteins. Herein, a fast, highly homogeneous and efficient glass functionalization by spontaneous self‐assembling of Vmh2 at liquid–solid interfaces is achieved (in 2 min). The Vmh2‐coated glass slides are proven to immobilize not only proteins but also nanomaterials such as graphene oxide (GO) and quantum dots (QDs). As models, bovine serum albumin labeled with Alexa 555 fluorophore, anti‐immunoglobulin G antibodies, and cadmium telluride QDs are patterned in a microarray fashion in order to demonstrate functionality, reproducibility, and versatility of the proposed substrate. Additionally, a GO layer is effectively and homogeneously self‐assembled onto the studied functionalized surface. This approach offers a quick and simple alternative to immobilize nanomaterials and proteins, which is appealing for new bioanalytical and nanobioenabled applications.     

The Impact of [C16Pyr][Amp] on the Aggressiveness in Breast and Prostate Cancer Cell Lines

Breast (BrCa) and prostate (PCa) cancers are the most common malignancies in women and men, respectively. The available therapeutic options for these tumors are still not curative and have severe side effects. Therefore, there is an urgent need for more effective antineoplastic agents. Herein, BrCa, PCa, and benign cell lines were treated with two ionic liquids and two quinoxalines and functional experiments were performed—namely cell viability, apoptosis, cytotoxicity, and colony formation assays. At the molecular level, an array of gene expressions encompassing several molecular pathways were used to explore the impact of treatment on gene expression. Although both quinoxalines and the ionic liquid [C2OHMIM][Amp] did not show any effect on the BrCa and PCa cell lines, [C16Pyr][Amp] significantly decreased cell viability and colony formation ability, while it increased the apoptosis levels of all cell lines. Importantly, [C16Pyr][Amp] was found to be more selective for cancer cells and less toxic than cisplatin. At the molecular level, this ionic liquid was also associated with reduced expression levels of CPT2, LDHA, MCM2, and SKP2, in both BrCa and PCa cell lines. Hence, [C16Pyr][Amp] was shown to be a promising anticancer therapeutic agent for BrCa and PCa cell lines.     

Hyperbranched polyglycerols,obtained from environmentally benign monomer,as reactive clays inhibitors for water‐based drilling fluids

To prevent the degradation of the borehole and also the disintegration and dispersion of drilled cuttings, different shale stabilizing additives are used in water‐based drilling fluids (WBFs). Glycols, poly(ethylene glycol), glycerols, and polyglycerol derivatives, also called polyols, have been used to inhibit shales containing reactive clays in WBF. These additives are normally used in conjunction with KCl to reduce clay swelling and dispersion of drilled cuttings. Highly branched polymers have become an important field in current polymer science. Such materials typically exhibit compact, globular structures in combination with an exceptionally high number of sites with functional groups. They have unique properties that differ significantly from their linear counterparts, and the hyperbranched polyglycerol (hPG) is an important hyperbranched polymer that can be produced from an environmentally benign monomer, the glycerol carbonate. In this article, the clay inhibitive properties of hPG were evaluated by different test methods including bentonite inhibition test, cuttings recovery, and X‐ray diffraction measurements. The results show that the hPG has a great potential to be used as an environmental friendly inhibitor additive in WBFs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40384.