Bacterial Killing by Light‐Triggered Release of Silver from Biomimetic Metal Nanorods

Illumination of noble metal nanoparticles at the plasmon resonance causes substantial heat generation, and the transient and highly localized temperature increases that result from this energy conversion can be exploited for photothermal therapy by plasmonically heating gold nanorods (NRs) bound to cell surfaces. Here, plasmonic heating is used for the first time to locally release silver from gold core/silver shell (Au@Ag) NRs targeted to bacterial cell walls. A novel biomimetic method of preparing Au@Ag core–shell NRs is employed, involving deposition of a thin organic polydopamine (PD) primer onto Au NR surfaces, followed by spontaneous electroless silver metallization, and conjugation of antibacterial antibodies and passivating polymers for targeting to gram‐negative and gram‐positive bacteria. Dramatic cytotoxicity of S. epidermidis and E. coli cells targeted with Au@Ag NRs is observed upon exposure to light as a result of the combined antibacterial effects of plasmonic heating and silver release. The antibacterial effect is much greater than with either plasmonic heating or silver alone, implying a strong therapeutic synergy between cell‐targeted plasmonic heating and the associated silver release upon irradiation. The findings suggest a potential antibacterial use of Au@Ag NRs when coupled with light irradiation, which has not been previously described.     

A study of electropolymerization of N,N-dimethylaniline

Electrochemical oxidation and polymerization of N,N-dimethylaniline at a gold electrode have been studied in an acidic solution. Both potential cycling and electrolysis at a controlled potential yield a thin film of a polymer that shows electrochemical activity in acidic and pH-neutral solutions. Raman spectra of sulfate- and polystyrenesulfonate-doped polymer have been obtained and analyzed. Two possibilities for electropolymerization have been considered – a simple polymerization yielding a “true” poly(N,N-dimethylaniline), and polymerization accompanied by a partial demethylation yielding poly(N-methylaniline). Based on the results obtained, the first one has been considered as most likely.     

The impact of Al2O3 amount on the synthesis of CASH samples and their influence on the early stage hydration of calcium aluminate cement

In this work the impact of Al₂O₃ amount on the synthesis (200?°C; 4–8?h) of calcium aluminium silicate hydrates (CSAH) samples and their influence on the early stage hydration of calcium aluminate cement (CAC) was examined. It was found that the amount of Al₂O₃ plays an important role in the formation of calcium aluminate hydrates (CAH) because in the mixtures with 2.7% Al₂O₃ only calcium silicate hydrates (CSH) intercalated with Al³⁺ ions were formed. While in the mixtures with a higher amount of Al₂O₃ (5.3–15.4%), calcium aluminate hydrate – C₃AH₆, is formed under all experimental conditions. It is worth noting that the largest quantity of mentioned compound was obtained after 4?h of hydrothermal treatment, in the mixtures with 15.4% of Al₂O₃. It was proved that synthesized C₃AH₆ remain stable up to 300?°C and at higher temperature (945?°C) recrystallized to mayenite (Ca₁₂Al₁₄O₃₃), which reacted with the rest part of CaO and amorphous structure compound, resulting in the formation of gehlenite (Ca₂Al₂SiO₇). Moreover, the synthesized C₃AH₆ addition induced the early stage of CAC hydration. Besides, in the samples with an addition, the induction period was effectively shortened: in a case of pure CAC (G70) paste, hydration takes about 6–6.5?h, while with addition – only 2–2.5?h. The synthesized and calcinated compounds was characterized by using XRD and STA analysis.     

Synthesis of the hole-transporting molecular glasses possessing pendant 3,6-dibromocarbazolyl moieties

Synthesis and properties of the well-defined 3,6-dibromocarbazolyl-containing molecular glasses are reported. They were prepared by the nucleophilic opening of the oxirane ring of 1,3-di(3,6-dibromocarbazol-9-yl)-2-propanol glycidyl ether with aniline, 4-fluoro-, 4-bromoanilines, 2,5-dimercapto-1,3,4-thiadiazole or glycidyl ether of 1,3-di(carbazol-9-yl)-2-propanol with 4,4′-thiobisbenzenethiol and 1,9-nonanedithiol followed by bromination. The obtained materials were examined by various techniques including differential scanning calorimetry, NMR, MS, UV, PL spectrometry. The electrophotographic parameters of the molecular glasses doped with difluoroboron-1,3-bis(4-metoxyphenyl)-1,3-propanedionate have been studied. The electrochemical properties and ionization potentials, measured by electron photoemission method in air, were investigated.     

Optical evaluation of carrier lifetime and diffusion length in synthetic diamonds

The key electronic parameters of high-pressure-high-temperature and chemical-vapor-deposition grown diamonds have been determined at interband (hν = 5.82 eV) or below bandgap (hν = 4.68 eV) photoexcitation, using a picosecond transient grating (TG) technique. TG kinetics directly provided the values of ambipolar diffusion coefficient (6–10 cm²/s) and carrier lifetime (in a range from 0.17 to 2.8 ns) for crystals grown under different conditions. The carrier diffusion length was found to vary from 0.5 μm in CVD layers to 1.6 μm for IIa type HPHT diamond crystal. The carrier lifetimes correlated well with the nitrogen-related defect density in both types of diamonds.     

Bioelectrochemical sensor based on PQQ-dependent glucose dehydrogenase

Bioelectrochemical responses of pyrroloquinoline quinone (PQQ) dependent glucose dehydrogenase (PQQ-GDH) have been studied with the use of two principal electrode configurations: (i) glassy carbon electrode, coated with Nafion layer, containing sorbed N-methylphenazonium (NMP), and overcoated by an enzyme layer, crosslinked by glutaraldehyde, and (ii) glassy carbon electrode, containing an electropolymerized layer of either Toluidine blue, or o-phenylenediamine, or pyrrole, and overcoated by a crosslinked enzyme layer. When operated within the potential window of 0.0–0.3 V, Nafion-coated and NMP-soaked bioelectrode shows an anodic current response to glucose without the presence of electron transfer mediator in solution. The current–concentration profile obtained resemble to that, typical for enzyme catalyzed reaction. Other configurations studied showed bioelectrochemical response to glucose only in the presence of soluble mediator NMP. Without any mediator, no electrochemical responses have been registered. It indicates that direct electron transfer between PQQ-GDH and all types of electrodes modified during current work is undetectable.     

Numerical modeling of structural transitions in few-particle confined 2D systems

We study classical strongly correlated few-particle systems in two-dimensional traps. Strong interaction between the particles leads to formation of ordered structure (the Wigner crystal), and the precise configuration of particles is determined by the shape of the confinement. Structural transitions in systems of four to seven particles induced by compression of the confining trap in one of two lateral directions are modeled numerically using the statistical Monte Carlo technique and distributed (grid) computing. We focus on the dependence of the specific heat on the eccentricity of the confinement, and show that rapid variations of the specific heat can be used to detect and classify changes of system configuration. These structural transitions are the finite-size analogues of phase transitions commonly defined for infinite systems.     

Multigene Profiling of Circulating Tumor Cells (CTCs) for Prognostic Assessment in Treatment-Naïve Metastatic Hormone-Sensitive Prostate Cancer (mHSPC)

The substantial biological heterogeneity of metastatic prostate cancer has hindered the development of personalized therapeutic approaches. Therefore, it is difficult to predict the course of metastatic hormone-sensitive prostate cancer (mHSPC), with some men remaining on first-line androgen deprivation therapy (ADT) for several years while others progress more rapidly. Improving our ability to risk-stratify patients would allow for the optimization of systemic therapies and support the development of stratified prospective clinical trials focused on patients likely to have the greatest potential benefit. Here, we applied a liquid biopsy approach to identify clinically relevant, blood-based prognostic biomarkers in patients with mHSPC. Gene expression indicating the presence of CTCs was greater in CHAARTED high-volume (HV) patients (52% CTC_high) than in low-volume (LV) patients (23% CTC_high; * p = 0.03). HV disease (p = 0.005, q = 0.033) and CTC presence at baseline prior to treatment initiation (p = 0.008, q = 0.033) were found to be independently associated with the risk of nonresponse at 7 months. The pooled gene expression from CTCs of pre-ADT samples found AR, DSG2, KLK3, MDK, and PCA3 as genes predictive of nonresponse. These observations support the utility of liquid biomarker approaches to identify patients with poor initial response. This approach could facilitate more precise treatment intensification in the highest risk patients.     

Molecular Design of Antifouling Polymer Brushes Using Sequence‐Specific Peptoids

Material systems that can be used to flexibly and precisely define the chemical nature and molecular arrangement of a surface would be invaluable for the control of complex biointerfacial interactions. For example, progress in antifouling polymer biointerfaces that prevents nonspecific protein adsorption and cell attachment, which can significantly improve the performance of an array of biomedical and industrial applications, is hampered by a lack of chemical models to identify the molecular features conferring their properties. Poly(N‐substituted glycine) “peptoids” are peptidomimetic polymers that can be conveniently synthesized with specific monomer sequences and chain lengths, and are presented as a versatile platform for investigating the molecular design of antifouling polymer brushes. Zwitterionic antifouling polymer brushes have captured significant recent attention, and a targeted library of zwitterionic peptoid brushes with different charge densities, hydration, separations between charged groups, chain lengths, and grafted chain densities, is quantitatively evaluated for their antifouling properties through a range of protein adsorption and cell attachment assays. Specific zwitterionic brush designs are found to give rise to distinct but subtle differences in properties. The results also point to the dominant roles of the grafted chain density and chain length in determining the performance of antifouling polymer brushes.     

Docking of Fatty Acids into the WIF Domain of the Human Wnt Inhibitory Factor-1

Palmitoylated Wnt proteins comprise a conserved family of secreted signaling molecules associated with variety of human cancers. WIF domain of the human WIF (Wnt inhibitory factor)-1 is sufficient for Wnt binding and signaling inhibition. Detailed interactions between Wnt and WIF-1 are not known. Computational docking was employed to identify a possible fatty acid binding site in the WIF domain. A putative binding site was identified inside the domain. WIF domain exhibited the highest affinity for C16:0–C18:0 (−22 kJ/mol free energy of binding) fatty acids. The results suggest a role of the WIF domain as a palmitoyl binding domain required for WIF-1 binding to palmitoylated Wnt and signaling inhibition. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.