Ferrocene/ β-cyclodextrin based supramolecular nanogels as theranostic systems

A supramolecular redox responsive nanogel (NG) with the ability to sense cancer cells and loaded with a releasing therapeutic agent was synthesized using hostguest interactions between polyethylene glycol-grafted-β-cyclodextrin and ferrocene boronic acid. Cyclic voltammetry matched with other spectroscopy and microscopy methods provided strong indications regarding host-guest interactions and formation of the NG. Moreover, the biological properties of the NG were evaluated using fluorescence silencing, confocal laser scanning microscopy, and cell toxicity assays. Nanogel with spherical core-shell architecture and 100–200 nm sized nanoparticles showed high encapsulation efficiency for doxorubicin (DOX) and luminol (LU) as therapeutic and sensing agents. High therapeutic and sensing efficiencies were manifested by complete release of DOX and dramatic quenching of LU fluorescence triggered by 0.05 mM H2O2 (as an ROS component). The NGs showed high ROS sensitivity. Taking advantage of a high loading capacity, redox sensitivity, and biocompatibility, the NGs can be used as strong theranostic systems in inflammation-associated diseases

Preserving π-conjugation in covalently functionalized carbon nanotubes for ptoelectronic applications

Covalent functionalization tailors carbon nanotubes for a wide range of applications in varying environments. Its strength and stability of attachment come at the price of degrading the carbon nanotubes sp2 network and destroying the tubes electronic and optoelectronic features. Here we present a non- destructive, covalent, gram-scale functionalization of single-walled carbon nanotubes by a new [2+1] cycloaddition. The reaction rebuilds the extended π-network, thereby retaining the outstanding quantum optoelectronic properties of carbon nanotubes, including bright light emission at high degree of functionalization (1 group per 25 carbon atoms). The conjugation method described here opens the way for advanced tailoring nanotubes as demonstrated for light-triggered reversible doping through photochromic molecular switches and nanoplasmonic gold-nanotube hybrids with enhanced infrared light emission

Metal-assisted and solvent-mediated synthesis of two-dimensional triazine structures on gram scale

We thank the German Science Foundation (DFG) for financial support within the grants SFB 765 and SFB 658. M.F.G. and J.P.R. also acknowledge the support of the Cluster of Excellence “Matters of Activity. Image Space Material” funded by the DFG under Germany’s Excellence Strategy EXC 2025-390648296. Furthermore, A.T. acknowledges the DFG for funding within the project TH 1463/12-1. We thank Dr. Andreas Schäfer and Maiko Schulze for solid NMR experiments and we appreciate the effort of Vahid Ahmadi Soureshjani in MALDI-TOF experiments. We acknowledge M. Eng. Jörg M. Stockmann for operating the XPS instrument at the BAM and Prof. Stephanie Reich and Dr. Antonio Setaro for fruitful discussions. 2DTs-HRTEM and -EELS studies were conducted at the Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Spain. R.A. gratefully acknowledges the support from the Spanish Ministry of Economy and Competitiveness (MINECO) through project grant MAT2016-79776-P (AEI/FEDER, UE) and from the European Union H2020 programs ETN projects “Graphene Flagship” (785219 and 881603), FLAG-ERA - Graphene (MICINN) GATES (PCI2018-093137) and “ESTEEM3” (823717).Peer reviewe

Synthese und kontrollierte zerstörungsfreie kovalente Funktionalisierung von niedrigdimensionalen Kohlenstoff-Nanomaterialien

Carbon materials have shown a great potential in the academic field and have been employed for plenty of applications. Graphene, a natural two dimensional polymer, and carbon nanotube (one dimensional analog) are meritorious candidates with fascinating physicochemical features. However, a chemical process is needed in order to customize their properties toward desired applications. Among different methods, covalent functionalization is the most promising approach for this purpose. On the other hand, the natural 2D polymer (graphene) inspired researchers to design and synthesize other 2D polymers. Nevertheless, the synthesis of 2DPs is still in its early stage and there is plenty of space for improvement in this field. Consequently, to expand these fascinating materials we conceived a new idea to functionalize graphene/carbon nanotube and synthesis of a 2D polymer by a new method. Scientific contribution of the thesis is in three main directions, which are addressing mentioned challenges for carbon nanotubes, graphene and 2D polymers. In the first part we intend to investigate a controlled, reproducible, and mild covalent functionalization of graphene by a one-pot reaction between triazine and sodium azide to generate dichlorotriazine intermediate which could provide a selective and controlled modification approach through substitution the reactive chlorine of the triazine groups. The different reactivity of chlorine allows us to perform stepwise post-modification on graphene by manipulating the temperature from 25 up to 65 °C. As a result, defined bifunctional 2D nanomaterials (graphene) were provided and covered with hyperbranched polyglycerol (hPG) in a controlled and stepwise manner. In the second part we intend to design and establish a new nondestructive covalent method to functionalize CNTs. We explored unique non-destructive covalent, gram-scale functionalization for CNT by a new nitrene [2+1] cycloaddition. By this method the reaction between CNT and dichlorotriazine intermediate resulted in dichlorotriazine functionality that rebuilds the extended π-system of CNTs, thereby preserving opteoelectronic properties of carbon nanotube. Lastly, the challenge of in-solution synthesis of a 2D polymer was investigated and a new nanostructure was prepared. We introduced a metal-assisted method, in which calcium carbide and triazine are monomers and dimethylformamide is the solvent. This reaction was directed in two dimensions by calcium ions derived from calcium carbide and induced 2DTHs with amorphous structures. Calcium ions coordinated with nitrogen atoms of triazine (ligand-metal interaction), which prevented bond rotation and provide enough rigidity for the desired 2D 193 structure. We investigated the chemical structure and physicochemical properties of the obtained 2D structure and evaluated the mechanism of the related reactions. Based on our investigations, the water content of the reaction medium was one of the crucial factors that affected the structure of the product dramatically. While pure 2DTHs were obtained under dry conditions, graphite/2DTHs mixture or even pure graphite was obtained by increasing the water content of the reaction medium. Taking advantage of their straightforward and gram-scale synthesis as well as fluorescence, photothermal and photodynamic properties, the synthesized two-dimensional triazine heterostructures are promising materials for a wide range of future applications

Potential use of protexin probiotic and black pepper powder on Cobb 500 broiler chicks

To evaluate the effect of protexin, black pepper powder on performance of broiler chicks 160 one day male broiler chicks were divided into 4 groups of 10 birds each and assigned to 4 treatment diets. Chicks were fed by basal diet as control with or without 0.2 % protexin probiotic or black pepper fine powder respectively. Feed intake (FI), body weight (BW) and feed conversion ratio (FCR) was measured in each period of aviculture. At the end of trial 2 birds from each group were slaughtered and carcass characteristics were evaluated. Blood serum triglyceride, high and low density lipoproteins also were determined. At 42 days old antibody titer against Newcastle Vaccine was estimated. Intestinal microbial populations for Escherichia coli and Lactobacillus were performed. The results showed that body weights and feed conversion ratios were improved significantly (p<0.05). As data reveled in this study, using of protexin and black pepper increased carcass yield compared to the control. Data showed those serum blood biochemical were changed significantly by using protexin and black pepper (p<0.05). Also E-Coli colonies were decreased and lactobacilli microbial population had significan tly (p<0.05) increased in chicks were fed by protexin and black pepper powder. It seems that inclusion of protexin and black pepper powder had good effects on performance, some blood biochemical values, and immunity parameters and microbial population in experimental Cobb 500 broiler chicks

Ferrocene/ β-cyclodextrin based supramolecular nanogels as theranostic systems

A supramolecular redox responsive nanogel (NG) with the ability to sense cancer cells and loaded with a releasing therapeutic agent was synthesized using hostguest interactions between polyethylene glycol-grafted-β-cyclodextrin and ferrocene boronic acid. Cyclic voltammetry matched with other spectroscopy and microscopy methods provided strong indications regarding host-guest interactions and formation of the NG. Moreover, the biological properties of the NG were evaluated using fluorescence silencing, confocal laser scanning microscopy, and cell toxicity assays. Nanogel with spherical core-shell architecture and 100–200 nm sized nanoparticles showed high encapsulation efficiency for doxorubicin (DOX) and luminol (LU) as therapeutic and sensing agents. High therapeutic and sensing efficiencies were manifested by complete release of DOX and dramatic quenching of LU fluorescence triggered by 0.05 mM H2O2 (as an ROS component). The NGs showed high ROS sensitivity. Taking advantage of a high loading capacity, redox sensitivity, and biocompatibility, the NGs can be used as strong theranostic systems in inflammation-associated diseases

Functional Surfactants for Molecular Fishing, Capsule Creation, and Single-Cell Gene Expression

Abstract Creating a single surfactant that is open to manipulation, while maintaining its surface activity, robustness, and compatibility, to expand the landscape of surfactant-dependent assays is extremely challenging. We report an oxidation-responsive precursor with thioethers and multiple 1,2-diols for creating a variety of functional surfactants from one parent surfactant. Using these multifunctional surfactants, we stabilize microfluidics-generated aqueous droplets. The droplets encapsulate different components and immerse in a bioinert oil with distinct interfaces where an azide-bearing surfactant allow fishing of biomolecules from the droplets, aldehyde-bearing surfactant allow fabrication of microcapsules, and hydroxyl-bearing surfactants, with/without oxidized thioethers, allow monitoring of single-cell gene expression. Creating multifunctional surfactants poses opportunities for broad applications, including adsorption, bioanalytics, catalysis, formulations, coatings, and programmable subset of emulsions

Linear triglycerol-based fluorosurfactants show high potential for droplet-microfluidics-based biochemical assays

Fluorosurfactants have expanded the landscape of high-value biochemical assays in microfluidic droplets, but little is known about how the spatial geometries and polarity of the head group contribute to the performance of fluorosurfactants. To decouple this, we design, synthesize, and characterize two linear and two dendritic glycerol- or tris-based surfactants with a common perfluoropolyether tail. To reveal the influence of spatial geometry, we choose inter-droplet cargo transport as a stringent test case. Using surfactants with linear di- and triglycerol, we show that the inter-droplet cargo transport is minimal compared with their dendritic counterparts. When we encapsulated a less-leaky sodium fluorescent dye into the droplets, quantitatively, we find that the mean fluorescence intensity of the PFPE-dTG stabilized PBS-only droplets after 72 h was ∼3 times that of the signal detected in PBS-only droplets stabilized by PFPE-lTG. We also demonstrate that the post-functionalization of PFPE-lTG having a linear geometry and four hydroxy groups enables the ‘from-Droplet’ fishing of the biotin–streptavidin protein complex without the trade-off between fishing efficiency and droplet stability. Thus, our approach to design user-friendly surfactants reveals the aspects of spatial geometry and facile tunability of the polar head groups that have not been captured or exploited before

Linear triglycerol-based fluorosurfactants show high potential for droplet-microfluidics-based biochemical assays

Fluorosurfactants have expanded the landscape of high-value biochemical assays in microfluidic droplets, but little is known about how the spatial geometries and polarity of the head group contribute to the performance of fluorosurfactants. To decouple this, we design, synthesize, and characterize two linear and two dendritic glycerol- or tris-based surfactants with a common perfluoropolyether tail. To reveal the influence of spatial geometry, we choose inter-droplet cargo transport as a stringent test case. Using surfactants with linear di- and triglycerol, we show that the inter-droplet cargo transport is minimal compared with their dendritic counterparts. When we encapsulated a less-leaky sodium fluorescent dye into the droplets, quantitatively, we find that the mean fluorescence intensity of the PFPE-dTG stabilized PBS-only droplets after 72 h was similar to 3 times that of the signal detected in PBS-only droplets stabilized by PFPE-lTG. We also demonstrate that the post-functionalization of PFPE-lTG having a linear geometry and four hydroxy groups enables the 'from-Droplet' fishing of the biotin-streptavidin protein complex without the trade-off between fishing efficiency and droplet stability. Thus, our approach to design user-friendly surfactants reveals the aspects of spatial geometry and facile tunability of the polar head groups that have not been captured or exploited before

COVID-19 Vaccination Willingness and Acceptability in Multiple Sclerosis Patients:A Cross Sectional Study in Iran

Multiple sclerosis (MS) is a chronic, predominantly immune-mediated degenerative disease of the central nervous system. Due to prolonged use of immunomodulatory and immunosuppressive medications, vaccine hesitancy could be common among MS patients. Our main aim in the current study was to evaluate the willingness and acceptability of COVID-19 vaccination in patients with MS. In our multicenter cross-sectional questionnaire-based clinical study, 892 patients completed the questionnaire between May to June 2021. The questionnaire consisted of demographic data, MS disease-related factors, history of COVID-19 infection/vaccination, and any existing comorbidities. Statistical analysis was performed using SPSS software version 19. Overall, 68% of the participants expressed willingness to be vaccinated. Major causes of vaccine refusal in our patients were the fear of reducing the efficacy of disease modifying drugs (DMDs) upon vaccination as well as distrusting the vaccines and overestimation bias in the power of their innate immunity and potential COVID-19 resistance. Some demographic factors affected vaccination enthusiasm in our study. Our findings did not show significant correlation between the age and comorbidity and vaccine willingness. Only one-third of our patients received their vaccine information from healthcare providers. The majority of them received these data from official broadcasting channels and social media. However, despite several concerns, the willingness of COVD-19 vaccination in the Iranian MS patients is remarkable