Three block polymers, viz., L31, L64, and P123, were used as reducing agents for the synthesis of gold (Au) nanoparticles (NPs) to determine the effect of their micelle size, structure transitions, and environments on the mechanism of the reduction process leading to the overall morphology of Au NPs. Aqueous phase reduction was monitored with time at constant temperature and under the effect of temperature variation from 20 to 70 °C by simultaneous measurement of UV–visible spectra. The ligand to metal charge transfer (LMCT) band around 300 nm, due to a charge transfer complex formation between the micelle surface cavities and AuCl4 – ions, and Au NP absorbance around 550 nm, due to the surface plasmon resonance, were simultaneously measured to understand the mechanism of the reduction process and its dependence on the micelle structure transitions and environment of TBPs micelles. L64 micelles showed dramatic shift in the LMCT band from lower to higher wavelength due to an increase in the reduction potential of surface cavities induced by the structure transitions under the effect of temperature variations. This effect was not observed for micelles of either L31 or P123 and is explained on the basis of a difference in their micelle environments. The morphology of Au NPs thus evolved from the reduction process was studied with the help of TEM and SEM studies. Smaller micelle size with few surface cavities, as in L31, produced small NPs in comparison to large micelles with several surface cavities as in P123. Structure transitions of L64 demonstrated direct influence on the final morphology of NPs, and stronger transitions produced fused and deformed NPs in comparison to weaker transitions. The results showed that efficient reduction by the surface cavities and uninterrupted nucleation without structure transitions lead to well-defined morphologies in the presence of P123 micelles.
Bovine serum albumen (BSA) conjugated gold (Au) nanoparticles (NPs) were directly synthesized by using BSA as a weak reducing agent against HAuCl4 in aqueous phase. A systematic variation in Au/BSA mole ratio showed a dramatic change in the size and shape of NPs which was very much dependent on the physical state of BSA. The nature of both colloidal NPs (due to surface plasmon resonance) and BSA (due to tryptophan residues) was monitored simultaneously by UV−visible measurements during the course of the reaction. A systematic variation in the reaction temperature from 20 to 70 °C demonstrated a clear denaturation process of BSA and how it influenced the synthesis of Au NPs. A predominantly native state of BSA that existed up to 40 °C proved to be a very mild reducing agent to convert Au(III) into Au(0). However, the reducing potential increased with unfolding of BSA beyond 40 °C and became maximum in the denaturation temperature range (i.e., 52−58 °C). Unfolded BSA conjugated NPs thus produced then started a seeding process with other similar NPs or free BSA to produce self-assembled colloidal assemblies in the form of soft film of BSA bearing NPs. SEM, TEM, and AFM studies were used to characterize the BSA conjugated NPs in the form of soft film. The soft film was used with water insoluble zein protein to produce very robust biodegradable protein films suitable for various food and pharmaceutical applications. Tensile strength and strain at failure measurements of zein protein films demonstrated that the film made with BSA conjugated NPs existed in the form of a soft film was much stronger and flexible in comparison to that made with nonaggregated NPs.
Lysozyme (Lys) and cytochrome c (Cyc,c) proteins were used as mild reducing and stabilizing agents to synthesize gold nanoparticles (NPs) at precisely 40 and 80 degrees C. All reactions were monitored simultaneously by UV-visible measurements to determine changes in the nature of the protein during the course of reaction. The synthesis of Au NPs caused the simultaneous denaturation of protein due to the formation of bioconjugate NPs, and the denaturation temperature decreased with the number of NPs. Lys entrapped NPs in a typical gel state, and Cyc,c carried them on well-defined micelles at 80 degrees C or in the form of long fibrils or strands at 40 degrees C. The shape, size, and arrangement of bioconjugate NPs were characterized by atomic force microscopy and transmission electron microscopy measurements. Purified bioconjugate NPs were further used in zein protein film formation. The resulting films were characterized by photophysical and mechanical measurements. The induction of bioconjugate NPs made protein films isotropic and relatively more brittle (with a greater effect for Cyc,c than for Lys conjugate NPs) than in their absence and was considered to be well suited for biomedical applications.
The flavin mononucleotide (FMN) riboswitch is an emerging target for the development of novel RNA-targeting antibiotics. We previously discovered an FMN derivative, 5FDQD, that protects mice against diarrhea-causing Clostridium difficile bacteria. Here, we present the structure-based drug design strategy that led to the discovery of this fluoro-phenyl derivative with antibacterial properties. This approach involved the following stages: (1) structural analysis of all available free and bound FMN riboswitch structures; (2) design, synthesis, and purification of derivatives; (3) in vitro testing for productive binding using two chemical probing methods; (4) in vitro transcription termination assays; and (5) resolution of the crystal structures of the FMN riboswitch in complex with the most mature candidates. In the process, we delineated principles for productive binding to this riboswitch, thereby demonstrating the effectiveness of a coordinated structure-guided approach to designing drugs against RNA.
Contemporaneous presence of both oxidized and reduced forms of electron carriers is mandatory in efficient flux by plant electron transport cascades. This requirement is considered as redox poising that involves the movement of electron from multiple sites in respiratory and photosynthetic electron transport chains to molecular oxygen. This flux triggers the formation of superoxide, consequently give rise to other reactive oxygen species (ROS) under adverse environmental conditions like drought, high, or low temperature, heavy metal stress etc.. . that plants owing during their life span. Plant cells synthesize ascorbate, an additional hydrophilic redox buffer, which protect the plants against oxidative challenge. Large pools of antioxidants also preside over the redox homeostasis. Besides, tocopherol is a liposoluble redox buffer, which efficiently scavenges the ROS like singlet oxygen. In addition, proteinaceous thiol members such as thioredoxin, peroxiredoxin, and glutaredoxin, electron carriers and energy metabolism mediators phosphorylated (NADP) and non-phosphorylated (NAD +) coenzyme forms interact with ROS, metabolize and maintain redox homeostasis.
Over the course of two years, 2012-2014, we have implemented a 'flipping' the classroom approach in three of our large enrolment first year calculus courses: differential and integral calculus for scientists and engineers. In this article we describe the details of our particular approach and share with the reader some experiences of both instructors and students.
Real-time monitoring of harmful gases is of great significance to identify the environmental hazards to people's lives. However, this application scenario requiring low-power consumption, superior sensitivity, portability, and self-driven operation of gas sensors remains a challenge. Herein, an electrospun triboelectric nanogenerator (TENG) is synthesized using highly electronegative and conducting MXene nanofibers (NFs) paired with biodegradable cellulose acetate NFs (CA-NFs) as triboelectric layers, which supports a sufficient power density (∼1361 mW/m 2 @2 MΩ) and shows a self-powered ability to operate the chemiresistive gas sensor fabricated in this work. Further, by using cellulose nanofibers (C-NFs) as a substrate, a new kind of MXene/TiO 2 /C-NFs heterojunction-based sensory component is developed for detection of NH 3 . This sensor exhibits excellent reproducibility, high selectivity, and sensitivity toward NH 3 (1−100 ppm) along with a fast response/recovery time (76 s/62 s) at room temperature. Finally, a monitoring system comprising a TENG-powered sensor, an equivalent circuit, and an LED visualizer has been assembled and successfully demonstrated as a fully self-powered device for NH 3 leakage detection. Thus, this work pushes forward the intelligent gas sensing network self-driven by human motion energy, dispensing the external battery dependence for environment monitoring to reduce the possible health effects.
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