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Spider silk is a protein material that exhibits extraordinary and nontrivial properties such as the ability to soften and decrease its length by up to ∼60% upon exposure to high humidity. This process is commonly called supercontraction and is the result of a transition from a highly oriented glassy phase to a disoriented rubbery phase. In this work, we derive a microscopically motivated and energy-based model that captures the underlying mechanisms that give rise to supercontraction. We propose that the increase in relative humidity and the consequent wetting of a spider silk have two main consequences (1) the dissociation of hydrogen bonds and (2) the swelling of the fiber. From a mechanical viewpoint, the first consequence leads to the formation of rubbery domains. This process is associated with an entropic gain and a loss of orientation of chains in the silk network, which motivates the contraction of the spider silk. The swelling of the fiber is accompanied by the extension of chains in order to accommodate the influx of water molecules. Supercontraction occurs when the first consequence is more dominant than the second. The model presented in this work allows us to qualitatively track the transition of the chains from glassy to rubbery states and determine the increase in entropy, the loss of orientation, and the swelling as the relative humidity increases. We also derive explicit expressions for the stiffness and the mechanical response of a spider silk under given relative humidity conditions. To illustrate the merit of this model, we show that the model is capable of capturing several experimental findings. PFK15 PFKFB inhibitor The insights from this work can be used as a microstructural design guide to enable the development of new materials with unique spider-like properties.Detection of environmental pollutants is crucial to safeguard ecological and public health. Here, we report a modular biosensing approach for the detection of contaminants based on the regulation of a minimal DNA signal amplifier and transducer circuit by allosteric transcription factors and their cognate ligands. We leverage the competition between allosteric proteins and an endonuclease to modulate cascade toehold-mediated strand displacement reactions, which are triggered in the presence of specific effectors and sustained by the endonuclease. We built two optical biosensors for the detection of tetracyclines and macrolides in water using repressors TetR and MphR, respectively. We demonstrate that our minimal, fast, and single-step biosensors can successfully detect antibiotics in nanomolar levels and apply them to report the presence of spiked-in antibiotics in water samples in a matter of minutes, suggesting great potential for monitoring of water contaminants.The hemocompatibility of blood-contacting medical devices remains one of the major challenges in medical device development. A common tool for the analysis of adherent and activated platelets on materials following in vitro tests is microscopy. Currently, most researchers develop their own routines, resulting in numerous different methods that are applied. The majority of those (semi-)manual methods analyze only a very small fraction of the material surface ( less then 1%), which neglects the inhomogeneity of platelet distribution and makes results hardly comparable. Within this study, we examined the relation between the fraction of analyzed sample area and the platelet adhesion result. By means of image segmentation and machine learning algorithms, 103 100 microscopy images were analyzed automatically. We discovered a crucial impact of the analyzed surface fraction and thus a misrepresentation of a surface's platelet adhesion unless up to 40% of the sample surface is analyzed. These findings underline the necessity of standardization in the field of in vitro hemocompatibility tests and analyses in particular and provide a first basis to make future tests more reliable and comparable.The dissemination of tumor metastasis in the peritoneal cavity, also called peritoneal metastasis (PM) or carcinomatosis, represents a late stage of gastrointestinal and gynecological cancer with very poor prognosis, even when cytoreductive surgery is effective, due to residual microscopic disease. Photodynamic therapy (PDT) in the management of peritoneal metastasis has been clinically limited by the low tumor selectivity of photosensitizers (PS) and important adverse effects. Here, we propose extracellular nanovesicles (EVs) derived from mesenchymal stem/stromal cells (MSCs) as the fourth generation of immune active PS vectors that are able to target peritoneal metastasis with superior selectivity, potentiate PDT cytotoxicity at the tumor site without affecting healthy tissues, modulate the tumor microenvironment of immunocompetent colorectal and ovarian carcinomatosis models, and promote an antitumor immune response. A pioneering strategy was developed for high yield, large-scale production of MSC-EVs encaur scalable manufacturing method appears like the clinically relevant fourth-generation PDT vehicle to overcome current limitations of PDT in the treatment of peritoneal metastasis and promote a hot tumor immune environment in PM.Chiral alkyl amines are omnipresent as bioactive molecules and synthetic intermediates. The catalytic and enantioselective synthesis of alkyl amines from readily accessible precursors is challenging. Here we develop a nickel-catalyzed hydroalkylation method to assemble a wide range of chiral alkyl amines from enecarbamates (N-Cbz-protected enamines) and alkyl halides with high regio- and enantioselectivity. The method works for both nonactivated and activated alkyl halides and is able to produce enantiomerically enriched amines with two minimally differentiated α-alkyl substituents. The mild conditions lead to high functional group tolerance, which is demonstrated in the postproduct functionalization of many natural products and drug molecules, as well as the synthesis of chiral building blocks and key intermediates to bioactive compounds.Actin molecules are essential structural components of the cellular cytoskeleton. Here, we report a comprehensive analysis of F-actin's deformation behavior and highlight underlying mechanisms using steered molecular dynamics simulations (SMD). The investigation of F-actin was done under tension, compression, bending, and torsion. We report that the dissociation pattern of conformational locks at intrastrand and interstrand G-actin interfaces regulates the deformation response of F-actin. The conformational locks at the G-actin interfaces are portrayed by a spheroidal joint, interlocking serrated plates' analogy. Further, the SMD simulation approach was utilized to evaluate Young's modulus, flexural rigidity, persistent length, and torsional rigidity of F-actin, and the values obtained were found to be consistent with available experimental data. The evaluation of the mechanical properties of actin and the insight into the fundamental mechanisms contributing to its resilience described here are necessary for developing accurate models of eukaryotic cells and for assessing cellular viability and mobility.Lanthanide(III)-based luminescent materials have attracted great research interests due to their unique optical, electronic, and chemical characteristics. Up to now, how to extend these materials into large, broad application fields is still a great challenging task. In this contribution, we are intended to present a simple but facile strategy to enhance the luminescence from lanthanide ions and impart lanthanide(III)-based luminescent materials with more applicable properties, leading to meet the requirements from different purposes, such as being used as highly emissive powders, hydrogels, films, and sensitive probes under external stimuli. Herein, a water soluble, blue color emissive, temperature sensitive, and film-processable copolymer (Poly-ligand) was designed and synthesized. Upon complexing with Eu3+ and Tb3+ ions, the red color-emitting Poly-ligand-Eu and green color-emitting Poly-ligand-Tb were produced. After finely tuning the ratios between them, a standard white color emitting Poly-ligand-Eu1Tb4 (CIE = 0.33 and 0.33) was obtained. Furthermore, the resulted materials not only possessed the emissive luminescent property but also inherited functions from the copolymer of Poly-ligand. Thus, these lanthanide(III)-based materials were used for fingerprint imaging, luminescent soft matters formation, colorful organic light-emitting diode device fabrication, and acid/alkali vapors detection.The emergence of two-dimensional (2D) materials launched a fascinating frontier of flatland electronics. Most crystalline atomic layer materials are based on layered van der Waals materials with weak interlayer bonding, which naturally leads to thermodynamically stable monolayers. We report the synthesis of a 2D insulator composed of a single atomic sheet of honeycomb structure BeO (h-BeO), although its bulk counterpart has a wurtzite structure. The h-BeO is grown by molecular beam epitaxy (MBE) on Ag(111) thin films that are also epitaxially grown on Si(111) wafers. Using scanning tunneling microscopy and spectroscopy (STM/S), the honeycomb BeO lattice constant is determined to be 2.65 Å with an insulating band gap of 6 eV. Our low-energy electron diffraction measurements indicate that the h-BeO forms a continuous layer with good crystallinity at the millimeter scale. Moiré pattern analysis shows the BeO honeycomb structure maintains long-range phase coherence in atomic registry even across Ag steps. We find that the interaction between the h-BeO layer and the Ag(111) substrate is weak by using STS and complementary density functional theory calculations. We not only demonstrate the feasibility of growing h-BeO monolayers by MBE, but also illustrate that the large-scale growth, weak substrate interactions, and long-range crystallinity make h-BeO an attractive candidate for future technological applications. More significantly, the ability to create a stable single-crystalline atomic sheet without a bulk layered counterpart is an intriguing approach to tailoring 2D electronic materials.Colloidal superlattices are fascinating materials made of ordered nanocrystals, yet they are rarely called "atomically precise". That is unsurprising, given how challenging it is to quantify the degree of structural order in these materials. However, once that order crosses a certain threshold, the constructive interference of X-rays diffracted by the nanocrystals dominates the diffraction pattern, offering a wealth of structural information. By treating nanocrystals as scattering sources forming a self-probing interferometer, we developed a multilayer diffraction method that enabled the accurate determination of the nanocrystal size, interparticle spacing, and their fluctuations for samples of self-assembled CsPbBr3 and PbS nanomaterials. The multilayer diffraction method requires only a laboratory-grade diffractometer and an open-source fitting algorithm for data analysis. The average nanocrystal displacement of 0.33 to 1.43 Å in the studied superlattices provides a figure of merit for their structural perfection and approaches the atomic displacement parameters found in traditional crystals.
Here's my website: https://www.selleckchem.com/products/pfk15.html
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