Salashusted2811

A sequential [3 + 2]/[2 + 1] annulation domino reaction of crotonate-derived sulfur ylides and Morita-Baylis-Hillman carbonates of isatins for the construction of oxospiro[bicyclo[3.1.0]hexane-6,3'-indolin] scaffolds in moderate to good yields with almost 11 diastereoselectivity has been developed. Mild reaction conditions and readily accessible starting materials as well as excellent functional group compatibility render this transformation a powerful tool for the synthesis of spirocyclopropyloxindoles. A gram-scale synthetic procedure was also successfully carried out and a plausible reaction mechanism could be proposed.We describe herein a path-dependent "history" effect wherein the film morphology generated in the second step of a two-step inorganic phototropic growth process depends on a preexisting structure that has been first grown under different optical stimulation conditions. Se-Te generated with static illumination exhibited a highly anisotropic lamellar morphology with a characteristic feature pitch proportional to the input wavelength. Growth using first a short wavelength of light, followed by growth using a longer wavelength, resulted in the second-stage morphology exhibiting termination of lamellae formed during the first growth step. The lamellar pitch at the end of the second growth step was larger than that effected in the first step. In contrast, use of the same input wavelengths but in the opposite order produced no change in the feature pitch but rather only linear feature extension. Analysis of light absorption in simulated structures, in tandem with the empirical data, indicated that the history effect and asymmetric path dependence are a result of emergent nanophotonic processes at the growth interface that dynamically shape the optical field and direct morphological evolution of the photodeposit in a continuous feedback loop.The creation of stable molecular monolayers on metallic surfaces is a fundamental challenge of surface chemistry. N-Heterocyclic carbenes (NHCs) were recently shown to form self-assembled monolayers that are significantly more stable than the traditional thiols on Au system. Here we theoretically and experimentally demonstrate that the smallest cyclic carbene, cyclopropenylidene, binds even more strongly than NHCs to Au surfaces without altering the surface structure. We deposit bis(diisopropylamino)cyclopropenylidene (BAC) on Au(111) using the molecular adduct BAC-CO2 as a precursor and determine the structure, geometry, and behavior of the surface-bound molecules through high-resolution X-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy. Our experiments are supported by density functional theory calculations of the molecular binding energy of BAC on Au(111) and its electronic structure. Our work is the first demonstration of surface modification with a stable carbene other than NHC; more broadly, it drives further exploration of various carbenes on metal surfaces.Superoxide dismutases (SODs) are a group of enzymes that have a crucial role in controlling oxidative stress in plants. Here, we synthesized an environmentally friendly SOD mimic, SODm-123, from L-aspartic acid and manganese oxide. SODm-123 showed similar enzymatic activity to Mn-SOD. To gain insights into the role of SODm-123 in oxidative stress tolerance, a series of experiments were conducted to assess the physiological and molecular responses of tomato plants when treated with SODm-123. The results showed that the levels of O2-• and H2O2 in tomato cells were affected by SODm-123 treatment, indicating that SODm-123 can control oxidative stress like Mn-SOD. The results also exhibited that SODm-123 increased the contents of photosynthetic pigments. However, it was noted that SODm-123 resulted in a reduction in the content of soluble sugar and MDA. These results indicate that SODm-123 promoted the efficiency of photosynthesis by regulating the content of H2O2. To further investigate the role of SODm-123 in controlling oxidative stress, a transcriptome analysis was used to identify differentially expressed genes (DEGs) associated with SODm-123 treatment. The results indicated that SODm-123 treatment resulted in 341 differentially expressed genes (DEGs) in treated tomato leaves at 96 h after treatment. Kyoto encyclopedia of genes and genomes (KEGG) revealed that DEGs were involved in pathways such as photosynthetic pigment biosynthesis, ABC transporters, sugar metabolism, and MAPK signaling, which further confirmed a positive role of SODm-123 in improving stress tolerance in plants. Overall, the results of this study suggest that SODm-123 promotes the growth and development of tomato seedlings and therefore can be used as a potential growth-promoting agent for plants.Genetically encoded fluorescent tags for visualization of proteins in living cells add six to several hundred amino acids to the protein of interest. While suitable for most proteins, common tags easily match and exceed the size of microproteins of 60 amino acids or less. The added molecular weight and structure of such fluorescent tag may thus significantly affect in vivo biophysical and biochemical properties of microproteins. Selleckchem KD025 Here, we develop single-residue terminal labeling (STELLA) tags that introduce a single noncanonical amino acid either at the N- or C-terminus of a protein or microprotein of interest for subsequent specific fluorescent labeling. Efficient terminal noncanonical amino acid mutagenesis is achieved using a precursor tag that is tracelessly cleaved. Subsequent selective bioorthogonal reaction with a cell-permeable organic dye enables live cell imaging of microproteins with minimal perturbation of their native sequence. The use of terminal residues for labeling provides a universally applicable and easily scalable strategy, which avoids alteration of the core sequence of the microprotein.In a remarkable example, we report a one-dimensional coordination polymer (CP) of Pb(II) showing photosalient (PS) properties triggered by [2 + 2] cycloaddition of olefinic ligands, which is seldom observed in CPs. Macroscopic rod-shaped crystals show various photomechanical effects such as jumping, splitting, rolling, and breaking upon UV illumination. In this rare example, we could determine the solid-state structure of the 100% dimerized product and three intermediate structures, even after the shattering of crystals into small pieces. Detailed mechanistic investigation from the single-crystal data indicates that the strain generated in the unit cell due to anisotropic expansion played a bigger role for the PS effects. Nucleated growth of the photoproduct crystal created different domains inside the single crystal, which multiplied the already developed stress leading to the photomechanical movements. This example falls in the gray area of a clean single-crystal-to-single-crystal (SCSC) transformation and violent PS effect.