Transition Metal-Catalyzed Enantioselective C−H Functionalization via Chiral Transient Directing Group Strategies

Transition metal-catalyzed enantioselective functionalization of C−H bond, the most abundant functionality in organic molecules, has emerged as an expedient synthetic approach to streamline the synthesis of complex chiral molecules. Despite significant progress, traditional directing group-enabled strategies require additional steps for the installation and removal of directing groups from the target molecule. The recently developed asymmetric C−H functionalization using chiral transient directing groups (cTDGs) offers a promising alternative that can circumvent this obstacle and therefore simplify the process. In this Minireview, we briefly discuss the advent and recent advances of this emerging concept, with an emphasis on discussing the creation of various stereogenic centers and the developments of cTDGs. Applications in natural product synthesis and ligand derivatizations are also discussed. We hope this Minireview will highlight the great potential of this strategy and help to inspire further endeavors.     

The Friedberg–Lee symmetry and minimal seesaw model

The Friedberg–Lee (FL) symmetry is generated by a transformation of a fermionic field q to q+ξz. This symmetry puts very restrictive constraints on allowed terms in a Lagrangian. Applying this symmetry to N fermionic fields, we find that the number of independent fields is reduced to N−1 if the fields have gauge interaction or the transformation is a local one. Using this property, we find that a seesaw model originally with three generations of left- and right-handed neutrinos, with the left-handed neutrinos unaffected but the right-handed neutrinos transformed under the local FL translation, is reduced to an effective theory of minimal seesaw which has only two right-handed neutrinos. The symmetry predicts that one of the light neutrino masses must be zero.     

Collider search of light dark matter model with dark sector decay

We explore the possibility that the dark matter relic density is not produced by a thermal mechanism directly, but by the decay of other heavier dark-sector particles which themselves can be produced by the thermal freeze-out mechanism. Using a concrete model with light dark matter from dark sector decay, we study the collider signature of the dark sector particles associated with Higgs production processes. We find that future lepton colliders could be a better place to probe the signature of this kind of light dark matter model than hadron colliders such as LHC. Also, we find that a Higgs factory with center-of-mass energy 250 GeV has a better potential to resolve the signature of this kind of light dark matter model than a Higgs factory with center-of-mass energy 350 GeV.     

The Constrained Solutions of Two Matrix Equations

We study the symmetric positive semidefinite solution of the matrix equation AX ₁ A ^T + BX ₂ B ^T = C, where A is a given real m×n matrix, B is a given real m×p matrix, and C is a given real m×m matric, with m, n, p positive integers; and the bisymmetric positive semidefinite solution of the matrix equation D ^T XD = C, where D is a given real n×m matrix, C is a given real m×m matrix, with m, n positive integers. By making use of the generalized singular value decomposition, we derive general analytic formulae, and present necessary and sufficient conditions for guaranteeing the existence of these solutions. Received December 17, 1999, Revised January 10, 2001, Accepted March 5, 2001     

Functional Ag porous films prepared by electrospinning

Face-centered cubic Ag porous films have been prepared directly from the heat treatment of AgNO₃-doped poly(vinyl alcohol) (PVA) electrospun nanofibers. Using Rhodamine B (RB) as the probing molecule, the surface-enhanced Raman scattering (SERS) effect of Ag porous films was demonstrated. The antibacterial activity of Ag porous films was also studied in this work. The propagation and biological activity of yeast cells were effectively inhibited by Ag porous films. These functional Ag porous films were expected to be applied in many fields, such as catalysis, diagnostics, sensors and antibacterial, etc.     

Stability evaluation of Tc-99m radiolabeled GRPr antagonist with amino acid chelators

In order to select a chelator with excellent stability, easier radiolabeling process and low cost, GRPr antagonist RM26 with the amino acid based chelator was radiolabeled with technetium-99m. The stability of the radiolabeled peptides in PBS, serum as well as in the presence of excess cysteine was compared.

     

Sialoside analogue arrays for rapid identification of high affinity siglec ligands

The siglec family of sialic acid binding proteins participates in diverse cell surface biology that includes regulation of immune cell signaling and the interaction of neuronal cells with glial cells. The weak intrinsic affinity of the natural sialoside ligands has hampered the development of synthetic ligand based probes needed to elucidate their roles in siglec function. In this report, we describe a glycan microarray comprising a library of 9-acyl-substituted sialic acids incorporated into sialosides containing the Neu5Acalpha2-3Gal and Neu5Acalpha-6Gal linkages commonly recognized by the siglecs. The array is demonstrated to exhibit utility for detecting 9-acyl substituents that increase the affinity of siglecs for their ligands. Substituents that increase affinity are anticipated to be useful for the design of high affinity ligand based probes of siglec function.     

On-virus construction of polyvalent glycan ligands for cell-surface receptors

Glycans arrayed on the exterior of virus particles were used as substrates for glycosyltransferase reactions to build di- and trisaccharides from the virus surface. The resulting particles exhibited tight and specific associations with cognate receptors on beads and cells, in one example defeating in cis cell-surface interactions in a manner characteristic of polyvalent binding. Combined with the ability of viruses to provide structurally well-defined attachment points, the methodology provides a convenient and powerful way to prepare complex carbohydrate ligands for clustered receptors.     

Electrosynthesis of α-Amino Acids from NO and other NOx species over CoFe alloy-decorated Self-standing Carbon Fiber Membranes

The conversion of industrial exhaust gases of nitrogen oxides into high-value products is significantly meaningful for global environment and human health. And green synthesis of amino acids is vital for biomedical research and sustainable development of mankind. Herein, we demonstrate an innovative approach for converting nitric oxide (NO) to a series of α-amino acids (over 13 kinds) through electrosynthesis with α-keto acids over self-standing carbon fiber membrane with CoFe alloy. The essential leucine exhibits a high yield of 115.4 μmol h⁻¹ corresponding a Faradaic efficiency of 32.4 %, and gram yield of products can be obtained within 24 hours in lab as well as an ultra-long stability (>240 h) of the membrane catalyst, which could convert NO into NH₂OH rapidly attacking α-keto acid and subsequent hydrogenation to form amino acid. In addition, this method is also suitable for other nitrogen sources including gaseous NO₂ or liquidus NO₃⁻ and NO₂⁻. Therefore, this work not only presents promising prospects for converting nitrogen oxides from exhaust gas and nitrate-laden waste water into high-value products, but also has significant implications for synthetizing amino acids in biomedical and catalytic science.     

Dual Photosensitizer Coupled Three-Dimensional Metal-Covalent Organic Frameworks for Efficient Photocatalytic Reactions

In this work, we innovatively assembled two types of traditional photosensitizers, that is pyridine ruthenium/ferrum (Ru(bpy)₃²⁺/Fe(bpy)₃²⁺) and porphyrin/metalloporphyrin complex (2HPor/ZnPor) by covalent linkage to get a series of dual photosensitizer-based three-dimensional metal-covalent organic frameworks (3D MCOFs), which behaved strong visible light-absorbing ability, efficient electron transfer and suitable band gap for highly efficient photocatalytic hydrogen (H₂) evolution. Rubpy-ZnPor COF achieved the highest H₂ yield (30 338 μmol g⁻¹ h⁻¹) with apparent quantum efficiency (AQE) of 9.68 %@420 nm, which showed one of the best performances among all reported COF based photocatalysts. Furthermore, the in situ produced H₂ was successfully tandem used in the alkyne hydrogenation with ≈99.9 % conversion efficiency. Theoretical calculations reveal that both the two photosensitizer units in MCOFs can be photoexcited and thus contribute optimal photocatalytic activity. This work develops a general strategy and shows the great potential of using multiple photosensitive materials in the field of photocatalysis.