Sensor Array Based Determination of Edman Degradated Amino Acids Using Poly(p-phenyleneethynylene)s

A cross-reactive optical sensor array based on poly(p-phenyleneethynylene)s (PPEs) determines Edman degraded amino acids. We report a sensor array composed of three anionic PPEs P1–P3 , and their electrostatic complexes with metal ions (Fe²⁺, Cu²⁺, Co²⁺). We recorded distinct fluorescence intensity response patterns as “fingerprints” of this chemical tongue toward standard phenylthiohydantoin (PTH) amino acids—degradation products of the Edman process. These “fingerprints” were converted into canonical scores by linear discrimination analysis (LDA), which differentiates all of the PTH-amino acids. This array discriminates PTH-amino acid residues degraded from an oligopeptide through Edman sequencing. This approach is complementary to chromatography approaches which rely on mass spectrometry; our array offers the advantage of simplicity.     

trans‐Selective Insertional Dihydroboration of a cis‐Diborene: Synthesis of Linear sp3‐sp2‐sp3‐Triboranes and Subsequent Cationization

The reaction of aryl‐ and amino(dihydro)boranes with dibora[2]ferrocenophane 1 leads to the formation 1,3‐trans‐dihydrotriboranes by formal hydrogenation and insertion of a borylene unit into the B=B bond. The aryltriborane derivatives undergo reversible photoisomerization to the cis‐1,2‐μ‐H‐3‐hydrotriboranes, while hydride abstraction affords cationic triboranes, which represent the first doubly base‐stabilized B₃H₄⁺ analogues.     

(Diazoalkyl)Phosphoranes from [4 + 1]-cycloadditions of tetrahalo-orthobenzoquinones to (diazoalkyl)phosphanes [1]

The (diazoalkyl)phosphanes 4a–e undergo [4 + 1]-cycloaddition reactions with the tetrahalo-orthobenzoquinones 5a,b to furnish the previously unknown (diazoalkyl)phosphoranes 6a–h . The structure of product 6h has been investigated by X-ray crystallography.     

3,5-Bis(2-hydroxyphenyl)-1<Emphasis Type="Italic">H</Emphasis>-1,2,4-triazole based ligands — protonation and metal complex formation

3,5-Bis(2-hydroxyphenyl)-1H-1,2,4-triazole (H₂L^a) and 4-[3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazol-1-yl]benzoic acid (H₃L^b) have been prepared, and crystal structure of the intermediate 2-(2-hydroxyphenyl)-4H-1,3-benzoxazin-4-one has been determined. Temperature dependent ¹H NMR spectroscopic measurements of H₂L^a indicated dynamic behavior with the equilibrium between the two asymmetric tautomers. For H₃L^b, pD-dependent ¹H NMR spectroscopic measurements showed small but characteristic shifts in the range of 0 ≤ pD ≤ 1, indicative of a triazole nitrogen atom protonation; the corresponding pK _a of 0.98 ± 0.04 was determined by spectrophotometric titrations. (H₂O, 26°C, 1 M KCl/HCl). Formation of [Fe^III(L^a)]⁺ (pH 2.5) and [Fe^III(L^a)₂]⁻ (pH > 6) was verified by UV-Vis spectroscopy. Complex formation of H₃L^b with Al³⁺ and VO²⁺ was investigated by ¹H NMR spectroscopic titration and cyclic voltammetry, respectively. Single crystals of the phenoxo bridged [V^VO(HL^b)(EtO)]₂·2EtOH were characterized by X-ray structural analysis. Dedicated to Professor Milan Melník on the occasion of his 70th birthday