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A new Schiff base, [H(4)pydmedpt](2+)·2Cl(-), derived from one of the forms of vitamin B(6) has been synthesized by condensation of pyridoxal hydrochloride with N,N-bis[3-aminopropyl]-methylamine (medpt) and characterized by analytical and spectroscopic methods. The molecular structure is calculated by density functional theory (DFT) procedures, and the donor properties of each individual donor atom are evaluated by calculation of the Fukui function. One pot reaction of pyridoxal and medpt with vanadyl acetylacetonate yields the brown complex [V(IV)O(H(2)pydmedpt)](2+)·2Cl(-)1, which upon recrystallization from water crystallizes as [V(IV)O(pydmedpt)]·5H(2)O 2. The compounds are characterized by analytical and spectroscopic methods, 2 being also characterized by single crystal X-ray diffraction. It displays a slightly distorted octahedral geometry around the vanadium atom involving the coordination of N(amine), two N(imine), and O(phenolato) donors of the ligand. One of the phenolato oxygen donors is positioned trans to the terminal O-oxido atom with relatively short V-O(phenolate) {2.041(3) Å} and long V-O(oxido) {1.625(4) Å} bond distances when compared to other known compounds. The two different pK(a) values (6.0 and 7.9) obtained for 1 are due to protonation of the pyridine ring nitrogen atoms having different basic characters, this being also substantiated by theoretical calculation of the proton affinity of the O- and N- atoms of the molecule. The spin Hamiltonian parameters are obtained from the electron paramagnetic resonance (EPR) spectra, but the A(z) value (ca. 155 × 10(-4) cm(-1)) is lower than expected by applying the additivity rule for the present set of equatorial donor atoms (ca. 162-163 × 10(-4) cm(-1)), this being attributed to the strong trans V-O(phenolate) bond. The UV-vis transitions and EPR spectral parameters are calculated by DFT procedures, and both the calculated electronic transitions and the hyperfine coupling constants agree well with those experimentally observed. The inhibitory effect of 1 on FFA release and % glucose uptake determined with isolated rat adipocyte cells gave IC(50) and EC(50) values lower than for V(IV)OSO(4) and of the same order of magnitude of other reported insulin enhancing vanadium compounds.

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This paper describes the activity of a Schiff base ligand, derived from pyridoxal, as a promising fluorescence probe for biologically important Zn(II) ion sensing. This is the first report of a vitamin based ligand as a fluorescent probe for sensing Zn(II) ions. The Schiff base H 2 pydmedpt, derived from the condensation of pyridoxal ( pyd) and N,N-bis[3-aminopropyl]methylamine (medpt), exhibits around a 325-fold increase in fluorescence quantum yield due to zinc triggered fluorescence switching. The response is specific for Zn(II) ions, and remains unaffected by the presence of alkali and alkaline earth metals but is suppressed to varying degrees by transition metal ions. The corresponding Zn(II)-complex, [Zn( pydmedpt], is isolated. The DFT optimized structure of the complex is compatible with elemental analysis, mass spectrometry, FT-IR, electronic and NMR spectra. The isolated complex, having pK a values of ∼5.3 and ∼5, is a moderate intercalator for DNA with an apparent binding constant of 2.3 × 10 6 M −1 . The complex also shows insulin-enhancing activity at par with other reported complexes, with an IC 50 value of 0.65 with respect to ZnSO 4 . † Electronic supplementary information (ESI) available. See

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Tryptophan (Trp) plays a variety of critical functional roles in protein biochemistry; however, owing to its low natural frequency and poor nucleophilicity, the design of effective methods for both single protein bioconjugation at Trp as well as for in situ chemoproteomic profiling remains a challenge. Here, we report a method for covalent Trp modification that is suitable for both scenarios by invoking photo-induced electron transfer (PET) as a means of driving efficient reactivity. We have engineered biaryl N-carbamoyl pyridinium salts that possess a donor–acceptor relationship that enables optical triggering with visible light whilst simultaneously attenuating the probe’s photo-oxidation potential in order to prevent photodegradation. This probe was assayed against a small bank of eight peptides and proteins, where it was found that micromolar concentrations of the probe and short irradiation times (10–60 min) with violet light enabled efficient reactivity toward surface exposed Trp residues. The carbamate transferring group can be used to transfer useful functional groups to proteins including affinity tags and click handles. DFT calculations and other mechanistic analyses reveal correlations between excited state lifetimes, relative fluorescence quantum yields, and chemical reactivity. Biotinylated and azide-functionalized pyridinium salts were used for Trp profiling in HEK293T lysates and in situ in HEK293T cells using 440 nm LED irradiation. Peptide-level enrichment from live cell labeling experiments identified 290 Trp modifications, with 82% selectivity for Trp modification over other π-amino acids, demonstrating the ability of this method to identify and quantify reactive Trp residues from live cells.