Fluorescence sensing based on cation-induced conformational switching: copper-selective modulation of the photoinduced intramolecular charge transfer of a donor-acceptor biphenyl fluorophore

The fluorescence emission energy of donor-acceptor substituted biphenyls is highly sensitive towards conformational changes of the interannular twist angle. By integrating 4-dimethylamino-4′-cyano-biphenyl into the ligand backbone of a thioether-rich metal receptor we designed a fluorescence sensor that exhibits high selectivity towards copper. Upon metal binding the ligand undergoes a significant conformational change, which induces a strong hypsochromic shift of the photoinduced charge-transfer emission. Steady-state absorption and fluorescence spectroscopy revealed a high affinity towards Cu(I) with a well-defined 1:1 metal-ligand complex stoichiometry. The nature of the conformational changes upon Cu(I) coordination were analyzed in detail by ¹H NMR and 2D NOESY experiments. The spectroscopic data provide a coherent picture, which is consistent with a Boltzmann ground-state distribution of several rotamers that are locked into a more flattened geometry upon coordination of Cu(I).     

Formal total synthesis of (−)-hamigeran B from a chemo-enzymatically prepared building block with quaternary chiral center

A formal total synthesis of (?)-hamigeran B was achieved in 17 steps from commercially available ethyl 2-oxocyclopentanecarboxylate. Carbonyl reductase-catalyzed asymmetric reduction and the subsequent chemical transformations furnished an enantiomerically pure synthetic intermediate, (R)-5-formyl-2-isopropyl-5-methylcyclopent-1-en-1-yl trifluoromethylsulfonate. Suzuki-Miyaura coupling with Gao's arylboronate [2-(2-formyl-3-methoxy-5-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane], under PdCl₂(dppf)?CH₂Cl₂ catalysis, and the subsequent cyclization by way of intramolecular reductive SmI₂-mediated 1,2-diol formation provided a tricyclic skeleton with a tetrasubstituted double bond between C-1 and C-9b. Upon hydrogenation of this double bond, the proper stereochemistry of the remaining chiral centers was established. Exclusive addition of the hydrogen atom from the β-face occurred, owing to the shielding of the α-face with a bulky TBS protective group on the C-4 alcohol. The hydrogenation products were transformed into Clive's synthetic precursor for (?)-hamigeran B.     

Modulation of calcium oxalate monohydrate crystallization by citrate through selective binding to atomic steps

The majority of human kidney stones are composed primarily of calcium oxalate monohydrate (COM) crystals. Thus, determining the molecular modulation of COM crystallization by urinary constituents is crucial for understanding and controlling renal stone disease. A comprehensive molecular-scale view of COM shape modification by citrate, obtained through a combination of in situ atomic force microscopy and molecular modeling, is presented here. We find that while the most important factors determining binding strength are coordination between COO- groups on citrate and Ca ions in the lattice, as well as H-bonds formed between the OH group of citrate and an oxalate group, the nonplanar geometry of the steps provides the most favorable environment due to the ability of the step-edge to accommodate all Ca-COO- coordinations with minimal strain. However, binding to all steps and terraces on the (010) face is much less favorable than on the (101) face due to electrostatic repulsion between oxalate and COO- groups. For example, the maximum binding energy, -166.5 kJ mol(-1), occurs for the [101] step on the (101) face, while the value for the [021] step on the (010) face is only -56.9 kJ mol(-1). This high selectivity leads to preferential binding to steps on the (101) face that pins step motion. Yet anisotropy in interaction strength on this face drives anisotropic changes in step kinetics that are responsible for shape modification of macroscopic COM crystals. Thus, the molecular scale growth kinetics and the bulk crystal habit are fully consistent with the simulations.     

X-ray structures,photophysical characterization,and computational analysis of geometrically constrained copper(I)--phenanthroline complexes

A series of three geometrically constrained C(2)-symmetric Cu(I) mono-phenanthroline complexes were characterized by X-ray structural analysis, and their photophysical properties were investigated by absorption and emission spectroscopy. Visible light excitation yielded metal-to-ligand charge-transfer (MLCT) excited states with luminescence lifetimes up to 155 ns. Ultrafast transient absorption spectroscopy provided further insights into the excited-state dynamics and suggests for all three complexes the formation of a phenanthroline radical anion. In agreement with electrochemical measurements, the data further indicate that coordinative rearrangements are involved in nonradiative deactivation of the excited states. According to time-dependent density functional theory calculations (B3LYP/6-31G), the major MLCT transitions are polarized along the C(2) axis of the complex and originate predominantly from the copper d(xz) orbital. The computational analysis identifies an excited-state manifold with a number of close-lying, potentially emissive triplet states and is in agreement with the multiexponential decay kinetics of the MLCT luminescence. The relationship between structural and photophysical data of the studied Cu(I) mono-phenanthroline complexes agrees well with current models describing the photophysics of the related Cu(I) bis-diimine complexes.     

Chemical states of tritium in solid lithium compounds irradiated with neutrons

Chemical states of tritium existing in neutron-irradiated solid lithium compounds were analyzed using a radiometric method. Nearly 100% of tritium was found in the T⁺ state in LiOH, Li₂O₂ and Li₃N, while the T^– state predominated in LiH, Li₇Pb₂ and Li₂C₂. Tritium incorporated in Li₂O, Li₂S, LiF, LiCl, LiBr and LiI was distributed over the T⁺, T^– and T⁰ states. In Li₂O crystals, the distribution of tritium in the T⁺ state increased from 58% to 81% with increasing neutron fluence from 2.5×10¹⁶ cm^–2 to 6.3×10¹⁷ cm^–2.     

Direct electrophilic diamination of functionalized alkenes without the use of any metal catalysts

A new direct electrophilic diamination reaction of alpha,beta-unsaturated ketones and esters has been established without the use of any metal catalysts. Three types of nitriles (CH(3)CN, CH(3)CH(2)CN, and CH(3)CH(2)CH(2)CN) were employed as nucleophilic nitrogen sources. A new mechanism has also been proposed to explain the resulting regio- and stereoselectivity.     

Screening, substrate specificity and stereoselectivity of yeast strains, which reduce sterically hindered isopropyl ketones

Towards the synthesis of sterically hindered optically active secondary alcohol 2, yeast strains (Candida floricola IAM 13115 and Trichosporon cutaneum IAM 12206) with si-face hydride attack on isopropyl phenylsulfonylmethyl ketone 1 were developed by screening. Strains with complementary re-facial selectivity (Pichia angusta IAM 12895 and Pichia minuta IAM 12215) were also found. Based on the substrate specificity studies of these four strains, microbial reduction was applied to the synthesis of (3S,5S)-2,6-dimethyl-3,5-heptanediol 12a.