Structure of a Complete ATP Synthase Dimer Reveals the Molecular Basis of Inner Mitochondrial Membrane Morphology

We determined the structure of a complete, dimeric F1Fo-ATP synthase from yeast Yarrowia lipolytica mitochondria by a combination of cryo-EM and X-ray crystallography. The final structure resolves 58 of the 60 dimer subunits. Horizontal helices of subunit a in Fo wrap around the c-ring rotor, and a total of six vertical helices assigned to subunits a, b, f, i, and 8 span the membrane. Subunit 8 (A6L in human) is an evolutionary derivative of the bacterial b subunit. On the lumenal membrane surface, subunit f establishes direct contact between the two monomers. Comparison with a cryo-EM map of the F1Fo monomer identifies subunits e and g at the lateral dimer interface. They do not form dimer contacts but enable dimer formation by inducing a strong membrane curvature of ∼100°. Our structure explains the structural basis of cristae formation in mitochondria, a landmark signature of eukaryotic cell morphology

Carbohydrate Metabolism in Hypoglycemia

Hypoglycemia is generated by mechanisms directly related to an increase in insulin secretion, by metabolic disorders that require increased glucose consumption or by a deficient metabolic production of glucose by the body. Mechanisms include high glucose intake, increased dose of oral hypoglycemic, exogenous administration of insulin, metabolic hepatic conditions that lead to an increase in the production of amino acids, growing tumors, and in diabetic pregnant woman with abnormal increase in glucose and amino acids that end up producing insulin hypersecretion in the newborn. Work that requires high glucose expenditure or reduction of insulin antagonist, such as cortisol and glucagon, ends up in hypoglycemia. Finally, hypoglycemia is generated by metabolic deficit in pathophysiological situations such as defects in enzymatic systems, alcoholic hepatitis, and insufficient nutrition. The most characteristic symptoms include bulimia, fits of sweating, and tremors due to a strong activation of the sympathetic system. Obviously, the CNS is strongly affected by the lack of glucose, which is even more complicated because also hypoglycemia leads to a situation of decreased lipolysis and ketone bodies that finally seriously compromise the supply of energy to the nervous system, producing losses of consciousness, spasms, and even irreversible brain damage

AN EXPERIMENTAL STUDY OF THE CONVECTIVE HEAT TRANSFER ENHANCEMENT: APPLICATION OF TURBULENCE PROMOTERS

This work presents an experimental study addressing the effects of turbulence promoters on heat transfer rate at circular cylinder in external cross flow. Within this framework, the work focuses on assessing the effects of three kind of turbulence promoters (with circular, square and hexagonal cross sections) on convective heat transfer enhancement. The distance from turbulence promoters to the circular cylinder (50, 100 and 150mm upstream), as well as the free stream velocity inside the wind tunnel (Reynolds number) were the parameters investigated. The validation of the experimental methodology was performed by comparing the present results with empiric correlations available in the literature. The main results indicate that the convective heat transfer coefficient was enhanced when using turbulence promoters. The highest heat transfer enhancement obtained was around 25% correponding to the case of square turbulence promoter placed closely (50mm) to the circular cylinder. Finally, it is worth mentioning that all the experimental results for the convective coefficient were condensed in a new empirical correlation with good accuracy

EXAFS investigation of the interaction of hafnium and thorium with humic acid and Bio-Rex 70

The interaction of hafnium(IV) and thorium(iv) with humic acid, HA, is studied using EXAFS and compared to the interaction of these metal ions with carboxylate groups of the cation exchanger Bio-Rex70. Fourier-f'fltered Hf and Th I-,3 edge transmission EXAFS for the first oxygen shell is analyzed. For both Hf(IV)- HA and Hf(IV)-Bio-Rex70, in wet paste and air-dried forms, 6-7 oxygen atoms at R=2.14 A are found. Th(IV)-HA also exhibits coordination similar to Th(IV)-Bio-Rex70. These observations support conclusions from previous studies on U(VI)-HA that metal cations are sorbed primarily onto HA carboxylate groups; other HA functional groups play a less significant role

Diquat Derivatives: Highly Active, Two-Dimensional Nonlinear Optical Chromophores with Potential Redox Switchability

In this article, we present a detailed study of structure−activity relationships in diquaternized 2,2′-bipyridyl (diquat) derivatives. Sixteen new chromophores have been synthesized, with variations in the amino electron donor substituents, π-conjugated bridge, and alkyl diquaternizing unit. Our aim is to combine very large, two-dimensional (2D) quadratic nonlinear optical (NLO) responses with reversible redox chemistry. The chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Their visible absorption spectra are dominated by intense π → π^* intramolecular charge-transfer (ICT) bands, and all show two reversible diquat-based reductions. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering with an 800 nm laser, and Stark spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large and increase with the extent of π-conjugation and electron donor strength. Extending the quaternizing alkyl linkage always increases the ICT energy and decreases the E_(1/2) values for diquat reduction, but a compensating increase in the ICT intensity prevents significant decreases in Stark-based β_0 responses. Nine single-crystal X-ray structures have also been obtained. Time-dependent density functional theory clarifies the molecular electronic/optical properties, and finite field calculations agree with polarized HRS data in that the NLO responses of the disubstituted species are dominated by ‘off-diagonal’ β_(zyy) components. The most significant findings of these studies are: (i) β_0 values as much as 6 times that of the chromophore in the technologically important material (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium tosylate; (ii) reversible electrochemistry that offers potential for redox-switching of optical properties over multiple states; (iii) strongly 2D NLO responses that may be exploited for novel practical applications; (iv) a new polar material, suitable for bulk NLO behavior

Evolution of Linear Absorption and Nonlinear Optical Properties in V-Shaped Ruthenium(II)-Based Chromophores

In this article, we describe a series of complexes with electron-rich cis-{Ru^(II)(NH_3)_4}^(2+) centers coordinated to two pyridyl ligands bearing N-methyl/arylpyridinium electron-acceptor groups. These V-shaped dipolar species are new, extended members of a class of chromophores first reported by us (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845−4859). They have been isolated as their PF_6− salts and characterized by using various techniques including ^1H NMR and electronic absorption spectroscopies and cyclic voltammetry. Reversible Ru^(III/II) waves show that the new complexes are potentially redox-switchable chromophores. Single crystal X-ray structures have been obtained for four complex salts; three of these crystallize noncentrosymmetrically, but with the individual molecular dipoles aligned largely antiparallel. Very large molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) with an 800 nm laser and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d → π^* metal-to-ligand charge-transfer (MLCT) and π → π^* intraligand charge-transfer (ILCT) bands. The latter measurements afford total nonresonant β_0 responses as high as ca. 600 × 10^(−30) esu. These pseudo-C_(2v) chromophores show two substantial components of the β tensor, β_(zzz) and β_(zyy), although the relative significance of these varies with the physical method applied. According to HRS, β_(zzz) dominates in all cases, whereas the Stark analyses indicate that β_(zyy) is dominant in the shorter chromophores, but β_(zzz) and β_(zyy) are similar for the extended species. In contrast, finite field calculations predict that β_(zyy) is always the major component. Time-dependent density functional theory calculations predict increasing ILCT character for the nominally MLCT transitions and accompanying blue-shifts of the visible absorptions, as the ligand π-systems are extended. Such unusual behavior has also been observed with related 1D complexes (Coe, B. J. et al. J. Am. Chem. Soc. 2004, 126, 3880−3891)