Activation of visual pigments by light and heat

Vision begins with photoisomerization of visual pigments. Thermal energy can complement photon energy to drive photoisomerization, but it also triggers spontaneous pigment activation as noise that interferes with light detection. For half a century, the mechanism underlying this dark noise has remained controversial. We report here a quantitative relation between a pigment's photoactivation energy and its peak-absorption wavelength, λ(max). Using this relation and assuming that pigment activations by light and heat go through the same ground-state isomerization energy barrier, we can predict the relative noise of diverse pigments with multi-vibrational-mode thermal statistics. The agreement between predictions and our measurements strongly suggests that pigment noise arises from canonical isomerization. The predicted high noise for pigments with λ(max) in the infrared presumably explains why they apparently do not exist in nature.     

Structural observation of the primary isomerization in vision with femtosecond-stimulated Raman

The primary event that initiates vision is the light-induced 11-cis to all-trans isomerization of retinal in the visual pigment rhodopsin. Despite decades of study with the traditional tools of chemical reaction dynamics, both the timing and nature of the atomic motions that lead to photoproduct production remain unknown. We used femtosecond-stimulated Raman spectroscopy to obtain time-resolved vibrational spectra of the molecular structures formed along the reaction coordinate. The spectral evolution of the vibrational features from 200 femtoseconds to 1 picosecond after photon absorption reveals the temporal sequencing of the geometric changes in the retinal backbone that activate this receptor.     

Dispersed polaron simulations of electron transfer in photosynthetic reaction centers

A microscopic method for simulating quantum mechanical, nuclear tunneling effects in biological electron transfer reactions is presented and applied to several electron transfer steps in photosynthetic bacterial reaction centers. In this "dispersed polaron" method the fluctuations of the protein and the electron carriers are projected as effective normal modes onto an appropriate reaction coordinate and used to evaluate the quantum mechanical rate constant. The simulations, based on the crystallographic structure of the reaction center from Rhodopseudomonas viridis, focus on electron transfer from a bacteriopheophytin to a quinone and the subsequent back-reaction. The rates of both of these reactions are almost independent of temperature or even increase with decreasing temperature. The simulations reproduce this unusual temperature dependence in a qualitative way, without the use of adjustable parameters for the protein's Franck-Condon factors. The observed dependence of the back-reaction on the free energy of the reaction also is reproduced, including the special behavior in the "inverted region."     

Methylhydroxycarbene: tunneling control of a chemical reaction

Chemical reactivity is conventionally understood in broad terms of kinetic versus thermodynamic control, wherein the decisive factor is the lowest activation barrier among the various reaction paths or the lowest free energy of the final products, respectively. We demonstrate that quantum-mechanical tunneling can supersede traditional kinetic control and direct a reaction exclusively to a product whose reaction path has a higher barrier. Specifically, we prepared methylhydroxycarbene (H(3)C-C-OH) via vacuum pyrolysis of pyruvic acid at about 1200 kelvin (K), followed by argon matrix trapping at 11 K. The previously elusive carbene, characterized by ultraviolet and infrared spectroscopy as well as exacting quantum-mechanical computations, undergoes a facile [1,2]hydrogen shift to acetaldehyde via tunneling under a barrier of 28.0 kilocalories per mole (kcal mol(-1)), with a half-life of around 1 hour. The analogous isomerization to vinyl alcohol has a substantially lower barrier of 22.6 kcal mol(-1) but is precluded at low temperature by the greater width of the potential energy profile for tunneling.     

Vibrational promotion of electron transfer

By using laser methods to prepare specific quantum states of gas-phase nitric oxide molecules, we examined the role of vibrational motion in electron transfer to a molecule from a metal surface free from the complicating influence of solvation effects. The signature of the electron transfer process is a highly efficient multiquantum vibrational relaxation event, where the nitrogen oxide loses hundreds of kilojoules per mole of energy on a subpicosecond time scale. These results cannot be explained simply on the basis of Franck-Condon factors. The large-amplitude vibrational motion associated with molecules in high vibrational states strongly modulates the energetic driving force of the electron transfer reaction. These results show the importance of molecular vibration in promoting electron transfer reactions, a class of chemistry important to molecular electronics devices, solar energy conversion, and many biological processes.     

影响马肉灌肠质量的主要因素

马肉具有独特的理化特性。灌肠加工工艺中对腌制时的pH值、机械处理条件以及熟制时的温度等对制品的持水性、结着性都有影响。其它色素含量较高,与维生素C相互作用,使制品色泽较深。为保持其原有的营养保健特点,建议不必采用化学褪色法处理,可对消费者进行宣传和引导。     

A membrane receptor for retinol binding protein mediates cellular uptake of vitamin A

Vitamin A has diverse biological functions. It is transported in the blood as a complex with retinol binding protein (RBP), but the molecular mechanism by which vitamin A is absorbed by cells from the vitamin A-RBP complex is not clearly understood. We identified in bovine retinal pigment epithelium cells STRA6, a multitransmembrane domain protein, as a specific membrane receptor for RBP. STRA6 binds to RBP with high affinity and has robust vitamin A uptake activity from the vitamin A-RBP complex. It is widely expressed in embryonic development and in adult organ systems. The RBP receptor represents a major physiological mediator of cellular vitamin A uptake.     

Electric power from differences in salinity: the dialytic battery

An array of alternating anion and cation exchange membranes can be used to generate electric power from the free energy of mixing of river and sea waters. A simple mathematical model, which predicts experimental results well, is useful in exploring conditions for optimization of the process. Major, but not impossible, improvements in technology would be required to bring the cost of power from the dialytic battery into line with foreseeable energy prices.     

Dynamics-driven reaction pathway in an intramolecular rearrangement

A critical role is traditionally assigned to transition states (TSs) and minimum energy pathways, or intrinsic reaction coordinates (IRCs), in interpreting organic reactivity. Such an interpretation, however, ignores vibrational and kinetic energy effects of finite temperature. Recently it has been shown that reactions do not necessarily follow the intermediates along the IRC. We report here molecular dynamics (MD) simulations that show that dynamics effects may alter chemical reactions even more. In the heterolysis rearrangement of protonated pinacolyl alcohol Me3C-CHMe-OH2+ (Me, methyl), the MD pathway involves a stepwise route with C-O bond cleavage followed by methyl group migration, whereas the IRC pathway suggests a concerted mechanism. Dynamics effects may lead to new interpretations of organic reactivity.     

化学反应中Gibbs自由能的改变

本文通过绘制G—ξ图进行讨论化学反应中Gibbs自由能的改变与反应方向和限度间的关系。同时阐明了△G和G(?)/(?)ξ的区别,明确了Gibbs自由能应该采取的单位。     

Strange floral attractors: pollinator attraction and the evolution of plant sexual systems

Individual plants of hummingbird-pollinated Besleria triflora display two flower morphs: staminate flowers, which have shortened styles and do not produce fruit, and hermaphrodite flowers. Experiments with B. triflora indicate that pollinator attraction can drive the evolution of a dimorphic plant sexual system. In field-manipulated plants, visitation increased at large floral displays; however, pollen receipt increased only when staminate flowers were used to enlarge the display. Laboratory experiments showed that staminate flowers do not remove pollen from visiting pollinators, effectively concentrating outcross pollen onto stigmas of fertile flowers. A dimorphic sexual system is favored because the morphology of staminate flowers enhances their role in pollinator attraction.     

Single reconstituted neuronal SNARE complexes zipper in three distinct stages

Soluble N-ethylmaleimide-sensitive factor attachment protein receptor (SNARE) proteins drive membrane fusion by assembling into a four-helix bundle in a zippering process. Here, we used optical tweezers to observe in a cell-free reconstitution experiment in real time a long-sought SNARE assembly intermediate in which only the membrane-distal amino-terminal half of the bundle is assembled. Our findings support the zippering hypothesis, but suggest that zippering proceeds through three sequential binary switches, not continuously, in the amino- and carboxyl-terminal halves of the bundle and the linker domain. The half-zippered intermediate was stabilized by externally applied force that mimicked the repulsion between apposed membranes being forced to fuse. This intermediate then rapidly and forcefully zippered, delivering free energy of 36 k(B)T (where k(B) is Boltzmann's constant and T is temperature) to mediate fusion.     

微孔板法测定功能性饮料中的维生素B_(12)

通过样品处理比较试验、色素影响评价、回收率试验和重复性试验,得到了微孔板法测定功能性饮料中维生素B12的有效方法。经测定,该方法测定限可达到0.005μg/L,1.0、2.0、20.0μg/L三个梯度水平的加标回收率为94.4%~101.8%,实际样品测定中相对标准偏差为0.35%~4.34%(n=6),灵敏度和重复性很高,可用于测定功能性饮料中微量的维生素B12。     

Direct measurement of energy thresholds to conformational isomerization in tryptamine

Stimulated emission pumping (SEP)-hole filling spectroscopy and SEP-induced population transfer spectroscopy have been used to place narrow bounds on the energy thresholds for isomerization between individual reactant-product isomer pairs involving the seven conformational minima of tryptamine. The thresholds for isomerizing conformer A to all six other conformations divided into three groups at 750 wavenumbers (cm-1)(A-->B, F), 1000 cm-1 [A-->C(2)], and 1280 to 1320 cm-1 [A-->D, E, and C(1)]. The appearance of the first band and the absence of the band below it were used to place upper and lower bounds to the barrier heights for each process. The thresholds for A-->B and B-->A isomerizations were also combined to determine the relative energies of these two lowest energy minima. The combined data from all X-->Y isomerizations identify important isomerization pathways on the potential energy surface linking the minima.     

The effect of the prepartum diet of the cow on the vitamin A reserves of her newborn offspring

Feeding vitamin A at the rate of a million U.S.P. units daily to individual dairy cows in the latter stages of gestation augmented significantly the vitamin A concentration in the blood and the livers of their newborn calves, but pasture grazing, providing an abundance of carotene in the prepartum diet of the dams, failed to effect an increase over that observed in calves from dams restricted to a standard winter ration. The explanation for these divergent results is obscure, but it is suggested that the placental membrane may be more permeable to the ester form of vitamin A than to the alcohol form. This high initial vitamin A reserve in the newborn calf should have practical value in the maintenance of its postnatal health.     

Do vibrational excitations of CHD3 preferentially promote reactivity toward the chlorine atom?

The influence of vibrational excitation on chemical reaction dynamics is well understood in triatomic reactions, but the multiple modes in larger systems complicate efforts toward the validation of a predictive framework. Although recent experiments support selective vibrational enhancements of reactivities, such studies generally do not properly account for the differing amounts of total energy deposited by the excitation of different modes. By precise tuning of translational energies, we measured the relative efficiencies of vibration and translation in promoting the gas-phase reaction of CHD3 with the Cl atom to form HCl and CD3. Unexpectedly, we observed that C-H stretch excitation is no more effective than an equivalent amount of translational energy in raising the overall reaction efficiency; CD3 bend excitation is only slightly more effective. However, vibrational excitation does have a strong impact on product state and angular distributions, with C-H stretch-excited reactants leading to predominantly forward-scattered, vibrationally excited HCl.     

Vitamin A deficiency effect on retina: dependence on light

The effects of vitamin A deficiency in the rat eye, as measured by the electroretinogram and changes in rhodopsin content, are critically dependent upon the levels of illumination to which the animals are exposed daily. Depleted animals kept in darkness maintained virtually normal electroretinogram function and rhodopsin content for 5 to 6 months while those kept in weak cyclic light lost rhodopsin continuously. A fraction of the retinol released from rhodopsin during illumination disappears presumably from the pigment epithelium into the blood and becomes unavailable for rhodopsin regeneration. A sequence of three first-order reactions was assumed to estimate the rate constant of this disappearance (0.03 per hour). Computer simulation supporting the experimental data illustrates the dependence of the retinal abnormalities on light.