Reaction of glucose catalyzed by framework and extraframework tin sites in zeolite beta

The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup, and is now being considered as an intermediate step in the possible route of biomass conversion into fuels and chemicals. Recently, it has been shown that a hydrophobic, large pore, silica molecular sieve having the zeolite beta structure and containing framework Sn⁴⁺ (Sn-Beta) is able to isomerize glucose into fructose in aqueous media. Here, I have investigated how this catalyst converts glucose to fructose and show that it is analogous to that achieved with metalloenzymes. Specifically, glucose partitions into the molecular sieve in the pyranose form, ring opens to the acyclic form in the presence of the Lewis acid center (framework Sn⁴⁺), isomerizes into the acyclic form of fructose and finally ring closes to yield the furanose product. Akin to the metalloenzyme, the isomerization step proceeds by intramolecular hydride transfer from C2 to C1. Extraframework tin oxides located within hydrophobic channels of the molecular sieve that exclude liquid water can also isomerize glucose to fructose in aqueous media, but do so through a base-catalyzed proton abstraction mechanism. Extraframework tin oxide particles located at the external surface of the molecular sieve crystals or on amorphous silica supports are not active in aqueous media but are able to perform the isomerization in methanol by a base-catalyzed proton abstraction mechanism. Post-synthetic exchange of Na⁺ with Sn-Beta alters the glucose reaction pathway from the 1,2 intramolecular hydrogen shift (isomerization) to produce fructose towards the 1,2 intramolecular carbon shift (epimerization) that forms mannose. Na⁺ remains exchanged onto silanol groups during reaction in methanol solvent, leading to a near complete shift in selectivity towards glucose epimerization to mannose. In contrast, decationation occurs during reaction in aqueous solutions and gradually increases the reaction selectivity to isomerization at the expense of epimerization. Decationation and concomitant changes in selectivity can be eliminated by addition of NaCl to the aqueous reaction solution. Thus, framework tin sites with a proximal silanol group are the active sites for the 1, 2 intramolecular hydride shift in the isomerization of glucose to fructose, while these sites with Na-exchanged silanol group are the active sites for the 1, 2 intramolecular carbon shift in epimerization of glucose to mannose.

Diurnal periodicity of winter activity in the perch, Perca fluviatilis L. [Translation from: Kalamies 1973(1) 3.]

Since 1967 data have been collected on the distribution of fish caught in a 24 hour period during the winter angling season. The present study on activity periods is based on data from nearly 2000 perch collected between 1967 and 1971. The distribution of number of fish caught during 24 hrs during December - May was studied. Of the total, the most productive period was found to be between 0600 - l600 hrs., with the peak period occurring between 0800 - 1000 hrs. The present data together show that during the darkest months of the year, the perch is only active in the mid-day period. Throughout the whole winter fishing season, activity only occurs during the time between surise and sunset.

On the diel rhythm of motor activity in perch [Translation from: Informatsionnyi Byulleten Biologiya Vnutrennikh Vod No.30, 12-14, 1976]

The river perch (Perca fluviatilis L.) is most active in the daytime hours, and displays seasonal changes of diel rhythm with a break of the rhythm in spring and autumn. In the present work data were obtained on the motor activity of 3 perch measuring l8-20 cm, caught by net in the littoral of a reservoir and spawned under laboratory conditions. The degree of intensity of movement of perch was judged by special experiments. The results are summarised in this short paper.

Control mechanisms in the human binocular oculomotor system

A study of human eye movements was made in order to elucidate the nature of the control mechanism in the binocular oculomotor system.

We first examined spontaneous eye movements during monocular and binocular fixation in order to determine the corrective roles of flicks and drifts. It was found that both types of motion correct fixational errors, although flicks are somewhat more active in this respect. Vergence error is a stimulus for correction by drifts but not by flicks, while binocular vertical discrepancy of the visual axes does not trigger corrective movements.

Second, we investigated the non-linearities of the oculomotor system by examining the eye movement responses to point targets moving in two dimensions in a subjectively unpredictable manner. Such motions consisted of hand-limited Gaussian random motion and also of the sum of several non-integrally related sinusoids. We found that there is no direct relationship between the phase and the gain of the oculomotor system. Delay of eye movements relative to target motion is determined by the necessity of generating a minimum afferent (input) signal at the retina in order to trigger corrective eye movements. The amplitude of the response is a function of the biological constraints of the efferent (output) portion of the system: for target motions of narrow bandwidth, the system responds preferentially to the highest frequency; for large bandwidth motions, the system distributes the available energy equally over all frequencies. Third, the power spectra of spontaneous eye movements were compared with the spectra of tracking eye movements for Gaussian random target motions of varying bandwidths. It was found that there is essentially no difference among the various curves. The oculomotor system tracks a target, not by increasing the mean rate of impulses along the motoneurons of the extra-ocular muscles, but rather by coordinating those spontaneous impulses which propagate along the motoneurons during stationary fixation. Thus, the system operates at full output at all times.

Fourth, we examined the relative magnitude and phase of motions of the left and the right visual axes during monocular and binocular viewing. We found that the two visual axes move vertically in perfect synchronization at all frequencies for any viewing condition. This is not true for horizontal motions: the amount of vergence noise is highest for stationary fixation and diminishes for tracking tasks as the bandwidth of the target motion increases. Furthermore, movements of the occluded eye are larger than those of the seeing eye in monocular viewing. This effect is more pronounced for horizontal motions, for stationary fixation, and for lower frequencies.

Finally, we have related our findings to previously known facts about the pertinent nerve pathways in order to postulate a model for the neurological binocular control of the visual axes.

Precious Corals in Hawaii: Discovery of a New Bed and Revised Management Measures for Existing Beds

The fishery for deepwater precious corals in the Hawaiian Islands has experienced an on-and-off history for almost 40 years. In spite of this, research, driven primarily by the precious coral jewelry industry, remains active. In this paper, the results of deepwater surveys in 2000 and 2001 are reported. In summary, a new bed on the summit of Cross Seamount is described and revised estimates of MSY’s for pink coral, Corallium secundum; red coral, Corallium regale; and gold coral, Ger ardia sp., in the two known beds off Makapuu, Oahu, and Keahole Point, Hawaii, in the main Hawaiian Islands, are presented. The population dynamics of each species is described, as well as their ecological limits on Hawaii’s deep reefs, island shelves, and seamounts. The local supply of precious coral in the main Hawaiian Islands is sufficient to support the local industry, but cost/ benefits of selective harvest requirements and weather constraints limit profitability of the fish

Survey and impact assessment of derelict fish traps in St. Thomas and St. John, U.S. Virgin Islands

Since 2001, NOAA National Centers for Coastal Ocean Science (NCCOS), Center for Coastal Monitoring and Assessment’s (CCMA) Biogeography Branch (BB) has been working with federal and territorial partners to characterize, monitor, and assess the status of the marine environment across the U.S. Virgin Islands (USVI). At the request of the St. Thomas Fisherman’s Association (STFA) and NOAA Marine Debris Program, CCMA BB developed new partnerships and novel technologies to scientifically assess the threat from derelict fish traps (DFTs). Traps are the predominant gear used for finfish and lobster harvesting in St. Thomas and St. John. Natural phenomena (ground swells, hurricanes) and increasing competition for space by numerous user groups have generated concern about increasing trap loss and the possible ecological, as well as economic, ramifications. Prior to this study, there was a general lack of knowledge regarding derelict fish traps in the Caribbean. No spatially explicit information existed regarding fishing effort, abundance and distribution of derelict traps, the rate at which active traps become derelict, or areas that are prone to dereliction. Furthermore, there was only limited information regarding the impacts of derelict traps on natural resources including ghost fishing. This research identified two groups of fishing communities in the region: commercial fishing that is most active in deeper waters (30 m and greater) and an unknown number of unlicensed subsistence and or commercial fishers that fish closer to shore in shallower waters (30 m and less). In the commercial fishery there are an estimated 6,500 active traps (fish and lobster combined). Of those traps, nearly 8% (514) were reported lost during the 2008-2010 period. Causes of loss/dereliction include: movement of the traps or loss of trap markers due to entanglement of lines by passing vessels; theft; severe weather events (storms, large ground swells); intentional disposal by fishermen; traps becoming caught on various bottom structures (natural substrates, wrecks, etc.); and human error.

Diurnal changes of behavior and respiration of Yangtze finless porpoises (Neophocaena phocaenoides asiaeorientalis) in captivity

A preliminary study was carried out to investigate diurnal changes of behavior of three, one adult mate, one adult female, and one juvenile female, Yangtze finless porpoises (Neophocaena phocaenoides asiaeorientalis) in captivity. The respiration and behavior of the porpoises were recorded for 222 hr across 42 days. Behavioral data were recorded for eight general categories: aerial display and fast swimming, begging for fish, playing, nonsexual socializing, sexual behavior, resting, rubbing, and miscellaneous (i.e., other behaviors not included in the above categories). Each behavioral category was scored using one-zero sampling with 10-min intervals. The adult male showed shorter mean respiratory intervals at night (19:00-7:00 h), whereas the mean respiratory intervals of the females were shorter during the day (7:00-19:00 h). Begging for fish of all individuals, playing of the juvenile female, nonsexual socializing, and miscellaneous behavior of the adult female and resting of the male were observed more easily in the day, and aerial display and fast swimming of the adults and resting of the females were observed more easily at night. No significant diurnal difference was found, however, in the remaining categories of each individual. Each of the three porpoises therefore showed a distinct diurnal pattern, but none was obviously more active in the daytime than during the nighttime. Results suggest that daytime-only feeding schedules may be insufficient to meet the energetic needs of marine mammals that show a 24-hr activity cycle, and that nighttime feeding may be a worthwhile addition to husbandry routines.

Raman and infrared properties and layer dependence of the phonon dispersions in multilayered graphene

The symmetry group analysis is applied to classify the phonon modes of N-stacked graphene layers (NSGLs) with AB and AA stacking, particularly their infrared and Raman properties. The dispersions of various phonon modes are calculated in a multilayer vibrational model, which is generalized from the lattice vibrational potentials of graphene to including the interlayer interactions in NSGLs. The experimentally reported redshift phenomena in the layer-number dependence of the intralayer optical C-C stretching mode frequencies are interpreted. An interesting low-frequency interlayer optical mode is revealed to be Raman or infrared active in even or odd NSGLs, respectively. Its frequency shift is sensitive to the layer number and saturated at about 10 layers.

Gas-bearing fluid influx sub-system for gas hydrate geological system in Shenhu Area, Northern South China Sea

Based on the comprehensive interpretation and study of the Neogene fracture system and diapiric structure, it can be concluded that the diapiric structures, high-angle fractures and vertical fissure system are the main gas-bearing fluid influx sub-system for gas hydrate geological system in Shenhu Area, northern South China Sea. The Neogene fractures widely developed in the study area may be classed into two groups: NW (NNW)-trending and NE (NNE)-trending. The first group was active in the Late Miocene, while the second one was active since the Pliocene. The NE (NNE)-trending fractures were characterized by lower activity strength and larger scale, and cut through the sediment layers deposited since the Pliocene. Within the top sediment layers, the high-angle fracture and vertical fissure system was developed. The diapiric structures display various types such as a turtle-back-like arch, weak piercing, gas chimney, and fracture (or crack, fissure). On the seismic profile, some diapiric structures show the vertical chimney pathway whose top is narrow and the bottom is wide, where some ones extend horizontally into pocket or flower-shaped structures and formed the seismic reflection chaotic zones. Within the overlying sediment layers of the diapiric structure, the tree branch, flower-shaped high-angle fractures and vertical fissures were developed and became the pathway and migration system of the gas-bearing fluid influx. In the study area, the diapiric structures indicate a high temperature/over pressure system ever developed. Closely associated and abundant bright-spots show the methane-bearing fluid influx migrated vertically or horizontally through the diapiric structures, high-angle fractures and vertical fissures. In the place where the temperature and pressure conditions were favor for the formation of gas hydrate, the hydrate reservoir deposition sub-system was developed.

DETERMINATION OF THE X-CONDUCTION-SUBBAND ENERGIES IN TYPE-II GAAS/ALAS/GAAS QUANTUM-WELL BY DEEP-LEVEL TRANSIENT SPECTROSCOPY

Using deep level transient spectroscopy (DLTS) the X conduction-subband energy levels in an AlAs well sandwiched by double GaAs layers were determined. Calculation gives eight subbands in the well with well width of 50 Angstrom. Among them, five levels and the other three remainders are determined by using the large longitudinal electron effective mass m(1)(1.1m(0)) and transverse electron effective mass m(t)(0.19m(0)) at X valley, respectively. Two subbands with the height energies were hardly detectable and the other six ones with lower energies are active in the present DLTS study. Because these six subbands are close to each other, we divided them into three groups. Experimentally, we observed three signals induced from the three groups. A good agreement between the calculation and experiment was obtained. (C) 1995 American Institute of Physics.

Promoting effects in hydrogenation and hydrodesulfurization reactions on the zirconia and titania supported catalysts

Tetralin hydrogenation (HYD) and thiophene hydrodesulfurization (HDS) were studied for the supported MoS2 and WS2 sulfides, either non-promoted or promoted with Co and Ni. The supports used were ZrO2, alumina-stabilized TiO2 and pure alumina. Preparation of catalysts included presulfidation of non-promoted system with subsequent addition of promoter and resulfidation. It has been found that the nature of promoter plays determining role for the catalytic performance. The most active in both HYD and HDS reactions are Ni-promoted Mo and W catalysts, supported on ZrO2. (C) 2003 Published by Elsevier B.V.

The Early Diagenetic Formation of Organic Sulfur in the Sediments of Mangrove Lake, Bermuda

Due to a low mineral content, the sapropelic sediments depositing in Mangrove Lake, Bermuda, provide an excellent opportunity to explore for possible additions of sulfur to organic matter during the early stages of diagenesis. We evaluated early diagenetic organic sulfur transformations by monitoring the concentrations and stable isotopic compositions of a number of inorganic and organic sulfur pools, thereby accounting for all of the sulfur in the sediments. We have identified and quantified the following sulfur pools: porewater sulfate, porewater sulfide, elemental sulfur, pyrite sulfur, hydrolyzable organic sulfur (HYOS), chromium-reducible organic sulfur (CROS), and nonchromium-reducible organic sulfur (Non-CROS). Of the organic sulfur pools, the Non-CROS pool is by far the largest, followed by CROS, and finally HYOS. By 60 cm depth these pools contribute, respectively, to 85, 7.9, and 3.6% of the total solid phase sulfur. The HYOS pool is probably of biological origin and shows no interaction with the sulfur compounds produced during diagenesis. By contrast, CROS is produced, most likely, from the diagenetic addition of polysulfides to functionalized lipids in the upper, H2S-poor, elemental sulfur-rich, region of the sediment. A portion of this sulfur pool is unstable and decomposes on contact with the H2S-rich porewaters. The portion of CROS that remains in the sulfidic waters appears to readily exchange sulfur isotopes with H2S. While some of the Non-CROS pool is of biological origin, some is also formed by the diagenetic addition of sulfur to organic compounds in the upper H2S-poor region of the sediment. By contrast with CROS, Non-CROS is not diagenetically active in the H2S-rich porewaters. Overall, somewhere between 27 and 53 % of the organic sulfur buried in Mangrove Lake sediments is of diagenetic origin, with the remaining organic sulfur derived from biosynthesis. We extrapolate our Mangrove Lake results and calculate that in typical coastal marine sediments between 11 and 29 μmol g−1 of organic sulfur will form during early diagenesis, of which 2–5 μmol g−1 will be chromium reducible.

THE CATALYTIC ACTIVITY OF HETEROPOLY ACIDS (SALTS) AND MONO-LACUNARY HETEROPOLY TUNGSTOPHOSPHORIC COMPOUND IN THE OXIDATION OF ALCOHOLS

The catalytic activity of heteropoly compounds in the oxidation of benzyl alcohol and cyclohexa nol under phase transfer conditions has been studied. The catalytic activity of six kinds of heteropoly acids with Keggin structure will drop by the order of GeMo12 (H4GeMo12O40). PW12, PMo12, SiMo12, GeW12 and SiW12. When the three protons of H3PW12O40 Were replaced by Na+ step by step, the catalytic activity will raise gradually with the drop of acidity. The addition of base and trace amount of sulfuric acid to the reaction system resulted in an increase of catalytic activity. It was found that catalytic activity of mono-lacunary heteropoly compounds is higher than that of the primary heteropoly acids (or salts). The catalytic oxidation system of HPA-H2O2-PTC is very active in the oxidation of benzyl alcohol ana cyclohexanol, but it has little activity in the oxidation of inactive compounds such as n(or iso)-proplalcohol. n-butyl alcohol and n-hexanol. Solvent has great effect on reaction, when polar compounds such as water were used as solvent, the catalytic activity is better than that when non-polar compounds were used as solvent.

Digestive gut structure and activity of protease, amylase, and alkaline phosphatase in Calanus sinicus during summer in the Yellow Sea and the East China Sea

Calanus sinicus aggregate at the depth of 40-60 m (ambient temperature is 16 degreesC) in the waters of the continental shelf of the Yellow Sea during summer. in animals found in near shore regions, there are changes in digestive gut cells structure, digestive enzyme activity (protease, amylase), and tissue enzyme (alkaline phosphatase (ALP)), which may represent adaptations by this cold-water animal to a sharp seasonal increase in temperature of 6-23 degreesC. The activities of the digestive enzymes (protease and amylase) are very low in animals at stations near the estuary of Yangtse River, whereas they are relatively high in animals at stations in the central Yellow Sea, During summer, B-cells of the intestine and the villi intestinalis disappear in animals that do not feed at stations near the estuary of the Yangtse River. Respiration rates were undetectable or quite low during summer in C. sinicus from stations near the estuary of the Yangtse River, whereas they were relatively high at stations in the central Yellow Sea. Based upon the morphological characteristics of the digestive gut structure, enzyme levels, respiration rates, and the distribution of C. sinicus, we concluded that C. sinicus might be dormant during summer in the near shore areas of the East China Sea while remaining active in the central Yellow Sea. (C) 2002 Elsevier Science B.V. All rights reserved.

Enhanced activity of an In-Fe2O3/H-ZSM-5 catalyst for NO reduction with methane

Selective reduction of NO by CH4 on an In-Fe2O3/H-ZSM-5 catalyst was investigated in the presence of excess oxygen. Compared with In/H-ZSM-5, the In-Fe2O3/H-ZSM-5 catalyst with high Fe2O3 contents showed higher activity in a wide range of reaction temperatures. It was found that the addition of Fe2O3 yielded a promotion effect on CH4 activation. The influence of water vapor on NO conversion was also investigated. The activity of the In/H-ZSM-5 catalyst has been found to be strongly inhibited by water vapor, while the In-Fe2O3/H-ZSM-5 catalyst remained fairly active in the presence of 3.3% steam. (C) 2000 Elsevier Science B.V. All rights reserved.