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At least 1,765 records · Page 98

The Chemical Basis for the Origin of the Genetic Code and the Process of Protein Synthesis

A model for the origin of protein synthesis. The essential features of the model are that 5'-AMP and perhaps other monoribonucleotides can serve as catalysts for the selective synthesis of L-based peptides. A unique set of characteristics of 5'-AMP is responsible for the selective catalysts and these characteristics are described in detail. The model involves the formation of diesters as intermediates and selectivity for use of the L-isomer occurs principally at the step of forming the diester. However, in the formation of acetyl phenylalanine-AMP monoester there is a selectivity for esterification by the D-isomer. Data showing this selectivity is presented. This selectivity for D-isomer disappears after the first step. The identity was confirmed of all four of possible diesters of acetyl-D- and -L phenylaline with 5'-AMP by nuclear magnetic resonance (NMR). The data using flourescence and NMR show the Trp ring can associate with the adenine ring more strongly when the D-isomer is in the 2' position than it can when in the 3' position. These same data also suggest a molecular mechanisim for the faster esterificaton of 5'-AMP by acetyl-D-phenylaline. Some new data is also presented on the possible structure of the 2' isomer of acetyl-D-tryptophan-AMP monoester. The HPLC elution times of all four possible acetyl diphenylalanine esters of 5'-AMP were studied, these peptidyl esters will be products in the studies of peptide formation on the ribose of 5'-AMP. Other studies were on the rate of synthesis and the identity of the product when producing 3'Ac-Phe-2'tBOC-Phe-AMP diester. HPLC purification and identification of this product were accomplished.

Lacey, James C., Jr.↗

The CO-12 and CO-13 J=2-1 and J=1-0 observations of hot and cold galaxies

Researchers observed the nuclear regions of the galaxies NGC 2146 and IC 342 in CO-12 and CO-13 J=1-0 and J=2-1 lines using the Five College Radio Astronomy Observatory (FCRAO) 14m telescope. NGC 2146 is a peculiar Sab spiral galaxy. Its complex optical morphology and strong nuclear radio continuum emission suggest that it is experiencing a phase of violent activity and could have a polar ring which may have resulted from an interaction. IC 342 is a nearby luminous Scd spiral galaxy. Strong CO, infrared and radio continuum emission from the nuclear region of IC 342 indicate enhanced star-forming activity, and interferometric CO-12 J=1-0 observations reveal a bar-like structure centered on the nucleus, along the dark lane in the NS direction. These two galaxies are selected based on their different dust temperatures and star formation efficiencies (SFE) as derived from the Infrared Astronomy Satellite (IRAS) S sub 60 mu/S sub 100 mu flux density ratio and L sub IR/M(H2), respectively, with a relatively high SFE and dust temperature of 45 K in NGC 2146 and a relatively low SFE and dust temperature of 35 K in IC 342. The data from the different CO-12 and CO-13 lines are used to study the physical conditions in the molecular clouds in the galaxies. Researchers also consider the radiative transfer to determine whether a warm and optically thin gas component exists in these galaxies, as has been suggested in the case of M82 (Knapp et al. 1980), and whether the warm gas is related to the dust properties. Since optically thin CO-12 gas is rarely detected in our own Galaxy (except in outflow sources), to confirm its existence in external galaxies is very important in understanding the molecular content of external galaxies and its relationship to star formation activity. The present CO-12 J=2-1 and CO-13 J=2-1 and J=1-0 data for NGC 2146 are the first detections of this galaxy to our knowledge. The CO-12 J=1-0 distribution in NGC 2146 has been measured as part of the FCRAO Extragalactic Survey. For the well-studied IC 342, the data are compared with 30m observations and other available data. Researchers present the observed results.

Xie, Shuding↗

Structure and functions of water-membrane interfaces and their role in proto-biological evolution

Among the most important developments in proto-biological evolution was the emergence of membrane-like structures. These are formed by spontaneous association of relatively simple amphiphilic molecules that would have been readily available in the primordial environment. The resulting interfacial regions between water and nonpolar interior of the membrane have several properties which made them uniquely suitable for promoting subsequent evolution. They can (1) selectively attract organic material and mediate its transport, (2) serve as simple catalysts for chemical reactions, and (3) promote the formation of trans-membrane electrical and chemical gradients which could provide energy sources for proto-cells. Understanding the structure of interfaces, their interactions with organic molecules and molecular mechanisms of their functions is an essential step to understanding proto-biological evolution. In our computer simulation studies, we showed that the structure of water at interfaces with nonpolar media is significantly different from that in the bulk. In particular, the average surface dipole density points from the vapor to the liquid. As a result, negative ions can approach the interface more easily than positive ions. Amphiphilic molecules composed of hydrocarbon conjugated rings and polar substituents (e.g., phenol) assume at the interface rigid orientations in which polar groups are buried in water while hydrocarbon parts are located in the nonpolar environment. These orientational differences are of special interest in connection with the ability of some of these molecules to efficiently absorb photons. Flexible molecules with polar substituents often adopt at interfaces conformations different from those in the bulk aquaeous solution and in the gas phase. As a result, in many instances both specificity and kinetics of chemical reactions in which these molecules can participate is modified by the presence of surfaces. Of special interest is the mechanism by which polar molecules are transferred across interface between water and a nonpolar medium. Our recent study showed that simple ionophores bind ions by the same mechanisms as ion channels and carriers from modern cells.

Pohorille, A.↗

NDE for the ARES I Upper Stage Common Bulkhead

The current design of the ARES 1 Upper Stage uses a common bulkhead to separate the liquid hydrogen and liquid oxygen tanks. The bulkhead consists of aluminum face sheets bonded to a Phenolic honeycomb core. The face sheets, or domes, are friction stir welded to Y-rings that connect the bulkhead to the barrel sections of the liquid hydrogen and liquid oxygen tanks. Load between the Y-rings is carried by an externally attached bolting ring. The development of nondestructive evaluation methods for the ARES I Upper Stage Common Bulkhead are outlined in this presentation. Methods for inspecting the various components of the bulkhead are covered focusing in on the dome skins, core-to-dome bond lines and friction stir welds as well as structural details like the fastener holes. Thermography, shearography and ultrasonic methods are discussed for the bond lines. Eddy current methods are discussed for the fastener holes and dome skins. A combination of phased array ultrasound, liquid penetrant and radiography are to being investigated for use on the friction stir welds. Keywords: Composite materials, NDE, Cryogenic structures

Walker, James↗

Tectonics of the Valhalla Structure on Callisto

The surficial morphology of Callisto is dominated by large concentric patterns of ridges, scarps, and furrows. The largest one, Valhalla, shows a smooth central area 350 km in radius, surrounded by concentric sinuous ridges which extend as far as 600km from the center. Beyond the ridged area, scarps and furrows are observed as far as 2000 km. The global azimuthal distribution of the scarps and furrows of the outer ring (beyond 700 km from the center) was analyzed. It is proposed that the local geometry and the global distribution of scarps and furrows around Valhalla are the results of the reactivation of an old pattern by the Valhalla event. The coincidence of these local directions of a preexisting pattern (NW-SE and NE-SW) with the directions of the grids observed on most bodies observed so far in the solar system would indicate that this local pattern is a part of a global calistean grid.

Thomas, P. G.↗

Regioselective On-Surface Synthesis of [3]Triangulene Graphene Nanoribbons

The integration of low-energy states into bottom-up engineered graphene nanoribbons (GNRs) is a robust strategy for realizing materials with tailored electronic band structure for nanoelectronics. Low-energy zero-modes (ZMs) can be introduced into nanographenes (NGs) by creating an imbalance between the two sublattices of graphene. This phenomenon is exemplified by the family of [n]triangulenes (n ϵ $\mathbb{N}$). Here, we demonstrate the synthesis of [3]triangulene-GNRs, a regioregular one-dimensional (1D) chain of [3]triangulenes linked by five-membered rings. Hybridization between ZMs on adjacent [3]triangulenes leads to the emergence of a narrow band gap, E g,exp ~ 0.7 eV, and topological end states that are experimentally verified using scanning tunneling spectroscopy. Tight-binding and first-principles density functional theory calculations within the local density approximation corroborate our experimental observations. Our synthetic design takes advantage of a selective on-surface head-to-tail coupling of monomer building blocks enabling the regioselective synthesis of [3]triangulene-GNRs. Detailed ab initio theory provides insights into the mechanism of on-surface radical polymerization, revealing the pivotal role of Au-C bond formation/breakage in driving selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic-scale insights into topotactic transformations in an extra-large-pore zeolite using time-resolved 3D electron diffraction

Understanding the atomic-scale structural dynamics of phase transformations is crucial for developing materials and tailoring their properties. However, many materials are obtained as polycrystalline powders with large unit cells and/or complex structures, making it challenging to investigate detailed structural changes using conventional X-ray diffraction techniques. Here we employ time-resolved three-dimensional electron diffraction to reveal the topotactic reactions and transformations that convert the extra-large-pore silicate zeolite ECNU-45 into ECNU-46. ECNU-45 features three-dimensional interconnecting 24 × 10 × 10-ring channels, while ECNU-46 consists of one-dimensional 24-ring channels connected to 10-ring pockets. ECNU-45 and ECNU-46 are both examples of pure silicate zeolites with pore openings larger than 22-ring. Our findings indicate changes at six distinct tetrahedral silicon sites, involving atom displacement, addition and removal of framework atoms through bond breakage and formation. This work presents the synthesis of zeolites and also provides atomic-level insights into the dynamic processes of topotactic reactions. Our results have implications for advancing materials engineering and understanding complex solid-state reactions at an atomic scale.

Inorganic chemistry↗

Relationship between molecular structure and corrugations in self-assembled polypeptoid nanosheets revealed by cryogenic electron microscopy

Designing conformationally dynamic molecules that self-assemble into predictable nanostructures remains an important unmet challenge. This paper describes how atomic-scale cryogenic transmission electron microscopy (cryo-TEM) can be used to explore the relationship between molecular structure and self-assembly of block copolymers. We examined sheetlike micelles formed in water using a series of diblock copolypeptoids with the same hydrophilic block and three distinct crystalline hydrophobic blocks. Our cryo-TEM images revealed all the structures share nansoscale features, but differ in their intermolecular packing geometries. Different molecular arrangements, parallel and antiparallel V-shaped crystal motifs, were revealed by two-dimensional atomic-scale through-plane images. However, images from tilted samples revealed an unexpected feature when the hydrophobic polypeptoid block comprised phenyl rings with substituted bromine atoms at the para position. The nanosheets contained atomic-scale corrugations that were absent in the other systems which comprised unsubstituted aliphatic and aromatic side chains. We hypothesize that these corrugations are due to the dipolar characteristics of the brominated phenyl group and interactions between this group and water molecules. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗

Late Life Supplementation of 25‐Hydroxycholesterol Reduces Aortic Stiffness and Cellular Senescence in Mice

ABSTRACT Stiffening of the aorta is a key antecedent to cardiovascular diseases (CVD) with aging. Age‐related aortic stiffening is driven, in part, by cellular senescence—a hallmark of aging defined primarily by irreversible cell cycle arrest. In this study, we assessed the efficacy of 25‐hydroxycholesterol (25HC), an endogenous cholesterol metabolite, as a naturally occurring senolytic to reverse vascular cell senescence and reduce aortic stiffness in old mice. Old (22–26 months) p16‐3MR mice, a transgenic model allowing for genetic clearance of p16‐positive senescent cells with ganciclovir (GCV), were administered vehicle, 25HC, or GCV to compare the efficacy of the experimental 25HC senolytic versus genetic clearance of senescent cells. We found that short‐term (5d) treatment with 25HC reduced aortic stiffness in vivo, assessed via aortic pulse wave velocity (p = 0.002) to a similar extent as GCV. Ex vivo 25HC exposure of aorta rings from the old p16‐3MR GCV‐treated mice did not further reduce elastic modulus (measure of intrinsic mechanical stiffness), demonstrating that 25HC elicited its beneficial effects on aortic stiffness, in part, through the suppression of excess senescent cells. Improvements in aortic stiffness with 25HC were accompanied by favorable remodeling of structural components of the vascular wall (e.g., lower collagen‐1 abundance and higher α‐elastin content) to a similar extent as GCV. Moreover, 25HC suppressed its putative molecular target CRYAB, modulated CRYAB‐regulated senescent cell anti‐apoptotic pathways, and reduced markers of cellular senescence. The findings from this study identify 25HC as a potential therapy to target vascular cell senescence and reduce age‐related aortic stiffness.

Cell Biology↗

Lightweight structural design of a bolted case joint for the space shuttle solid rocket motor

The structural design of a bolted joint with a static face seal which can be used to join Space Shuttle Solid Rocket Motor (SRM) case segments is given. Results from numerous finite element parametric studies indicate that the bolted joint meets the design requirement of preventing joint opening at the O-ring locations during SRM pressurization. A final design recommended for further development has the following parameters: 180 one-in.-diam. studs, stud centerline offset of 0.5 in radially inward from the shell wall center line, flange thickness of 0.75 in, bearing plate thickness of 0.25 in, studs prestressed to 70 percent of ultimate load, and the intermediate alcove. The design has a mass penalty of 1096 lbm, which is 164 lbm greater than the currently proposed capture tang redesign.

Dorsey, John T.↗

Optimal design of geodesically stiffened composite cylindrical shells

An optimization system based on the finite element code Computations Structural Mechanics (CSM) Testbed and the optimization program, Automated Design Synthesis (ADS), is described. The optimization system can be used to obtain minimum-weight designs of composite stiffened structures. Ply thickness, ply orientations, and stiffener heights can be used as design variables. Buckling, displacement, and material failure constraints can be imposed on the design. The system is used to conduct a design study of geodesically stiffened shells. For comparison purposes, optimal designs of unstiffened shells and shells stiffened by rings and stingers are also obtained. Trends in the design of geodesically stiffened shells are identified. An approach to include local stress concentrations during the design optimization process is then presented. The method is based on a global/local analysis technique. It employs spline interpolation functions to determine displacements and rotations from a global model which are used as 'boundary conditions' for the local model. The organization of the strategy in the context of an optimization process is described. The method is validated with an example.

Gendron, G.↗

Plasma Heating and Flow in an Auroral Arc

We report direct observations of the three-dimensional velocity distribution of selected topside ionospheric ion species in an auroral context between 500 and 550 km altitude. We find heating transverse to the local magnetic field in the core plasma, with significant heating of 0(+), He(+), and H(+), as well as tail heating events that occur independently of the core heating. The 0(+) velocity distribution departs from bi-Maxwellian, at one point exhibiting an apparent ring-like shape. However, these observations are shown to be aliased within the auroral arc by temporal variations that arc not well-resolved by the core plasma instrument. The dc electric field measurements reveal superthermal plasma drifts that are consistent with passage of the payload through a series of vortex structures or a larger scale circularly polarized hydromagnetic wave structure within the auroral arc. The dc electric field also shows that impulsive solitary structures, with a frequency spectrum in the ion cyclotron frequency range, occur in close correlation with the tail heating events. The drift and core heating observations lend support to the idea that core ion heating is driven at low altitudes by rapid convective motions imposed by the magnetosphere. Plasma wave emissions at ion frequencies and parallel heating of the low-energy electron plasma are observed in conjunction with this auroral form; however, the conditions are much more complex than those typically invoked in previous theoretical treatments of superthermal frictional heating. The observed ion heating within the arc clearly exceeds that expected from frictional heating for the light ion species H(+) and He(+), and the core distributions also contain hot transverse tails, indicating an anomalous transverse heat source.

Moore, T. E.↗

Breccia Formation at a Complex Impact Crater: Slate Islands, Lake Superior, Ontario, Canada

The Slate Islands impact structure is the eroded remnant of a approximately 30-32 km-diameter complex impact structure located in northern Lake Superior, Ontario, Canada. Target rocks are Archean supracrustal and igneous rocks and Proterozoic metavolcanics, metasediments, and diabase. A wide variety of breccias occurs on the islands, many of which contain fragments exhibiting shock metamorphic features. Aphanitic, narrow and inclusion-poor pseudotachylite veins, commonly with more or less parallel boundaries and apophyses branching off them, represent the earliest breccias formed during the compression stage of the impact process. Coarse-grained, polymictic elastic matrix breccias form small to very large, inclusion-rich dikes and irregularly shaped bodies that may contain altered glass fragments. These breccias have sharp contacts with their host rocks and include a wide range of fragment types some of which were transported over minimum distances of approximately 2 km away from the center of the structure. They cut across pseudotachylite veins and contain inclusions of them. Field and petrographic evidence indicate that these polymictic breccias formed predominantly during the excavation and central uplift stages of the impact process. Monomictic breccias, characterized by angular fragments and transitional contacts with their host rocks, occur in parautochthonous target rocks, mainly on the outlying islands of the Slate Islands archipelago. A few contain fragmented and disrupted, coarse-grained, polymictic clastic matrix breccia dikes. This is an indication that at least some of these monomictic breccias formed late in the impact process and that they are probably related to a late crater modification stage. A small number of relatively large occurrences of glass-poor, suevitic breccias occur at the flanks of the central uplift and along the inner flank of the outer ring of the Slate Islands complex crater. A coarse, glass-free, allogenic breccia, containing shatter-coned fragments derived from Proterozoic target rocks (upper target strata), observed at two locations may be analogous to the 'Bunt Breccia' of the Ries crater in Germany. At one of these locations this breccia lies close to a crater suevite deposit. At the other, it overlies parautochthonous, monomictic breccia. The State Islands impact breccias are superbly exposed, much better than breccias in most other terrestrial impact structures. Observations, including those indicative of multiple and and sequential processes, provide insight on how impact breccias form and how they relate to the various phases of the impact process. Eventually they will lead to an improved understanding of planetary impact processes.

Dressler, B. O.↗

Discontinuous Inter-Granular Separations (DIGS) in the Gas Nitride Layer of ISS Race Rings

The starboard solar alpha rotary joint (SARJ) race ring on the International space station (ISS) failed due to severe spalling of the outer diameter, 45 degree (outer canted) nitrided surface. Subsequent analysis at NASA-KSC revealed that almost all of the debris generated due to the failure was nitrided 15-5 stainless steel. Subsequent analysis of the nitride control coupons (NCC) at NASA-JSC revealed the presence of discontinuous inter-granular separations (DIGS) in the gas nitride layer. These DIGS were present in the inter-granular networking located in the top 2 mils of the nitride layer. The manufacturer's specification requires the maximum white structure to be 0.0003 inches and intergranular networking below the allowable white structure depth to be cause for rejection; a requirement that the NCCs did not meet. Subsequent testing and analysis revealed that lower DIGS content significantly lowered the probability of nitride spalling in simulated, dry condition runs. One batch of nitride samples with DIGS content similar to the port SARJ (did not fail on orbit) which exhibited almost no nitride spalling after being run on one test rig. Another batch of nitride samples with DIGS content levels similar to the starboard SARJ exhibited significant nitride spalling on the same test rig with the same load under dry conditions. Although DIGS were not the root cause of starboard race ring failure, testing indicates that increased DIGS reduced the robustness of the gas nitride layer under dry operating conditions.

Figert, John↗

Ni-catalysed dicarbofunctionalization for the synthesis of sequence-encoded cyclooctene monomers

The properties of polymeric materials can be modulated by factors such as sequence control or functional group modifications. However, the synthesis of new macromolecular scaffolds is limited by the accessibility of structurally diverse monomers. This work describes a one-step, nickel-catalysed synthesis of 5,6-diaryl cyclooctene monomers from the feedstock chemical 1,5-cyclooctadiene. The reaction proceeds in a modular, regio- and diastereoselective fashion, granting access to both homo- and hetero-diaryl cyclooctene monomers that smoothly undergo ring-opening metathesis polymerization (ROMP). The resulting 1,2-diaryl-substituted polymers possess sequences with head-to-head styrene dyads that have not been previously explored, giving rise to unique and tunable properties. Density functional theory calculations highlight mechanistic aspects of the nickel-catalysed diarylation reaction and the ruthenium-catalysed ROMP process, revealing a previously unappreciated role of the boronic ester in promoting migratory insertion, which was leveraged to provide enantioinduction.

Catalytic mechanisms↗

A new survey of multiring impact basins on Mars

Literature data on Martian multiring impact basins with diameters greater than 500 km are summarized, and evidence is found for eight new such basins. The pattern of changes of basin morphology with increasing basin size suggests three subclasses of multiring basins: (1) multiring basins with diameters up to about 1850 km, which are characterized by the Orientale type concentric structure and cumulative frequency power law slope of -0.75; (2) the Argyre-type basins (with diameters between 1850 and 3600 km, defined by rugged concentric annnuli and a power law slope of nearly -2.0; and (3) the Chryse-type basins (with diameters greater than 3600 km), which exhibit multiple concentric rings and very shallow topographic profiles. Multiring basins are found in all parts of Mars, including the northern lowlands, Tharsis, and surrounding highlands, and are associated with much of the subsequent resurfacing of cratered terrain.

Schultz, Richard A.↗

Collisional Grooming Models of the Kuiper Belt Dust Cloud

We modeled the three-dimensional structure of the Kuiper Belt (KB) dust cloud at four different dust production rates, incorporating both planet-dust interactions and grain-grain collisions using the collisional grooming algorithm. Simulated images of a model with a face-on optical depth of approximately 10 (exp -4) primarily show an azimuthally- symmetric ring at 40-47 AU in submillimeter and infrared wavelengths; this ring is associated with the cold classical KB. For models with lower optical depths (10 (exp -6) and 10 (exp-7)), synthetic infrared images show that the ring widens and a gap opens in the ring at the location of Neptune; this feature is caused by trapping of dust grains in Neptune's mean motion resonances. At low optical depths, a secondary ring also appears associated with the hole cleared in the center of the disk by Saturn. Our simulations, which incorporate 25 different grain sizes, illustrate that grain-grain collisions are important in sculpting today's KB dust, and probably other aspects of the solar system dust complex; collisions erase all signs of azimuthal asymmetry from the submillimeter image of the disk at every dust level we considered. The model images switch from being dominated by resonantly trapped small grains ("transport dominated") to being dominated by the birth ring ("collision dominated") when the optical depth reaches a critical value of r approximately v/c, where v is the local Keplerian speed.

Kuchner, Marc J.↗

Fluorescent aromatic sensors and their methods of use

Aromatic molecules that can be used as sensors are described. The aromatic sensors include a polycyclic aromatic hydrocarbon core with a five-membered imide rings fused to the core and at least two pendant aryl groups. The aromatic sensor molecules can detect target analytes or molecular strain as a result of changes in their fluorescence, in many cases with on-off behavior. Aromatic molecules that fluoresce at various frequencies can be prepared by altering the structure of the aromatic core or the substituents attached to it. The aromatic molecules can be used as sensors for various applications such as, for example, the detection of dangerous chemicals, biomedical diagnosis, and the detection of damage or strain in composite materials. Methods of preparing aromatic sensor molecules are also described.

Meador, Michael A.↗