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At least 235 records · Page 13

Nanopore Device for Reversible Ion and Molecule Sensing or Migration

Disclosed are methods and devices for detection of ion migration and binding, utilizing a nanopipette adapted for use in an electrochemical sensing circuit. The nanopipette may be functionalized on its interior bore with metal chelators for binding and sensing metal ions or other specific binding molecules such as boronic acid for binding and sensing glucose. Such a functionalized nanopipette is comprised in an electrical sensor that detects when the nanopipette selectively and reversibly binds ions or small molecules. Also disclosed is a nanoreactor, comprising a nanopipette, for controlling precipitation in aqueous solutions by voltage-directed ion migration, wherein ions may be directed out of the interior bore by a repulsing charge in the bore.

Pourmand, Nader↗

TRIDENT Drill Validation at Mars and Lunar Analog Field Sites

Drilling on Earth is typically a human-intensive activity. Drilling on other planets is further complicated by the lack of prior local field surveys of their target area, hence blindly drilling into uncertain target rocks. Field conditions on the Moon or Mars are also different than for shallow drilling on Earth: lower temperatures and pressures, less power available, low masses (hence less weight-on-bit). Given the cost of transport from Earth, no drilling muds or working fluids are likely to be available to carry away cuttings. And impact-gardened regolith and dust vary mechanically and texturally from most terrestrial soils. The Regolith and Ice Drill for Exploration of New Terrains (TRIDENT) is a rotary-percussive 1m-class drill from Honeybee Robotics. It is low-power (rotary and percussive actuators are 200 W each) and lightweight (<20 kg) with the maximum weight on bit limited to 200 N. TRIDENT has been manifested for the Volatiles Investigating Polar Exploration Rover (VIPER) and PRIME-1 lunar south pole missions in 2024, has previously been field tested at a hot, dry analog site in the Atacama Desert, and in lunar conditions in thermal vacuum chamber tests. TRIDENT was also part of the 2019 Icebreaker Mars Discovery proposal, as well as in the Mars Life Explorer concept. During ARADS tests, drill control and fault recovery automation software enabled hands-off operations of a rover-mounted TRIDENT drill. TRIDENT Drill Analog Site Validation: Past TRIDENT tests in thermal vacuum (TVAC) chambers targeted containers of manufactured lunar simulants with added volatiles. 2022 TRIDENT ambient testing at NASA Ames drilled into cemented lunar simulant materials. Low cuttings-permeability led to cuttings buildup, and drill choking and binding was observed. The Atacama analog site in ARADS had desiccated unconsolidated sediments that did not challenge the TRIDENT design. However, lunar polar regolith is expected to be diverse and heterogeneous with varying clast sizes, with abundant impactites and perhaps subsurface ice deposits. Neither the simulants nor Atacama testing had completely covered the TRIDENT-targeted field characteristics, motivating further analog tests prior to the planned lunar missions. To gain more insight into the behavior of the TRIDENT hardware in diverse impactites and subsurface ice, and to verify the software automation in that environment, in August 2023 TRIDENT was brought to Haughton Crater, a field analog site in the Canadian Arctic. In September 2023 the same drill was brought to the Bishop Tuff in southern California to verify whether drilling binding behaviors previously seen in lunar simulant testing would be observed in naturally occurring fine-grained massive layers. The ~22 Ma Haughton Crater impact structure is located at 75 ̊22’ N, 89 ̊41’ W, on northwestern Devon Island, Nunavut, Canada. Numerous deposits of pale-grey crater-fill polymictic impact-melt breccia are found within the crater with a typical thickness reaching ~125 m or greater and covering ~60 km -2 . An approximately 600m-thick permafrost layer is also present with ice typically found within 0.5-0.6m of the surface. The volcanic tableland north of Bishop, CA exposes densely welded tuff laid down during the eruption that created the Long Valley Caldera at approximately 0.76 Ma. Extensional faults and the Owens River gorge expose cross-sections across the plateau. The area is viewed as an analog site for Mars features believed to be of pyroclastic origin. Results: Haughton Crater.Drilling tests were conducted 8-13 August 2023 at a previously undisturbed area separated 5-10 m from past years’ Drill Hill test sites (75.4208, -089.7613). In six days, TRIDENT drilled 8 holes to nearly 1 m depth each, totaling 7.80 m. The active layer/ice boundary was at ~67 cm depth, with a total of approximately 2.4 m drilled into ice or ice-cemented impact breccia. During drilling, five drill fault states were observed and successfully recovered. Holes 23-1, 4 and 7 were drilled under manual control, using Honeybee’s Thorax user interface. Holes 23-5, 6, and 8 were drilled with the Ames IBexec automated drilling control software. TRIDENT was observed to have little difficulty in the thawed uncemented impact breccia above the active layer boundary, but required percussion to make slower headway in the ice-cemented breccia. In Hole 23-7 (Fig.1), drilling slowed down in a massive unit just above the active-layer boundary (perhaps a large rock extending into the ice-cementation?), with only 7cm progress made in 27 minutes of high auger torque and constant percussion, leading to a choking fault and then a binding fault. A similar pattern had been observed in TRIDENT Rio Tinto test data from 2017 [6] as well as in the 2022laboratory tests.Bishop Tuff.A team from NASA Ames and the US Geological Survey deployed the same TRIDENT drill to Bishop Sites 1B and 1C (37.4203, -118.4289; 37.4265, -118.4215) on 13-16 September 2023, on the Bishop Tuff plateau. A third drill site was used 17-18 September 2023(37.4598, -118.3667) in an abandoned pumice mine. Four holes (totaling 2.5m depth) were drilled into the fine-grained, meters-thick tuff units at Sites 1B and 1C, and a further two boreholes (totaling 1.98m depth) were made at the pumice site. Drill behavior in the tuff below 10 cm depth was similar to that seen at 65-74 cm depth in Haughton Hole 23-7 (Fig. 1) and that seen in the 2022 lab simulant drilling. Drill safety torque limits were exceeded multiple times resulting in drill stops downhole. These freezes then required external added torques (with a pipe wrench) to resume rotation, to unstick the drill for withdrawal. To prevent this choking and binding behavior we found that more-frequent cuttings removal was necessary, e.g., reducing the “drill bite” size from the nominal 10 cm to 2 cm per bite --bringing the auger up to the surface more frequently, as seen in Bishop Site 1C Hole 2 (Fig.2). This permitted slow progress without drill binding and without external interventions. Conversely, TRIDENT drilling in the more porous pumice target material showed no cuttings buildup issue, and single bites as large as 40 cm were demonstrated. Discussion: We observed that TRIDENT easily penetrated unconsolidated heterogeneous soils (both above the active layer boundary at Haughton and previously in the Atacama). Cemented or consolidated targets that were cuttings-permeable (icy impact breccia, pumice) required more energy applied and percussion. However, in non-cuttings-permeable targets (welded microporous tuff, cemented simulants, boulder) TRIDENT was observed to be prone to excessive cuttings accumulation leading to choking/binding faults and stalling. The wedge cutting bit, used by TRIDENT in field tests and in its flight versions, pulverizes the target rock and creates fine cuttings that ideally are transported up the auger spirals for removal. In porous, fractured or vesicular target materials (such as at the Bishop pumice site) a significant portion of the cuttings are pushed aside, but for non-fractured, microporous targets the cuttings remain in the borehole and accumulate. Rock powder is relatively incompressible as a working fluid at only 100-200N downward force (TRIDENT limits) and hence eventual drilling progress slows or stops. Our recommended strategy for improving TRIDENT cuttings removal in massive target units with low cuttings-permeability is to reduce TRIDENT bite sizes when encountering these units, from 10cm to as little as 1-2cm, to effectively bail the accumulating cuttings. This approach was demonstrated to reduce choking and allowed slow progress to continue in cuttings-impermeable microporous target units (viz. the Bishop tuff in our September 2023 tests or cemented simulants in 2022 ambient tests).

robotic drilling↗

CCAAT/enhancer-binding protein delta activates insulin-like growth factor-I gene transcription in osteoblasts. Identification of a novel cyclic AMP signaling pathway in bone

Insulin-like growth factor-I (IGF-I) plays a key role in skeletal growth by stimulating bone cell replication and differentiation. We previously showed that prostaglandin E2 (PGE2) and other cAMP-activating agents enhanced IGF-I gene transcription in cultured primary rat osteoblasts through promoter 1, the major IGF-I promoter, and identified a short segment of the promoter, termed HS3D, that was essential for hormonal regulation of IGF-I gene expression. We now demonstrate that CCAAT/enhancer-binding protein (C/EBP) delta is a major component of a PGE2-stimulated DNA-protein complex involving HS3D and find that C/EBPdelta transactivates IGF-I promoter 1 through this site. Competition gel shift studies first indicated that a core C/EBP half-site (GCAAT) was required for binding of a labeled HS3D oligomer to osteoblast nuclear proteins. Southwestern blotting and UV-cross-linking studies showed that the HS3D probe recognized a approximately 35-kDa nuclear protein, and antibody supershift assays indicated that C/EBPdelta comprised most of the PGE2-activated gel-shifted complex. C/EBPdelta was detected by Western immunoblotting in osteoblast nuclear extracts after treatment of cells with PGE2. An HS3D oligonucleotide competed effectively with a high affinity C/EBP site from the rat albumin gene for binding to osteoblast nuclear proteins. Co-transfection of osteoblast cell cultures with a C/EBPdelta expression plasmid enhanced basal and PGE2-activated IGF-I promoter 1-luciferase activity but did not stimulate a reporter gene lacking an HS3D site. By contrast, an expression plasmid for the related protein, C/EBPbeta, did not alter basal IGF-I gene activity but did increase the response to PGE2. In osteoblasts and in COS-7 cells, C/EBPdelta, but not C/EBPbeta, transactivated a reporter gene containing four tandem copies of HS3D fused to a minimal promoter; neither transcription factor stimulated a gene with four copies of an HS3D mutant that was unable to bind osteoblast nuclear proteins. These results identify C/EBPdelta as a hormonally activated inducer of IGF-I gene transcription in osteoblasts and show that the HS3D element within IGF-I promoter 1 is a high affinity binding site for this protein.

NASA Discipline Musculoskeletal↗

Identification of a TAAT-containing motif required for high level expression of the COL1A1 promoter in differentiated osteoblasts of transgenic mice

Our previous studies have shown that the 49-base pair region of promoter DNA between -1719 and -1670 base pairs is necessary for transcription of the rat COL1A1 gene in transgenic mouse calvariae. In this study, we further define this element to the 13-base pair region between -1683 and -1670. This element contains a TAAT motif that binds homeodomain-containing proteins. Site-directed mutagenesis of this element in the context of a COL1A1-chloramphenicol acetyltransferase construct extending to -3518 base pairs decreased the ratio of reporter gene activity in calvariae to tendon from 3:1 to 1:1, suggesting a preferential effect on activity in calvariae. Moreover, chloramphenicol acetyltransferase-specific immunofluorescence microscopy of transgenic calvariae showed that the mutation preferentially reduced levels of chloramphenicol acetyltransferase protein in differentiated osteoblasts. Gel mobility shift assays demonstrate that differentiated osteoblasts contain a nuclear factor that binds to this site. This binding activity is not present in undifferentiated osteoblasts. We show that Msx2, a homeodomain protein, binds to this motif; however, Northern blot analysis revealed that Msx2 mRNA is present in undifferentiated bone cells but not in fully differentiated osteoblasts. In addition, cotransfection studies in ROS 17/2.8 osteosarcoma cells using an Msx2 expression vector showed that Msx2 inhibits a COL1A1 promoter-chloramphenicol acetyltransferase construct. Our results suggest that high COL1A1 expression in bone is mediated by a protein that is induced during osteoblast differentiation. This protein may contain a homeodomain; however, it is distinct from homeodomain proteins reported previously to be present in bone.

NASA Discipline Cell Biology↗

Complex high affinity interactions occur between MHCI and superantigens

Staphylococcal enterotoxins A and C1 (SEA or SEC1) bound to major histocompatibility-I (MHCI) molecules with high affinity (binding constants ranging from 1.1 microM to 79 nM). SEA and SEC1 directly bound MHCI molecules that had been captured by monoclonal antibodies specific for H-2Kk, H-2Dk, or both. In addition, MHCI-specific antibodies inhibited the binding of SEC1 to LM929 cells and SEA competitively inhibited SEC1 binding; indicating that the superantigens bound to MHCI on the cell surface. The affinity and number of superantigen binding sites differed depending on whether MHCI was expressed in the membrane of LM929 cells or whether it was captured. These data support the hypothesis that MHCI molecules can serve as superantigen receptors.

NASA Discipline Cell Biology↗

Identification of the cAMP response element that controls transcriptional activation of the insulin-like growth factor-I gene by prostaglandin E2 in osteoblasts

Insulin-like growth factor-I (IGF-I), a multifunctional growth factor, plays a key role in skeletal growth and can enhance bone cell replication and differentiation. We previously showed that prostaglandin E2 (PGE2) and other agents that increase cAMP activated IGF-I gene transcription in primary rat osteoblast cultures through promoter 1 (P1), the major IGF-I promoter, and found that transcriptional induction was mediated by protein kinase A. We now have identified a short segment of P1 that is essential for full hormonal regulation and have characterized inducible DNA-protein interactions involving this site. Transient transfections of IGF-I P1 reporter genes into primary rat osteoblasts showed that the 328-base pair untranslated region of exon 1 was required for a full 5.3-fold response to PGE2; mutation in a previously footprinted site, HS3D (base pairs +193 to +215), reduced induction by 65%. PGE2 stimulated nuclear protein binding to HS3D. Binding, as determined by gel mobility shift assay, was not seen in nuclear extracts from untreated osteoblast cultures, was detected within 2 h of PGE2 treatment, and was maximal by 4 h. This DNA-protein interaction was not observed in cytoplasmic extracts from PGE2-treated cultures, indicating nuclear localization of the protein kinase A-activated factor(s). Activation of this factor was not blocked by cycloheximide (Chx), and Chx did not impair stimulation of IGF-I gene expression by PGE2. In contrast, binding to a consensus cAMP response element (CRE; 5'-TGACGTCA-3') from the rat somatostatin gene was not modulated by PGE2 or Chx. Competition gel mobility shift analysis using mutated DNA probes identified 5'-CGCAATCG-3' as the minimal sequence needed for inducible binding. All modified IGF-I P1 promoterreporter genes with mutations within this CRE sequence also showed a diminished functional response to PGE2. These results identify the CRE within the 5'-untranslated region of IGF-I exon 1 that is required for hormonal activation of IGF-I gene transcription by cAMP in osteoblasts.

NASA Discipline Musculoskeletal↗

Characterization of atrial natriuretic peptide receptors in brain microvessel endothelial cells

Atrial natriuretic peptide (ANP) binding and ANP-induced increases in cyclic guanosine monophosphate (cGMP) levels have been observed in brain microvessels (Chabrier et al., 1987; Steardo and Nathanson, 1987), suggesting that this fluid-regulating hormone may play a role in the fluid homeostasis of the brain. This study was initiated to characterize the ANP receptors in primary cultures of brain microvessel endothelial cells (BMECs). The apparent equilibrium dissociation constant, Kd, for ANP increased from 0.25 nM to 2.5 nM, and the number of ANP binding sites as determined by Scatchard analysis increased from 7,100 to 170,000 sites/cell between 2 and 10 days of culture following monolayer formation. Time- and concentration-dependent studies on the stimulation of cGMP levels by ANP indicated that guanylate cyclase-linked ANP receptors were present in BMECs. The relative abilities of ANP, brain natriuretic peptide (BNP), and a truncated analog of ANP containing amino acids 5-27 (ANP 5-27) to modulate the accumulation of cGMP was found to be ANP greater than BNP much greater than ANP 5-27. Affinity cross-linking with disuccinimidyl suberate and radiolabeled ANP followed by gel electrophoresis under reducing conditions demonstrated a single band corresponding to the 60-70 kD receptor, indicating the presence of the nonguanylate cyclase-linked ANP receptor. Radiolabeled ANP binding was examined in the presence of various concentrations of either ANP, BNP, or ANP 5-27 and suggested that a large proportion of the ANP receptors present in blood-brain barrier endothelial cells bind all of these ligands similarly. These data indicate both guanylate cyclase linked and nonguanylate cyclase linked receptors are present on BMECs and that a higher proportion of the nonguanylate cyclase linked receptors is expressed. This in vitro culture system may provide a valuable tool for the examination of ANP receptor expression and function in blood-brain barrier endothelial cells.

Endothelium, Vascular/chemistry↗

Adhesion of a bimetallic interface

The Hohenberg-Kohn and Kohn-Sham formalisms are used to examine binding (binding energy as a function of separation) for combinations of the simple metals Al(111), Zn(0001), Mg(0001), and Na(110) in contact. Similar metal contacts between Al, Zn, Mg, and Na are examined self-consistently in an ab initio calculation using the Kohn-Sham formalism. Crystallinity is included using the Aschroft pseudopotential via first order perturbation theory for the electron-ion interaction; and the ion-ion interaction is included exactly via a lattice sum. Binding energy was determined both in the local-density approximation and including gradient corrections to the exchange and correlation energy. Binding was found in all cases. In dissimilar metal contacts, interfacial bonding was greater than that in the weaker material predicting the possibility of metallic transfer. The nonzero position of the energy minimum in like metal contacts is explained in terms of consistency between the Ashcroft pseudopotential and the bulk charge density. Good agreement with experimental surface energies is obtained in the self-consistent calculation when nonlocal terms are included.

Ferrante, J.↗

Nonbonded interactions in membrane active cyclic biopolymers. IV - Cation dependence

Interactions of valinomycin and form of its analogs in several conformations with the central ions Li(+), Na(+), K(+), Rb(+) and Cs(+) are investigated as part of a study of the specific preference of valinomycin for potassium and the mechanisms of carrier-mediated ion transport across membranes. Ion binding energies and conformational potential energies are calculated taking into account polarization energy formulas and repulsive energy between the central ion and the ligand atoms for conformations representing various stages in ion capture and release for each of the two ring chiralities of valinomycin and its analogs. Results allow the prediction of the chirality and conformation most likely to be observed for a given analog, and may be used to synthesize analogs with a desired rigidity or flexibility. The binding energies with the alkali metal cations are found to decrease with increasing ion size, and to be smaller than the corresponding ion hydration energies. It is pointed out that the observed potassium preference may be explainable in terms of differences between binding and hydration energies. Binding energies are also noted to depend on ligand conformation.

Radhakrishnan, R.↗

A semiempirical model for heavy element depletion in the interstellar medium

An empirical relationship is derived which reproduces the observed depletion factors in interstellar gas by relating them to some preshock distribution factor and the binding energy of the elements in appropriate compounds. By fitting this equation to the data, estimates are obtained for both the distribution factor and the critical binding energy, which is related to the shock strength at which grains are completely destroyed. The critical binding energy value therefore provides an estimate of the energy involved in the most recent shock event, while the preshock distribution factor is related to the preshock elemental distribution between gas and dust. It is noted that the minerals most likely to survive are the refractory ones with the largest binding energies.

Trivedi, B. M. P.↗

Interaction of metal ions and amino acids - Possible mechanisms for the adsorption of amino acids on homoionic smectite clays

A semiempirical molecular orbital method is used to characterize the binding of amino acids to hexahydrated Cu(2+) and Ni(2+), a process presumed to occur when they are adsorbed in the interlamellar space of homoionic smectite clays. Five alpha-amino acids, beta-alanine, and gamma-aminobutyric acid were used to investigate the metal ion and amino acid specificity in binding. It was assumed that the alpha, beta, and gamma-amino acids would bind as bidentate anionic ligands, forming either 1:1 or 1:2 six-coordinated five, six, and seven-membered-ring chelate complexes, respectively. Energies of complex formation, optimized geometries, and electron and spin distribution were determined; and steric constraints of binding of the amino acids to the ion-exchanged cations in the interlamellar spacing of a clay were examined. Results indicate that hexahydrated Cu(2+) forms more stable complexes than hexahydrated Ni(2+) with all the amino acids studied. However, among these amino acids, complex formation does not favor the adsorption of the biological subset. Calculated energetics of complex formation and steric constraints are shown to predict that 1:1 rather than 1:2 metal-amino acid complexes are generally favored in the clay.

Gupta, A.↗

Complexes of polyadenylic acid and the methyl esters of amino acids

A study of amino acid methyl esters binding to polyadenylic acid supports the theory that the genetic code originated through weak but selective affinities between amino acids and nucleotides. NMR, insoluble complex analysis, and ultraviolet spectroscopy are used to illustrate a correlation between the hydrophybicities of A amino acids and their binding constants, which, beginning with the largest, are in the order of Phe (having nominally a hydrophobic AAA anticodon), Ile, Leu, Val and Gly (having a hydrophilic anticodon with no A). In general, the binding constants are twice the values by Reuben and Polk (1980) for monomeric AMP, which suggests that polymer amino acids are interacting with only one base. No real differences are found betwen poly A binding for free Phe, Phe methyl ester or Phe amide, except that the amide value is slightly lower.

Khaled, M. A.↗

Modulation of the cytosolic androgen receptor in striated muscle by sex steroids

The influence of orchiectomy (GDX) and steroid administration on the level of the cytosolic androgen receptor in the rat levator ani muscle and in rat skeletal muscles (tibialis anterior and extensor digitorum longus) was studied. Androgen receptor binding to muscle cytosol was measured using H-3 methyltrienolone (R1881) as ligand, 100 fold molar excess unlabeled R1881 to assess nonspecific binding, and 500 fold molar excess of triamcinolone acetonide to prevent binding to glucocorticoid and progestin receptors. Results demonstrate that modification of the levels of sex steroids can alter the content of androgen receptors of rat striated muscle. Data suggest that: (1) cytosolic androgen receptor levels increase after orchiectomy in both levator ani muscle and skeletal muscle; (2) the acute increase in receptor levels is blocked by an inhibitor of protein synthesis; and (3) administration of estradiol-17 beta to castrated animals increases receptor binding in levator ani muscle but not in skeletal muscle.

Rance, N. E.↗

Photoemission studies of core level shifts in HgCdTe, CdMnTe, and HgZnTe

The results of photoemission studies of core level shifts in the Hg(1-x)Cd(x)Te, Cd(1-x)Mn(x)Te, and Hg(1-x)Zn(x)Te alloys are discussed. In Hg(0.7)Cd(0.3)Te, the Hg 5d level is found to shift to lower binding energy by 0.1 eV, and the Cd 4d level to shift to higher binding energy by 0.25 eV upon alloying (relative to their binaries). The Born-Haber cycle is used to determine core level binding energies relative to the valence-band maximum in the context of tight-binding theory, and calculated core level shifts upon alloying in HgCdTe are shown to be too small to account for the observed values. A natural valence-band offset between HgTe and CdTe of 0.35 eV is found.

Shih, C. K.↗

Classic-Ada(TM)

The SPS product, Classic-Ada, is a software tool that supports object-oriented Ada programming with powerful inheritance and dynamic binding. Object Oriented Design (OOD) is an easy, natural development paradigm, but it is not supported by Ada. Following the DOD Ada mandate, SPS developed Classic-Ada to provide a tool which supports OOD and implements code in Ada. It consists of a design language, a code generator and a toolset. As a design language, Classic-Ada supports the object-oriented principles of information hiding, data abstraction, dynamic binding, and inheritance. It also supports natural reuse and incremental development through inheritance, code factoring, and Ada, Classic-Ada, dynamic binding and static binding in the same program. Only nine new constructs were added to Ada to provide object-oriented design capabilities. The Classic-Ada code generator translates user application code into fully compliant, ready-to-run, standard Ada. The Classic-Ada toolset is fully supported by SPS and consists of an object generator, a builder, a dictionary manager, and a reporter. Demonstrations of Classic-Ada and the Classic-Ada Browser were given at the workshop.

Valley, Lois↗

Theoretical study of the bonding of Nb(2+) to CH2, C2H2, and C2H4

The bonding of Nb(2+) with CH2, C2H2, and C2H4 is studied by using electronic structure calculations that include high levels of electron correlation. The binding energy for NbCH2(2+) is in good agreement with the lower bound determined from the reaction with CH4 but is significantly smaller than the value determined from the binding energy and ionization potential of NbCH2(+). The calculations and a new interpretation of the experiment indicate that the larger value is in error primarily because the ionization potential of NbCH2(+) determined from bracketing charge-exchange reactions is too small. The computed binding energy of NbC2H2(2+) is in good agreement with experiment. The calculations show that the bonding is predominantly covalent in character for both NbCH2(2+) and NbC2H2(2+), whereas for NbC2H4(2+) the electronic states that are predominantly ionic and covalent are nearly degenerate. The trend in binding energies, CH2 greater than C2H2 greater than C2H4, is consistent with the energy required to prepare the ligands for bonding.

Bauschlicher, Charles W., Jr.↗

Theoretical study of the BeLi, BeNa, MgLi, MgNa, and AlBe molecules and their negative ions

The alkaline earth-alkali diatomics are found to have weak bonds, because the diffuse alkali valence s orbitals cannot form a bond of sufficient strength to pay the promotion energy of the alkaline-earth atoms. This leads to van der Waals bonding in the neutrals as well as the negative ions. In fact, the negative ions have larger binding energies than the neutrals as a result of the much larger polarizability of the negative ion. The binding energy of AlBe is significantly larger than the Be-alkali molecules, due to a covalent contribution to the bonding. The binding energy in AlBe(-) is considerably larger than AlBe; the binding energy of the X 3Sigma(-) state of AlBe(-) is computed to be 1.36 eV, as compared with 0.57 eV for the X 2Pi state of AlBe.

Bauschlicher, Charles W., Jr.↗

Structure of V(H2)n(+) Clusters for n = 1-6

Geometries, vibrational frequencies, spin states, H2 binding energies, and Delta(S) values have been determined for V(H2)n(+), for n = 1-6, using the B3LYP hybrid functional. The binding energies and Delta(S) values are in good agreement with experiment, thus showing that the B3LYP functional offers a reliable approach for optimizing the geometry and determining the H2 binding energies for this system. The calculations show that the increase in the binding energy and entropy associated with the addition of the sixth H2 to V(+) is due to a change in spin state from quintet for the smaller clusters to triplet for V(H2)6(+). The results for V(H2)n(+) are compared with those for CO(H2)n(+).

Maitre, Philippe↗