Physical investigations of small particles : (I) aerosol particle charging and flux enhancement and (II) whispering gallery mode sensing

Part I

Particles are a key feature of planetary atmospheres. On Earth they represent the greatest source of uncertainty in the global energy budget. This uncertainty can be addressed by making more measurement, by improving the theoretical analysis of measurements, and by better modeling basic particle nucleation and initial particle growth within an atmosphere. This work will focus on the latter two methods of improvement.

Uncertainty in measurements is largely due to particle charging. Accurate descriptions of particle charging are challenging because one deals with particles in a gas as opposed to a vacuum, so different length scales come into play. Previous studies have considered the effects of transition between the continuum and kinetic regime and the effects of two and three body interactions within the kinetic regime. These studies, however, use questionable assumptions about the charging process which resulted in skewed observations, and bias in the proposed dynamics of aerosol particles. These assumptions affect both the ions and particles in the system. Ions are assumed to be point monopoles that have a single characteristic speed rather than follow a distribution. Particles are assumed to be perfect conductors that have up to five elementary charges on them. The effects of three body interaction, ion-molecule-particle, are also overestimated. By revising this theory so that the basic physical attributes of both ions and particles and their interactions are better represented, we are able to make more accurate predictions of particle charging in both the kinetic and continuum regimes.

The same revised theory that was used above to model ion charging can also be applied to the flux of neutral vapor phase molecules to a particle or initial cluster. Using these results we can model the vapor flux to a neutral or charged particle due to diffusion and electromagnetic interactions. In many classical theories currently applied to these models, the finite size of the molecule and the electromagnetic interaction between the molecule and particle, especially for the neutral particle case, are completely ignored, or, as is often the case for a permanent dipole vapor species, strongly underestimated. Comparing our model to these classical models we determine an “enhancement factor” to characterize how important the addition of these physical parameters and processes is to the understanding of particle nucleation and growth.

Part II

Whispering gallery mode (WGM) optical biosensors are capable of extraordinarily sensitive specific and non-specific detection of species suspended in a gas or fluid. Recent experimental results suggest that these devices may attain single-molecule sensitivity to protein solutions in the form of stepwise shifts in their resonance wavelength, \lambda_{R}, but present sensor models predict much smaller steps than were reported. This study examines the physical interaction between a WGM sensor and a molecule adsorbed to its surface, exploring assumptions made in previous efforts to model WGM sensor behavior, and describing computational schemes that model the experiments for which single protein sensitivity was reported. The resulting model is used to simulate sensor performance, within constraints imposed by the limited material property data. On this basis, we conclude that nonlinear optical effects would be needed to attain the reported sensitivity, and that, in the experiments for which extreme sensitivity was reported, a bound protein experiences optical energy fluxes too high for such effects to be ignored.

Studies of ion energy and yield from argon clusters heated by intense femtosecond laser pulses

Using time-of-flight spectrometry, the interaction of intense femtosecond laser pulses with argon clusters has been studied by measuring the energy and yield of emitted ions. With two different supersonic nozzles, the dependence of average ion energy (E) over bar on cluster size (n) over bar in a large range of (n) over bar approximate to 3 x 10(3) similar to 3 x 10(6) has been measured. The experimental results indicate that when the cluster size (n) over bar <= 3 x 10(5), the average ion energy (E) over bar proportional to (n) over bar (0.5), Coulomb explosion is the dominant expansion mechanism. Beyond this size, the average ion energy gets saturated gradually, the clusters exhibit a mixed Coulomb-hydrodynamic expansion behavior. We also find that with the increasing gas backing pressure, there is a maximum ion yield, the ion yield decreases as the gas backing pressure is further increased.

Interactions of a femtosecond intense laser with rare gas clusters in a dense jet\

A study on the interactions of high intensity (similar to 10(16) W/cm(2)) femtosecond laser pulses with rare gas clusters in a dense jet is performed. Energy absorption by Ar and Xe clusters is measured and it can be as high as 90%. Very energetic ions produced in the laser interaction with a dense cluster jet are detected by time-of-flight spectrometry and the maximum ion energy of Xe is up to 1.3 MeV. The average ion energies are found to increase with increasing cluster size and get saturated gradually. The average ion energies also show a strong directionality and the average ion energy in the direction parallel to the laser polarization vector is 40% higher than that perpendicular to it. The findings are discussed in terms of a model of charge-dependent ion acceleration.

Design, operation and economics of a small-scale hatchery for the larval rearing of sugpo, Penaeus monodon Fab.

One of the major problems in the mass production of sugpo is how to obtain a constant supply of fry. Since ultimately it is the private sector which should produce the sugpo fry to fill the needs of the industry, the Barangay Hatchery Project under the Prawn Program of the Aquaculture Department of SEAFDEC has scaled down the hatchery technology from large tanks to a level which can be adopted by the private sector, especially in the villages, with a minimum of financial and technical inputs. This guide to small-scale hatchery operations is expected to generate more enthusiasm among fish farmers interested in venturing into sugpo culture.

Reactions of small molecules facilitated by metal-acceptor interactions

The role of metal-acceptor interactions arising from M–BR3 and M–PR3 bonding is discussed with respect to reactions between first-row transition metals and N2, H2, and CO. Thermally robust, S = 1/2 (TPB)Co(H2) and (TPB)Co(N2) complexes (TPB = tris(2- (diisopropylphosphino)phenyl)borane) are described and the energetics of N2 and H2 binding are measured. The H2 and N2 ligands are bound more weakly in the (TPB)Co complexes than in related (SiP3)M(L) complexes (SiP3 = tris(2- (diisopropylphosphino)phenyl)silyl). Comparisons within and between these two ligand platforms allow for the factors that affect N2 (and H2) binding and activation to be delineated. The characterization and reactivity of (DPB)Fe complexes (DPB = bis(2- (diisopropylphosphino)phenyl)phenylborane) in the context of N2 functionalization and E–H bond addition (E = H, C, N, Si) are described. This platform allows for the one-pot transformation of free N2 to an Fe hydrazido(-) complex via an Fe aminoimide intermediate. The principles learned from the N2 chemistry using (DPB)Fe are applied to CO reduction on the same system. The preparation of (DPB)Fe(CO)2 is described as well as its reductive functionalization to generate an unprecedented Fe dicarbyne. The bonding in this highly covalent complex is discussed in detail. Initial studies of the reactivity of the Fe dicarbyne reveal that a CO-derived olefin is released upon hydrogenation. Alternative approaches to uncovering unusual reactivity using metal- acceptor interactions are described in Chapters 5 and 6, including initial studies on a new π-accepting tridentate diphosphinosulfinyl ligand and strategies for designing ligands that undergo site-selective metallation to generate heterobimetallic complexes.

Sunyaev-Zel'dovich observations using large-format millimeter arrays

Galaxy clusters are the largest gravitationally bound objects in the observable universe, and they are formed from the largest perturbations of the primordial matter power spectrum. During initial cluster collapse, matter is accelerated to supersonic velocities, and the baryonic component is heated as it passes through accretion shocks. This process stabilizes when the pressure of the bound matter prevents further gravitational collapse. Galaxy clusters are useful cosmological probes, because their formation progressively freezes out at the epoch when dark energy begins to dominate the expansion and energy density of the universe. A diverse set of observables, from radio through X-ray wavelengths, are sourced from galaxy clusters, and this is useful for self-calibration. The distributions of these observables trace a cluster's dark matter halo, which represents more than 80% of the cluster's gravitational potential. One such observable is the Sunyaev-Zel'dovich effect (SZE), which results when the ionized intercluster medium blueshifts the cosmic microwave background via Compton scattering. Great technical advances in the last several decades have made regular observation of the SZE possible. Resolved SZE science, such as is explored in this analysis, has benefitted from the construction of large-format camera arrays consisting of highly sensitive millimeter-wave detectors, such as Bolocam. Bolocam is a submillimeter camera, sensitive to 140 GHz and 268 GHz radiation, located at one of the best observing sites in the world: the Caltech Submillimeter Observatory on Mauna Kea in Hawaii. Bolocam fielded 144 of the original spider web NTD bolometers used in an entire generation of ground-based, balloon-borne, and satellite-borne millimeter wave instrumention. Over approximately six years, our group at Caltech has developed a mature galaxy cluster observational program with Bolocam. This thesis describes the construction of the instrument's full cluster catalog: BOXSZ. Using this catalog, I have scaled the Bolocam SZE measurements with X-ray mass approximations in an effort to characterize the SZE signal as a viable mass probe for cosmology. This work has confirmed the SZE to be a low-scatter tracer of cluster mass. The analysis has also revealed how sensitive the SZE-mass scaling is to small biases in the adopted mass approximation. Future Bolocam analysis efforts are set on resolving these discrepancies by approximating cluster mass jointly with different observational probes.

Coulomb expansion of deuterated methane clusters irradiated by an ultrashort intense laser pulse

The simulations of three-dimensional particle dynamics show that when irradiated by an ultrashort intense laser pulse, the deuterated methane cluster expands and the majority of deuterons overrun the more slowly expanding carbon ions, resulting in the creation of two separated subclusters. The enhanced deuteron kinetic energy and a narrow peak around the energy maximum in the deuteron energy distribution make a considerable contribution to the efficiency of nuclear fusion compared with the case of homonuclear deuterium clusters. With the intense laser irradiation, the nuclear fusion yield increases with the increase of the cluster size, so that deuterated heteronuclear clusters with larger sizes are required to achieve a greater neutron yield.

Optimizing the benefits from Nigerian small and medium size reservoirs through cooperative management approach

The paper traces the different management practices adopted for Nigerian inland water bodies from the Colonial era to independence. It observes that the full potentials of these waters have never been realized over the years due to the absence of an effective management. The replacement of the traditional fisheries management by the centralized top-down approach by government after independence has not helped matters. Lately, the cooperative/community-based management approach has taken the centre stage worldwide. This has been identified to offer the most viable and equitable option towards the attainment of an optimum utilization of the fisheries resource. The entire community sensing security of tenure and enjoying some of the benefits from access control will actively take responsibility and enforcement. The paper drew experiences from some water bodies in Bangladesh, Philippines, Benin Republic and Malawi showing sound management strategy that, if adopted for our small and medium size reservoirs and other water bodies, would help optimize on an sustainable manner the benefits from those water bodies

Financial analysis of small-scale fish farming enterprises to alleviate poverty in homestead

This paper focuses on the financial analysis involved in setting up of fish farming on a small-scale in a homestead. About 0.5 acres of land was used for the construction of pond which as a stock of Clarias spp/ Heterobranchus spp and Tilapia spp at the ratio of one to three for a period of 12 months. The land/land development cost is N26,500.00, pond construction cost, N35,700.00, equipment cost, N2,650.00 and stock/Input requirement cost N155,727.00 while the revenue from sales is N376,000.00. A cash flow analysis is also calculated for the fish farm, which is N155,423.00 for first year cash flow, and appropriate profit/mosses were calculated for five-year production cycle of N1,036,515.00 million. At the end appreciable profit is realized from the enterprises. This type of enterprises is viable for small-scale farmers to practices and adopted for financial support for their family

Fish distribution in a small domestic water supply reservoir: a case study of Kangimi Reservoir, Kaduna, Nigeria

A study of the composition and distribution of fish populations in the inshore, surface and bottom water habitats of Kangimi Reservoir showed that the most abundant family was the Cichlidae followed in order of abundance by the familiesCyprinidae, Schilbeidae, Mormyridae, Mochokidae, Characidae, centropomidae and Bagridae. Though the overall composition of families caught inn the three habitats did not vary significantly (P>0.05) only family Cichlidae showed habitat preference: there was a preponderance of Cichlidae in the inshore water habitat (P<0.05). The families Bagridae and Centropomidae were caught only in the inshore and bottom water habitats while the other families were caught from all habitats and showed no habitat preference. The dominance of primary and secondary consumers indicates high fish production potential under adequate management

Small Indigenous Freshwater Fish Species: their Role in Poverty Alleviation, Food Security and Conservation of Biodiversity, 23-25 February 2010, Central Inland Fisheries Research Institute, Barrackpore, Kolkata, West Bengal. Workshop report

This is the report on the workshop on “Small Indigenous Freshwater Fish Species: Their Role in Poverty Alleviation, Food Security and Conservation of Biodiversity”, organized by the International Collective in Support of Fishworkers(ICSF) in collaboration with the Inland Fisheries Society of India (IFSI). The workshop was a forum for exchange of views on the role of small indigenous freshwater fish species (SIFFS) in enhancing rural food supply and livelihood security, and in conserving biodiversity. The workshop also discussed the socioeconomic and cultural contexts for the culture and capture of SIFFS, and how to enhance access—especially for women—to better incomes, livelihoods and nutritional security, through appropriate policy spaces. This report provides a fresh focus on SIFFS, usually regarded as ‘trash’ fish. It urges scientists, researchers and decisionmakers to develop policy and legislative measures to ensure the conservation and promotion of SIFFS, both in capture- and culture-fisheries systems. This report will be useful for fishworker organizations, researchers, policymakers, fish farmers, members of civil society and anyone interested in fisheries and livelihoods. (PDF contains 86 pages)

Towards conditional RNAi : shape and sequence transduction with small conditional RNAs

RNA interference (RNAi) is a powerful biological pathway allowing for sequence-specific knockdown of any gene of interest. While RNAi is a proven tool for probing gene function in biological circuits, it is limited by being constitutively ON and executes the logical operation: silence gene Y. To provide greater control over post-transcriptional gene silencing, we propose engineering a biological logic gate to implement “conditional RNAi.” Such a logic gate would silence gene Y only upon the expression of gene X, a completely unrelated gene, executing the logic: if gene X is transcribed, silence independent gene Y. Silencing of gene Y could be confined to a specific time and/or tissue by appropriately selecting gene X.

To implement the logic of conditional RNAi, we present the design and experimental validation of three nucleic acid self-assembly mechanisms which detect a sub-sequence of mRNA X and produce a Dicer substrate specific to gene Y. We introduce small conditional RNAs (scRNAs) to execute the signal transduction under isothermal conditions. scRNAs are small RNAs which change conformation, leading to both shape and sequence signal transduction, in response to hybridization to an input nucleic acid target. While all three conditional RNAi mechanisms execute the same logical operation, they explore various design alternatives for nucleic acid self-assembly pathways, including the use of duplex and monomer scRNAs, stable versus metastable reactants, multiple methods of nucleation, and 3-way and 4-way branch migration.

We demonstrate the isothermal execution of the conditional RNAi mechanisms in a test tube with recombinant Dicer. These mechanisms execute the logic: if mRNA X is detected, produce a Dicer substrate targeting independent mRNA Y. Only the final Dicer substrate, not the scRNA reactants or intermediates, is efficiently processed by Dicer. Additional work in human whole-cell extracts and a model tissue-culture system delves into both the promise and challenge of implementing conditional RNAi in vivo.

Selective hydroxylation of small alkanes by the particulate methane monooxygenase

The particulate methane monooxygenase (pMMO) catalyzes the oxidation of methane to methanol under ambient temperatures and pressures. Other small alkanes and alkenes are also substrates of this enzyme. We measured and compared the initial rate constants of oxidation of small alkanes (C1 to C5) catalyzed by pMMO. Both primary and secondary alcohols were formed from oxidation of n-butane and n-pentane. The alcohols produced from alkane oxidation can be further oxidized, probably by pMMO, to aldehydes and ketones. The apparent regioselectivity for n-butane and n-pentane is 100% 2-alcohols because the formation of primary alcohols is slower than further oxidation of these alcohols. The hydroxylation at the secondary carbons is highly stereoselective: (R)-alcohols are preferentially formed. The enantiomeric excess increases slightly with decreasing reaction temperature. The steric course of hydroxylation on primary carbons was also studied by using isotopically substituted ethane: (S)- or (R)-CH_3-CHDT, and (S)- or (R)-CD_3- CHDT and the reactions were found to proceed with 100% retention of configuration. A primary isotopic effect of k_H/k_D=5.0 was observed in these experiments.

Pure Coulomb explosions of highly charged methane clusters investigated by a simple electrostatic model

The pure Coulomb explosions of the methane clusters (CA(4))(n), (light atom A = H or D) have been investigated by a simplified electrostatic model for both a single cluster and an ensemble of clusters with a given cluster size distribution. The dependence of the energy of ions produced from the explosions on cluster size and the charge state of the carbon ions has been analysed. It is found that, unlike the average proton energy which increases with the charge q of the carbon ions, the average deuteron energy tends to saturate as q becomes larger than 4. This implies that when the laser intensity is sufficiently high for the (CD4)(n) to be ionized to a charge state of (C4+D4+)(n), the neutron yield from a table-top laser-driven Coulomb explosion of deuterated methane clusters (CD4)(n) could be increased significantly by increasing the interaction volume rather than by increasing the laser intensity to produce the higher charge state (C6+D4+)(n). The flight-time spectra of the carbon ions and the light ions have also been studied.

Nuclear fusion from Coulomb explosions of deuterated methane clusters subjected to ultraintense femtosecond laser pulses

This paper reports that Coulomb explosions taken place in the experiment of heteronuclear deuterated methane clusters ((CD4)(n)) in a gas jet subjected to intense femtosecond laser pulses (170 mJ, 70 fs) have led to table-top laser driven DD nuclear fusion. The clusters produced in supersonic expansion had an average energies of deuterons produced in the laser-cluster interaction were 60 and 1.5 KeV, respectively. From DD collisons of energetic deuterons, a yield of 2.5(+/-0.4)x10(4) fusion neutrons of 2.45 MeV per shot was realized, giving rise to a neutron production efficiency of about 1.5 x 10(5) per joule of incident laser pulse energy. Theoretical calculations were performed and a fairly good agreement of the calculated neutron yield with that obtained from the present experiment was found.