Spectroscopic investigation of the quantum dynamics of small molecules encapsulated inside fullerene cages

The encapsulation of a small molecule inside a fullerene cage through advances in synthetic chemistry have created a new platform to study the dynamics of a freely rotating and translating quantum rotors entrapped inside a symmetric cage potential. These endohedral fullerene complexes are of great interest because the fullerene cages uniquely provide the entrapped molecules a high level of isolation, homogeneity, symmetry and stability. The endohedral fullerene complexes discussed in this thesis are the H2@C60, H2@C70 and H2O@C60. Both variants of small molecules studied in this thesis, H2 and H2O, exhibits spin isomerism, where the spins of both protons in the molecule are able to combine either symmetrically with total spin I=1 (ortho) or anti-symmetrically with total spin I=0 (para). The H2@C60 is the union between the simplest molecule and the most symmetrical molecule in the universe. This thesis discusses the temperature dependence of cold neutron scattering study in this complex to investigate the statistical distribution of the energy states. The H2@C70 is a less symmetric endohedral fullerene which has a prolate ellipsoidal symmetry cage. This thesis discusses the low temperature thermal neutron scattering and the temperature dependence of cold neutron scattering investigations in the complex to study the effect of the ellipsoidal cage on the quantum dynamics of the molecules. H2O@C60 is different to the dihydrogen variant of the small molecule endohedral fullerenes because H2O has a permanent electric dipole moment and is less symmetric than H2. The quantum dynamics of the H2O@C60 is investigated using low temperature thermal neutron scattering, temperature dependence cold neutron scattering and milli-Kelvin NMR. Unlike the dihydrogen endohedral fullerenes, the H2O@C60 also exhibits slow nuclear spin-isomer conversion at low temperatures. This low temperature ortho-H2O to para-H2O conversion process is investigated with both INS and NMR to study the conversion mechanism

UTAR heats up as inti falters

The team from Tunku Abdul rahman Universiti (UTAR) showed all shades of ferocity as they took the International Islamic Universiti Malaysia (IIUM) apart, 89-46, making up for their previous lackluster performance against Multimedia Universiti (MMU) in the Universiti College Basketball League (UCBL)

Effect of forest fire on stand structure in Raja Musa Peat Swamp Forest Reserve, Selangor, Malaysia

The objective of this study was to investigate the effect of forest fire on forest structure in the peat swamp forest. The study was conducted in Raja Musa Forest Reserve which has been experiencing fire occurrences since 1996. Ten plots each measuring 50x20 m were systematically set up both in the burnt and unburnt area and plant inventory were conducted between September 2001 to June 2002. Results showed that there were 10 families and 22 families in burnt and unburnt area, respectively. In terms of family, Euphorbiaceae (61.9%) rank first in the burnt area. Imperata cylindrica from family of Poaceae had the most coverage on burnt plot. For tree diameter distribution, trees with diameter class of 10.1-15.0 cm and 15.1-20.0 cm had the highest number in the unburnt area while trees with diameter class of 5.1-10.0 cm was the highest in burnt area. Shannon’s diversity index in burnt area was 1.62, lower compared to unburnt area which was 2.40. Evenness index for burnt area was 0.68, lower than unburnt area which was 0.71. This study shows that fire affects the species composition and stand structure of the forest and herbaceous vegetation, such as Poaceae was found to be abundant in burnt area compared to unburnt area

Spectroscopic investigation of the quantum dynamics of small molecules encapsulated inside fullerene cages

The encapsulation of a small molecule inside a fullerene cage through advances in synthetic chemistry have created a new platform to study the dynamics of a freely rotating and translating quantum rotors entrapped inside a symmetric cage potential. These endohedral fullerene complexes are of great interest because the fullerene cages uniquely provide the entrapped molecules a high level of isolation, homogeneity, symmetry and stability. The endohedral fullerene complexes discussed in this thesis are the H2@C60, H2@C70 and H2O@C60. Both variants of small molecules studied in this thesis, H2 and H2O, exhibits spin isomerism, where the spins of both protons in the molecule are able to combine either symmetrically with total spin I=1 (ortho) or anti-symmetrically with total spin I=0 (para). The H2@C60 is the union between the simplest molecule and the most symmetrical molecule in the universe. This thesis discusses the temperature dependence of cold neutron scattering study in this complex to investigate the statistical distribution of the energy states. The H2@C70 is a less symmetric endohedral fullerene which has a prolate ellipsoidal symmetry cage. This thesis discusses the low temperature thermal neutron scattering and the temperature dependence of cold neutron scattering investigations in the complex to study the effect of the ellipsoidal cage on the quantum dynamics of the molecules. H2O@C60 is different to the dihydrogen variant of the small molecule endohedral fullerenes because H2O has a permanent electric dipole moment and is less symmetric than H2. The quantum dynamics of the H2O@C60 is investigated using low temperature thermal neutron scattering, temperature dependence cold neutron scattering and milli-Kelvin NMR. Unlike the dihydrogen endohedral fullerenes, the H2O@C60 also exhibits slow nuclear spin-isomer conversion at low temperatures. This low temperature ortho-H2O to para-H2O conversion process is investigated with both INS and NMR to study the conversion mechanism

Probing hydrogen bond interactions in a shear thickening polysaccharide using nonlinear shear and extensional rheology

Mamaku gum is a polysaccharide extracted from the fronds of the black tree fern found in New Zealand. The cooked pith has traditionally been used for various medicinal purposes and as a food source by the Maori people of New Zealand. It has potential applications as a thickener in the food industry and as a palliative for patients with dysphagia. Studies on the shear rheology of Mamaku gum have revealed that the gum exhibits shear thickening at a critical shear rate due to a transition from intra- to inter-molecular chain interactions upon shear-induced chain elongation. In this paper, we demonstrate that these interactions are primarily due to hydrogen bonding. We perform extensional rheology on mixtures of Mamaku gum and urea (a known disruptor of hydrogen bonds) to quantify the nature of these interactions. Capillary Breakup Extensional Rheometry (CaBER) performed on the pure Mamaku gum solutions yield plateau values of the Trouton ratio as high as ∼10[superscript 4], showing that the viscoelasticity of the gum in uniaxial elongation is much higher than in shear. For all Mamaku concentrations tested, the extensional viscosity decreases upon increasing urea concentration. Furthermore, the relaxation time decreases exponentially with increasing urea concentration. This exponential relationship is independent of the Mamaku concentration, and is identical to the relationships between urea concentration and characteristic timescales measured in nonlinear shear rheology. We show using the sticky reptation model for polymers with multiple sticker groups along the backbone how such a relationship is consistent with a linear decrease in the free energy for hydrogen bond dissociation. We then demonstrate that a time-concentration superposition principle can be used to collapse the viscoelastic properties of the Mamaku-gum/urea mixtures.United States. National Aeronautics and Space Administration (Grant NNX09AV99G

Effect of Celluclast 1.5L on the Physicochemical Characterization of Gold Kiwifruit Pectin

The effects of Celluclast 1.5L concentration on the physicochemical characterization of gold kiwifruit pectin was evaluated. Varying the enzyme concentration affected the pectin yield and pectin physicochemical properties. The viscosity of extracted pectin was largely dependent on the enzyme concentration. Celluclast 1.5L with medium concentration exhibited the highest viscosity. Varying the enzyme concentration also influenced the molecular weight distribution. High molecular weight (Mw) pectin (1.65 × 106 g/mol) was obtained when the medium concentration was used. Overall, the study clearly reflects the importance of taking into consideration the amount of cellulytic enzyme added in order to determine the final quality of pectin

The copper resistome of group B Streptococcus reveals insight into the genetic basis of cellular survival during metal ion stress

In bacteria, copper (Cu) can support metabolic processes as an enzymatic cofactor but can also cause cell damage if present in excess, leading to intoxication. In group B Streptococcus (GBS), a system for control of Cu efflux based on the prototypical cop operon supports survival during Cu stress. In some other bacteria, genetic systems additional to the cop operon are engaged during Cu stress and also contribute to the management of cellular Cu homeostasis. Here, we examined genetic systems beyond the cop operon in GBS for regions that contribute to survival of GBS in Cu stress using a forward genetic screen and probe of the entire bacterial genome. A high-density mutant library, generated using pGh9-ISS1, was used to expose GBS to Cu stress and compare it to nonexposed controls en masse. Eight genes were identified as essential for GBS survival in Cu stress, whereas five genes constrained GBS growth in Cu stress. The genes encode varied factors including enzymes for metabolism, cell wall synthesis, transporters, and cell signaling factors. Targeted mutation of the genes validated their roles in GBS resistance to Cu stress. Excepting copA, the genes identified are new to the area of bacterial metal ion intoxication. We conclude that a discrete and limited suite of genes beyond the cop operon in GBS contributes to a repertoire of mechanisms used to survive Cu stress in vitro and achieve cellular homeostasis

Cellular management of zinc in group B Streptococcus supports bacterial resistance against metal intoxication and promotes disseminated infection

Zinc is an essential trace element for normal bacterial physiology but, divergently, can intoxicate bacteria at high concentrations. Here, we define the molecular systems for Zn detoxification in Streptococcus agalactiae, also known as group B streptococcus, and examine the effects of resistance to Zn stress on virulence. We compared the growth of wild-type bacteria and mutants deleted for the Zn exporter, czcD, and the response regulator, sczA, using Zn-stress conditions in vitro. Macrophage antibiotic protection assays and a mouse model of disseminated infection were used to assess virulence. Global bacterial transcriptional responses to Zn stress were defined by RNA sequencing and quantitative reverse transcription-PCR. czcD and sczA enabled S. agalactiae to survive Zn stress, with the putative CzcD efflux system activated by SczA. Additional genes activated in response to Zn stress encompassed divalent cation transporters that contribute to regulation of Mn and Fe homeostasis. In vivo, the czcD-sczA Zn management axis supported virulence in the blood, heart, liver, and bladder. Additionally, several genes not previously linked to Zn stress in any bacterium, including, most notably, arcA for arginine deamination, also mediated resistance to Zn stress, representing a novel molecular mechanism of bacterial resistance to metal intoxication. Taken together, these findings show that S. agalactiae responds to Zn stress by sczA regulation of czcD, with additional novel mechanisms of resistance supported by arcA, encoding arginine deaminase. Cellular management of Zn stress in S. agalactiae supports virulence by facilitating bacterial survival in the host during systemic infection. Importance Streptococcus agalactiae, also known as group B streptococcus, is an opportunistic pathogen that causes various diseases in humans and animals. This bacterium has genetic systems that enable zinc detoxification in environments of metal stress, but these systems remain largely undefined. Using a combination of genomic, genetic, and cellular assays, we show that this pathogen controls Zn export through CzcD to manage Zn stress and utilizes a system of arginine deamination never previously linked to metal stress responses in bacteria to survive metal intoxication. We show that these systems are crucial for survival of S. agalactiae in vitro during Zn stress and also enhance virulence during systemic infection in mice. These discoveries establish new molecular mechanisms of resistance to metal intoxication in bacteria; we suggest these mechanisms operate in other bacteria as a way to sustain microbial survival under conditions of metal stress, including in host environments

Regulatory cross-talk supports resistance to Zn intoxication in Streptococcus

Metals such as copper (Cu) and zinc (Zn) are important trace elements that can affect bacterial cell physiology but can also intoxicate bacteria at high concentrations. Discrete genetic systems for management of Cu and Zn efflux have been described in several bacterial pathogens, including streptococci. However, insight into molecular cross-talk between systems for Cu and Zn management in bacteria that drive metal detoxification, is limited. Here, we describe a biologically consequential cross-system effect of metal management in group B Streptococcus (GBS) governed by the Cu-responsive copY regulator in response to Zn. RNAseq analysis of wild-type (WT) and copY-deficient GBS subjected to metal stress revealed unique transcriptional links between the systems for Cu and Zn detoxification. We show that the Cu-sensing role of CopY extends beyond Cu and enables CopY to regulate Cu and Zn stress responses that effect changes in gene function for central cellular processes, including riboflavin synthesis. CopY also supported GBS intracellular survival in human macrophages and virulence during disseminated infection in mice. In addition, we show a novel role for CovR in modulating GBS resistance to Zn intoxication. Identification of the Zn resistome of GBS using TraDIS revealed a suite of genes essential for GBS growth in metal stress. Several of the genes identified are novel to systems that support bacterial survival in metal stress and represent a diverse set of mechanisms that underpin microbial metal homeostasis during cell stress. Overall, this study reveals a new and important mechanism of cross-system complexity driven by CopY in bacteria to regulate cellular management of metal stress and survival