title: Chemical aspects of some ovine hepatogenous photosensitization diseases

authors: Deng, Dawei

abstract: Current understandings of the chemistry, aetiology of saponin-associated hepatogenous photosensitization diseases of ruminants (sheep, cattle, goats and deer), the distribution of saponins in causative plants (Agave lecheguilla, Brachiaria decumbens, Narthecium ossifragum, Nolina texana, Tribulus terrestris and some Panicum species), and the ovine metabolism of saponins implicated in the development of hepatogenous photosensitization diseases, are reviewed. 

Sarsasapogenin β-D-glucoside and 3β-D-epismilagenin β-D-glucoside were synthesised from sarsasapogenin and α-acetoglucosyl bromide via three and five step reaction sequences respectively. The structures of intermediates and the product glucosides were established using a combination of GC-MS, ES-MS and 400 MHz one- and two- dimensional NMR spectral data.  

20,23,23-D₃-sarsasapogenin was prepared from sarsasapogenin using deuterioacetic acid, and the stability (exchangeability) of the deuterium atoms was determined in a series of pH 1-8 buffer solutions at 37°C, and in acetic acid at room temperature and 37°c.

Administration of an ethanol-water suspension of sarsasapogenin β-D-glucoside to a sheep afforded a maximum level of episarsasapogenin in bile samples 12 hours after dosing. Elevated levels of free sarsasapogenin and low levels of conjugated sarsasapogenin, free and conjugated episarsasapogenins and free and conjugated sarsasapogenones were detected in a rumen sample. 

Administration of mixtures of sarsasapogenin β-D-glucoside and 20,23,23-D₃-sarsasapogenin to two sheep afforded a maximum level of episarsasapogenin in bile samples 7-16 hours after dosing. Unexpected loss of deuterium atoms occurred during ovine metabolism.

Analyses of mass spectral ion ratio data, determined for the mixed dosing experiment (using free and conjugated sarsasapogenins) and an experiment in which only 23,23,23-D₃-sarsasapogenin was dosed, showed that when administered as an ethanol-water suspension sarsasapogenin β-D-glucoside was ca 1.7 times more bioavailable than sarsasapogenin.

Dosing of 3β-D-epismilagenin β-D-glucoside to two sheep showed that oxidation and reduction at C-3 was a reversible process, and that epismilagenin (α-OH), rather than smilagenin (3β-OH), was the favoured reduction product of smilagen-3-one. Deuterium loss occurred at different rates for free and conjugated epismilagenins in different metabolic regions (e.g. the rumen and the jejunum). The ion ratio profile of jejunum epismilagenin conjugates was similar to that of bile epismilagenin conjugates. 

Six saponins (faroecin, asiaticin, asiaticioside, narthecin, narthecioside and 22-methoxy-narthecioside) were isolated from a Norwegian collection of N. ossifragum and their structures were elucidated using ES-MS and one- and two-dimensional NMR spectral data. Three of these saponins, faroecin, asiaticioside and narthecioside, were identified as new compounds. Elevated levels of sarsasapogenin and smilagenin glycosides were found in some N. ossifragum samples (up to 2121 and 557 mg/kg respectively). 

The furostenol tetrasaccharide, (25R/S)-furost-5-ene-3β,22α,26-triol 3-O-{O-α-L-rhamnopyranosyl-(1→2)-O-[O-α-L-rhamnopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranosyl}-26-O-β-D-glucopyranoside, was isolated from a USA collection of P. virgatum. Variable levels of diosgenin and yamogenin glycosides were found in 13 USA P. virgatum collections (up to 288 and 42 mg/kg of diosgenin and yamogenin glycosides respectively). 

The furostenol tetrasaccharide, (25R/S)-furost-5-ene-3β,22α,26-triol 3-O-{O-α-L-rhamnopyranosyl-(1→2)-O-[O-α-L-rhamnopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranosyl}-26-O-β-D-glucopyranoside and the corresponding spirostenol tetrasaccharide, (25R/S)-spirost-5-en-3β-ol 3-O-{O-α-L-rhamnopyranosyl(1→2)-O-[O-α-L-rhamnopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranoside}, were isolated from a New Zealand collection of P. miliaceum.

Hydrolysis of the ethanol-water extracts of a USA collection of N. texana afforded three dihydroxy sapogenins, ruscogenin, neoruscogenin and spirosta-5,25(27)-diene-1β,3β-diol, in a ratio of ca 1:1.2:2.5. Three monoglycosylated saponins, spirosta-5,25(27)-diene- 1β,3β-diol 1-O-α-D-fucopyranoside, spirosta-5,25(27)-diene-1β,3β-diol 1-O-α-L-arabinopyranoside and spirosta-5,25(27)-diene-1β,3β-diol 1-O-β-D-galactopyranoside, were identified as constituents of the N. texana ethanol-water extract. 

The levels of saponins in 82 Papua New Guinea collections of B. decumbens and 4 Iranian collections of Tribulus terrestris were determined. Variable levels of diosgenin and yamogenin glycosides (B. decumbens samples), and diosgenin, smilagenin, sarsasapogenin, tigogenin, neotigogenin, hecogenin and neohecogenin glycosides (T. terrestris samples) were identified.

text: Chemical aspects of some ovine hepatogenous photosensitization diseases Current understandings of the chemistry, aetiology of saponin-associated hepatogenous photosensitization diseases of ruminants (sheep, cattle, goats and deer), the distribution of saponins in causative plants (Agave lecheguilla, Brachiaria decumbens, Narthecium ossifragum, Nolina texana, Tribulus terrestris and some Panicum species), and the ovine metabolism of saponins implicated in the development of hepatogenous photosensitization diseases, are reviewed. 

Sarsasapogenin β-D-glucoside and 3β-D-epismilagenin β-D-glucoside were synthesised from sarsasapogenin and α-acetoglucosyl bromide via three and five step reaction sequences respectively. The structures of intermediates and the product glucosides were established using a combination of GC-MS, ES-MS and 400 MHz one- and two- dimensional NMR spectral data.  

20,23,23-D₃-sarsasapogenin was prepared from sarsasapogenin using deuterioacetic acid, and the stability (exchangeability) of the deuterium atoms was determined in a series of pH 1-8 buffer solutions at 37°C, and in acetic acid at room temperature and 37°c.

Administration of an ethanol-water suspension of sarsasapogenin β-D-glucoside to a sheep afforded a maximum level of episarsasapogenin in bile samples 12 hours after dosing. Elevated levels of free sarsasapogenin and low levels of conjugated sarsasapogenin, free and conjugated episarsasapogenins and free and conjugated sarsasapogenones were detected in a rumen sample. 

Administration of mixtures of sarsasapogenin β-D-glucoside and 20,23,23-D₃-sarsasapogenin to two sheep afforded a maximum level of episarsasapogenin in bile samples 7-16 hours after dosing. Unexpected loss of deuterium atoms occurred during ovine metabolism.

Analyses of mass spectral ion ratio data, determined for the mixed dosing experiment (using free and conjugated sarsasapogenins) and an experiment in which only 23,23,23-D₃-sarsasapogenin was dosed, showed that when administered as an ethanol-water suspension sarsasapogenin β-D-glucoside was ca 1.7 times more bioavailable than sarsasapogenin.

Dosing of 3β-D-epismilagenin β-D-glucoside to two sheep showed that oxidation and reduction at C-3 was a reversible process, and that epismilagenin (α-OH), rather than smilagenin (3β-OH), was the favoured reduction product of smilagen-3-one. Deuterium loss occurred at different rates for free and conjugated epismilagenins in different metabolic regions (e.g. the rumen and the jejunum). The ion ratio profile of jejunum epismilagenin conjugates was similar to that of bile epismilagenin conjugates. 

Six saponins (faroecin, asiaticin, asiaticioside, narthecin, narthecioside and 22-methoxy-narthecioside) were isolated from a Norwegian collection of N. ossifragum and their structures were elucidated using ES-MS and one- and two-dimensional NMR spectral data. Three of these saponins, faroecin, asiaticioside and narthecioside, were identified as new compounds. Elevated levels of sarsasapogenin and smilagenin glycosides were found in some N. ossifragum samples (up to 2121 and 557 mg/kg respectively). 

The furostenol tetrasaccharide, (25R/S)-furost-5-ene-3β,22α,26-triol 3-O-{O-α-L-rhamnopyranosyl-(1→2)-O-[O-α-L-rhamnopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranosyl}-26-O-β-D-glucopyranoside, was isolated from a USA collection of P. virgatum. Variable levels of diosgenin and yamogenin glycosides were found in 13 USA P. virgatum collections (up to 288 and 42 mg/kg of diosgenin and yamogenin glycosides respectively). 

The furostenol tetrasaccharide, (25R/S)-furost-5-ene-3β,22α,26-triol 3-O-{O-α-L-rhamnopyranosyl-(1→2)-O-[O-α-L-rhamnopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranosyl}-26-O-β-D-glucopyranoside and the corresponding spirostenol tetrasaccharide, (25R/S)-spirost-5-en-3β-ol 3-O-{O-α-L-rhamnopyranosyl(1→2)-O-[O-α-L-rhamnopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranoside}, were isolated from a New Zealand collection of P. miliaceum.

Hydrolysis of the ethanol-water extracts of a USA collection of N. texana afforded three dihydroxy sapogenins, ruscogenin, neoruscogenin and spirosta-5,25(27)-diene-1β,3β-diol, in a ratio of ca 1:1.2:2.5. Three monoglycosylated saponins, spirosta-5,25(27)-diene- 1β,3β-diol 1-O-α-D-fucopyranoside, spirosta-5,25(27)-diene-1β,3β-diol 1-O-α-L-arabinopyranoside and spirosta-5,25(27)-diene-1β,3β-diol 1-O-β-D-galactopyranoside, were identified as constituents of the N. texana ethanol-water extract. 

The levels of saponins in 82 Papua New Guinea collections of B. decumbens and 4 Iranian collections of Tribulus terrestris were determined. Variable levels of diosgenin and yamogenin glycosides (B. decumbens samples), and diosgenin, smilagenin, sarsasapogenin, tigogenin, neotigogenin, hecogenin and neohecogenin glycosides (T. terrestris samples) were identified.

year: 1999

title: Acceptance culture theory: A constructivist grounded theory on bullying of junior doctors in the New Zealand healthcare system

authors: Bashir, Sarah

subjects: Workplace bullying

abstract: Workplace bullying has been a serious workplace concern for centuries, with individuals confronting various forms of abuse, mistreatment and bullying at work. Historical accounts indicate that the powerful Egyptian pharaohs strategically lured tribal people to work at their construction sites, which led to submission, slavery and bullying. Regardless of the era, the enduring nature of bullying issues illustrates that individuals can misuse their power by using bullying to establish control and authority over other individuals. In contemporary environments such as New Zealand (NZ) healthcare organisations, workplace bullying remains a significant threat that exposes healthcare workers, including junior doctors, to health and safety issues. 
Despite literature documenting the prevalence and harmful impacts of bullying on NZ junior doctors, there is a lack of theoretical explanations behind bullying in this context. This notable gap in understanding the explanations of bullying impedes effective prevention and management of workplace bullying among NZ junior doctors. The research aimed to explain the bullying process among NZ junior doctors with the objective of facilitating prevention and management. 
Twenty doctors (n=20) from various specialities in medicine and surgery participated in in-depth interviews. Data collection and analysis were guided by the Constructivist Grounded Theory (CGT) approach. Seven core categories resulted from the data analysis. Six provided explanations of bullying, highlighting the complex interplay of many factors, including social and individual characteristics of the bullies and victims, team dynamics, hierarchy, organisational culture, systemic factors, and acceptance culture. The seventh core category described the prevention and management of bullying. 
CGT analysis of the data led to the development of Acceptance Culture Theory (ACT), which is the contribution of this study. ACT outlines the social process of acceptance of bullying at multiple levels of individuals’ ecological systems. An acceptance of bullying at the micro level caused individuals to endure and accept bullying, with effects seen at multiple levels (micro, meso, exo and macro) that perpetuated an acceptance culture of bullying in the individuals’ work environments, keeping them trapped in a cycle of bullying. 
Effective prevention and management are possible by breaking the acceptance culture using comprehensive approaches encompassing macro, meso, exo, and micro levels. Alleviating hierarchal structures, frequent changes in leadership, organisational support, changes in policies and procedures, and a robust reporting system are critical for the effective prevention and management of bullying. By addressing the root causes of workplace bullying, a safe and healthy workplace can be offered for NZ junior doctors.

text: Acceptance culture theory: A constructivist grounded theory on bullying of junior doctors in the New Zealand healthcare system Workplace bullying has been a serious workplace concern for centuries, with individuals confronting various forms of abuse, mistreatment and bullying at work. Historical accounts indicate that the powerful Egyptian pharaohs strategically lured tribal people to work at their construction sites, which led to submission, slavery and bullying. Regardless of the era, the enduring nature of bullying issues illustrates that individuals can misuse their power by using bullying to establish control and authority over other individuals. In contemporary environments such as New Zealand (NZ) healthcare organisations, workplace bullying remains a significant threat that exposes healthcare workers, including junior doctors, to health and safety issues. 
Despite literature documenting the prevalence and harmful impacts of bullying on NZ junior doctors, there is a lack of theoretical explanations behind bullying in this context. This notable gap in understanding the explanations of bullying impedes effective prevention and management of workplace bullying among NZ junior doctors. The research aimed to explain the bullying process among NZ junior doctors with the objective of facilitating prevention and management. 
Twenty doctors (n=20) from various specialities in medicine and surgery participated in in-depth interviews. Data collection and analysis were guided by the Constructivist Grounded Theory (CGT) approach. Seven core categories resulted from the data analysis. Six provided explanations of bullying, highlighting the complex interplay of many factors, including social and individual characteristics of the bullies and victims, team dynamics, hierarchy, organisational culture, systemic factors, and acceptance culture. The seventh core category described the prevention and management of bullying. 
CGT analysis of the data led to the development of Acceptance Culture Theory (ACT), which is the contribution of this study. ACT outlines the social process of acceptance of bullying at multiple levels of individuals’ ecological systems. An acceptance of bullying at the micro level caused individuals to endure and accept bullying, with effects seen at multiple levels (micro, meso, exo and macro) that perpetuated an acceptance culture of bullying in the individuals’ work environments, keeping them trapped in a cycle of bullying. 
Effective prevention and management are possible by breaking the acceptance culture using comprehensive approaches encompassing macro, meso, exo, and micro levels. Alleviating hierarchal structures, frequent changes in leadership, organisational support, changes in policies and procedures, and a robust reporting system are critical for the effective prevention and management of bullying. By addressing the root causes of workplace bullying, a safe and healthy workplace can be offered for NZ junior doctors.

year: 2024

title: Māori child rearing and infant sleep practices

authors: Jones, Horiana Majorie

abstract: Sleep is important to a healthy lifestyle for parents and children, and having effective ways of putting a child to sleep contributes significantly to mental and physical wellbeing. Cultural groups around the world have developed a variety of approaches to this task, for example, rocking, co-sleeping, bed-sharing, breastfeeding to sleep, and encouraging infants to self soothe through various methods of infant sleep training. In New Zealand the continuation of traditional Māori approaches to infant sleep, e.g. co-sleeping, bed-sharing, responsivity to infant cues have been over-shadowed by its negative association with sudden infant death syndrome (SIDS) and dependence on parent interaction when initiating infant sleep. In this study, we were interested in the approaches Māori parents used to put their pēpi (child, 2 months-2 years of age) to sleep and the various factors that have influenced these approaches. Data were collected through online surveys (n =58) and face-to-face interviews (n =10) with Māori parents. Survey results indicated that being held and breast or bottle fed to sleep were the most practiced techniques by Māori parents. Parent assisted approaches, e.g., rocking, feeding, lying with baby until they go to sleep, were the most practiced. Many parents planned for their babies to sleep separately but very few actually persisted with self-soothing approaches due to a number of factors, such as discomfort with listening to their babies cry, culture, whānau (extended families) influences safety, and convenience. The majority of participants expressed a desire for separate sleep; however, few within the interview group actually successfully practiced separate sleep regularly.

text: Māori child rearing and infant sleep practices Sleep is important to a healthy lifestyle for parents and children, and having effective ways of putting a child to sleep contributes significantly to mental and physical wellbeing. Cultural groups around the world have developed a variety of approaches to this task, for example, rocking, co-sleeping, bed-sharing, breastfeeding to sleep, and encouraging infants to self soothe through various methods of infant sleep training. In New Zealand the continuation of traditional Māori approaches to infant sleep, e.g. co-sleeping, bed-sharing, responsivity to infant cues have been over-shadowed by its negative association with sudden infant death syndrome (SIDS) and dependence on parent interaction when initiating infant sleep. In this study, we were interested in the approaches Māori parents used to put their pēpi (child, 2 months-2 years of age) to sleep and the various factors that have influenced these approaches. Data were collected through online surveys (n =58) and face-to-face interviews (n =10) with Māori parents. Survey results indicated that being held and breast or bottle fed to sleep were the most practiced techniques by Māori parents. Parent assisted approaches, e.g., rocking, feeding, lying with baby until they go to sleep, were the most practiced. Many parents planned for their babies to sleep separately but very few actually persisted with self-soothing approaches due to a number of factors, such as discomfort with listening to their babies cry, culture, whānau (extended families) influences safety, and convenience. The majority of participants expressed a desire for separate sleep; however, few within the interview group actually successfully practiced separate sleep regularly.

year: 2017