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Abstract |
Palm
Vitamin E for Aquaculture Feeds
In this overview, our current research on the use of palm oil-based
vitamin E in aquaculture feeds will be highlighted. While most vegetable
oils contain almost exclusively tocopherols, palm oil is notable because
tocotrienols represent about 80% of the vitamin E content. Almost
all vitamin E research in fish nutrition has focused on a-tocopherol,
usually supplied as the synthetic all-rac-a-tocopherol acetate, as
it is deemed the most potent of all the isoforms. Several feeding
trials were carried out to investigate the deposition of vitamin E
and their antioxidant activity in various tissues of tilapia and catfish
fed various palm oil products and vitamin E sources. We were the first
group of researchers to show that (1) the tocotrienol-rich fraction
(TRF) extracted from palm oil is more potent than all-rac-a-tocopherol
acetate as an antioxidant when used in tilapia diets; (2) fish tissues
varied in their ability to accumulate tocotrienols with the highest
concentrations being found in perivisceral adipose tissues, followed
by liver, skin and muscle; (3) tissue concentrations of a-tocopherol,
a-tocotrienol and ?-tocotrienol increased linearly in response to
increasing dietary concentrations originating from added TRF. As a
potent in vivo antioxidant in fish tissues, palm vitamin E will have
positive impacts on seafood quality such as prolonging shelf-life,
maintaining colouration of pigmented seafood and enhancing the nutritional
value of seafood.
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Palm
Oil-based Methyl Ester Sulphonate as an Oil Well Stimulation Agent
Methyl ester sulphonate (MES) is a surfactant (surface-active agent)
that can reduce interfacial tension between water and oil. The compound
can be diluted not only in water but also in oil. MES surfactant can
be used in chemical stimulation processes to increase and enhance
oil recovery (EOR) from reservoirs by reducing the interfacial tension
between the oil and water formation. One of the success criteria in
surfactant application as a stimulation agent is its effect on the
interfacial value between oil and water droplets in a particular saline
condition. Hence, the palm oil-based MES oil well stimulation agent
was tested in three saline conditions before it was injected into
the core. This study was aimed at determining the total oil recovery
from a crude oil reservoir after injection of the palm oil-based MES
stimulation agent into the core. The formulation of the palm oil-based
MES as a stimulation agent consists of 70% palm oil-based MES, 20%
solvent, 7% non-ionic surfactant and 3% co-solvent. Using 0.5% and
1% concentrations of the stimulation agent tested at 10 000, 20 000
and 30 000 ppm water salinity, the interfacial tension between oil
and water was reduced to 10-4 dyne cm-1. The total oil recovery with
a 0.5% concentration of the palm oil-based MES stimulation agent was
between 88% and 94%. However, the total oil recovery increased in
the range of 90%-99% with the injection of a 1% palm oil-based MES
stimulation agent into the core. Based on these results, the palm
oil-based MES surfactant can be used effectively as a stimulation
agent in a real crude oil reservoir.
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Production
of Carotenoid and Tocols Concentrates from Palm Oil Using Supercritical
Carbon Dioxide
A method using supercritical carbon dioxide to produce concentrated
carotenoids and tocols from palm oil is described. The free fatty acids
of crude palm oil were esterified by acid-catalysis followed by transesterification
of the triglycerides into methyl esters. Methyl esters are considerably
more soluble in supercritical carbon dioxide than the triglycerides
and free fatty acids, and are preferentially dissolved leaving a solution
of highly concentrated carotenoids (20.11 wt%) and tocols (10.66 wt%).
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Biodiesel
Production from Different Feedstocks in Pilot Scale System
In this study, the preparations of biodiesel from three different feedstocks,
including rapeseed oil, high acidified Chinese wood oil and trap grease,
were carried out in a pilot scale of 200 t yr-1 biodiesel production
system. The optimum operating conditions for transesterification of
rapeseed oil in plug flow reactor were found to be as follows: the catalyst
dosage is 1.2 wt%; the retention time is about 17 min; the bed temperature
is 65oC; the oil/methanol ratio is 1:6; the content of methyl ester
is 96.33% under these conditions. A kind of ion exchange resin, a solid
acid catalyst, filled in the fixed bed reactor was used as the esterification
catalyst for the pretreating of high acidified oil. The acid value of
Chinese wood oil could be reduced from 7 to 0.8 mg KOH•g-1 after
88 min, the optimum operating conditions were obtained as follow: molar
ratio of methanol to oil is about 6:1 , the temperature of the fixed
bed, 65oC and the retention time, about 88 min. Also a kind of acidified
oil, namely trap grease, with the acid value being 114 mg KOH•g-1
could be equally converted to a good biodiesel product through this
system. Generally, the refined biodiesel product generated through this
system could meet China #0 Biodiesel Standard, as well as Germany Biodiesel
Standard for most indexes. It indicates that the designed process in
this system has a good adaptability for different kinds of oil.
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Advanced
Carbon Product from Oil Palm Biomass
A method was developed
to produce advanced carbon products from oil palm biomass. Oil palm
empty fruit bunch (EFB) contains polymeric lignocellulosic components
such as hemicellulose, cellulose and lignin, and is therefore a potential
raw material for producing advanced materials such as carbon electrode
and molecular sieve carbon. Carbon precursors were prepared by slow
pyrolysis of EFB under vacuum at 280oC. Powder obtained from grinding
and ball milling the semi-pyrolysed EFB was then treated with 0.2, 0.4
and 0.6 M H2SO4 and dried at 100ºC. The chemical changes of the
treated EFB carbon precursors are discussed by their Thermogravimetric
(TGA) results. Green body pellets were then prepared by molding of the
carbon precursors powder at 10 t of compression force and then carbonized
at 600ºC, 800ºC and 1000ºC using multiple heating profiles
under nitrogen gas flow. The carbon pellets prepared from 0.4 M H2SO4
gave the highest density (?), Young’s modulus (E), Rockwell hardness
(H) and electrical conductivity (s). These indicated that the treatment
had increased the crystallinity of the carbon as also evidenced by the
XRD analysis results. BET surface area analysis was carried out and
it was found that the carbon precursors treated with 0.6 M H2SO4 produced
the activated carbon with the highest porosity. The carbon pellets produced
from the treatment with 0.6 M H2SO4 and carbonized at different temperatures
were further activated with CO2 to further increase their porosity,
and the effects of different carbonization temperature on the pore structure
and adsorptive properties for oxygen and nitrogen were investigated.
This study has identified oil palm EFB as a potentially suitable raw
material for the preparation of carbon electrode and molecular sieve
carbon.
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Gamma
Tocotrienol and Prostate Cancer: The Regulation of Two Independent
Pathways to Potentiate Cell Growth Inhibition and Apoptosis
Dietary
vitamin E, highly expressed in palm oil, exists as either tocopherols
or tocotrienols. Evidence indicates that vitamin Es may be potent
cancer preventive agents. In this study, the y- and d- isoforms of
vitamin E were found to be the most effective at cancer cell growth
inhibition, with the tocotrienols being more effective than the tocopherols
in androgen-independent PC-3 prostate cancer cells. To assure that
these compounds were selective toward cancer cells, the growth arrest
of PrEC normal prostate cells was compared to PC-3 cells. At concentrations
of =30 µM dietary, y-vitamin Es showed no significant growth
arrest on PrEC cell growth, but selectively inhibited growth in the
PC-3 cancer cells. Moreover y-tocotrienol demonstrated a greater potential
to inhibit growth in cancer cells at these lower concentrations than
did y-tocopherol. Two independent pathways important in carcinogenesis
were tested: PPAR yand NFkB. The PPAR y was up regulated by both dietary
y-vitamin Es by the modulation of the endogenous ligand 15-S-HETE,
while NFkB was only regulated by y-tocotrienol. The modulation of
NFkB was confirmed by the down regulation of the pro-apoptotic proteins
cIAP, xIAP, and BcL-2 which potentiate apoptosis and are down stream
effectors of NFkB.
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Preparation
of a Low Viscosity and Light Coloured Fatty Acid-based Polyol
Chemical synthesis of a low viscosity and light coloured fatty acid-based
polyol was conducted via a threestep reaction. The reaction variables,
namely, temperature, pressure, amount of catalyst used, molar ratio
of reactants and reaction time were investigated for their effects
on the properties of the final polyol produced. Temperature and reduced
pressure were found to have a profound impact on the rate of the first
reaction step, which was an esterification reaction. In addition,
it was observed that the amount of catalyst had a great influence
on the colour of the product as well as the rate of the reaction.
In the second reaction step, which was an epoxidation reaction, the
molar ratio of reactants and reaction time play crucial roles in determining
the properties of the final product. At the same time, temperature
control was another important factor in this second step. The final
reaction step was alcoholysis, in which the amount of catalyst used
was one of the important factors that affected the properties of the
final product. Depending on the reaction parameters for this three-step
reaction, fatty acid-based polyols with various properties could be
prepared. However, polyols with low viscosity and light colour characteristics
are preferred because they have the properties that are suitable for
the production of 2K polyurethanes for the CASE industry.
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| Bio-
based Polyols of the Flexible Slabstock Foam Industry
During the last few years, interest in polyols derived from natural
oils has been constantly increasing for a variety of polyurethane applications.
Bio-based polyol chemistry brings new product supply options that are
produced from renewable resources, have supply stability and provide
the opportunity for differentiation in the foam market-place. These
are some of the key drivers for the polyurethane processors to look
at ways to utilize such products. Until now, the successful use of natural
oil-based polyols in flexible slabstock applications has been limited
due to issues with quality consistency, odour, impact on physical properties
and processing limitations. Most recently, Cargill Incorporated introduced
its BiOHTM polyol product line for the production of flexible foams
leveraging on the company’s integrated supply chain and deep knowledge
in processing oilseeds and vegetable oils on a global basis. Commercially
available BiOH polyols are produced predominantly from soya-based feedstock.
However, this article will show that Cargill can produce equally high
quality polyols using palm feedstock. BiOH polyols are performance products
produced with a chemistry that is completely detached from propylene
or ethylene oxide. BiOH polyols have also resolved the odour and quality
consistency issues previously encountered with other natural oil-based
polyols. This article will describe the large-scale evaluation results
of the first generation BiOH polyols in different foam grades and their
ability to deliver the following: ease of processing with commercially
available catalysts, surfactants and additives; improved flammability;
improved hydrolysis resistance; performance enhancement in different
foam grades such as viscoelastic; same level of microbial activity;
more efficient load-bearing building capabilities than SAN copolymer
polyols and smaller environmental footprint.
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| Variable
Density Plantings for Oil Palms (Elaeis guineensis) in Peninsular
Malaysia
The current planting density is a fixed option based on the duration
of the economic life cycle of the oil palm, which is about 25 years
in Malaysia. As space requirement increases as palm grows bigger with
age, the density giving greatest yield therefore decreases gradually
from high to a lower stable density at some point in the planting cycle.
This behaviour is premise for one of the key options investigated in
this project, the concept of variable density (VD). In this option,
palms are planted at high densities and thinned when the starting density
is no longer the optimum density for the given period. Because of the
morphology of the oil palm, planting patterns influence greatly the
yields obtained both before and after thinning. The project investigated
several of the key elements in the VD concept. They are the starting
and finishing densities, planting patterns, thinning periods, intensity
of thinning and manuring requirements (one of the high cost items affected
by density). A second option investigated is the concept of fixed high
density planting (HDP) on a shorter 18-20-year cycle. This allows a
quicker introduction of newer varieties which yield better or with special
traits (high iodine value, disease resistant, low height increment,
etc.) in successive replants with concomitant better profitability.
This option is also suitable for land under acquisition threat or development
potential. The strategies are evaluated over six experiments on both
coastal and inland soils. Results to date suggest both strategies are
viable and have potential. Results from the spacing experiments indicate
that HDP, on a shorter replanting cycle is more economical. However,
on conventional planting cycles of 25 years, current fixed planting
densities are still valid. The results from the VD options suggest that
initial starting densities at triangular spacing are better than other
planting pattern despite the resultant spacing after thinning being
asystematic. Starting densities at 180 – 200 palms ha-1 at triangular
spacing and thinned at around the 12th – 14th year of planting
by 14% – 25%, appears to be viable. Future research directions
and experimental limitations are also discussed.
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Palm
Oil Tocotrienols as Antioxidants and Chemopreventive Agents
Breast cancer leads all cancer incidence among American women, accounting
for 32% of the 2005 estimated new cases in the United States. It is
the second leading cause of cancer deaths, estimated at 40 000 yr-1.
Estrogens, natural or synthetic, used widely in a variety of clinical
conditions, from estrogen replacement therapy to cancer treatment, are
themselves carcinogenic, causing uterine and breast cancers. However,
the mechanism of their carcinogenic action is still not well understood.
We found that both 17ß-estradiol (E2) and estrone (E1) could be
activated by the versatile epoxide-forming oxidant dimethyldioxirane
(DMDO) to inhibit nuclear RNA synthesis and to bind DNA forming estrogen-DNA
adducts both in vitro and in vivo. Since DNA adducts can cause mutation,
and mutation is the molecular basis for the initiation of carcinogenesis,
our findings strongly suggest the possibility that both E2 and E1 are
the initiators for uterine and breast carcinogenesis. Based on this
new insight, a method to screen chemopreventive agents against breast
cancer, at the initiation, was developed. This screening test determines
whether a chemical is able to prevent the formation of E2 or E1 epoxide
as measured by both the loss of the ability of E2 or E1 to inhibit nuclear
DNA-dependent RNA synthesis and the ability of [3H] E2 or E1 to bind
DNA. This article summarizes the results of our recent studies on the
preventive effects of Red Palm Oil, tocopherols and tocotrienols on
the epoxidation of several carcinogens including E2, E1 and aflatoxin
B1 (AFB1). Our data suggest that tocotrienols are more potent chemopreventive
agents than tocopherols against the epoxide formation of E2 , E1 and
AFB1. As a dietary supplement, tocopherols and especially tocotrienols
may have the potential to prevent breast and liver cancers.
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| Planting
Material as Key Input for Sustainable Palm Oil
The trends generally agreed for the future of palm oil as an important
commodity are the combination of a demand for food that will double
over the next 20 years, the emergence of new uses as a renewable energy
source, and (until the recent price exuberance over biodiesel) the falling
price trend of palm oil in real terms on the world market. For more
than 30 years, the average crop yield of the land under exploitation
in the world does not exceed 3 t ha-1 yr-1. The boom in availability
of the commodity is thus, almost entirely due to the large increase
in cultivated surface area, resulting in competition with the other
food crops for arable land, and participating in the disappearance of
tropical rain forest and needless environmental degradation. In turn,
this fuels the regular disparaging media campaigns against the oil palm
industry. The principles and criteria for sustainable palm oil were
adopted by the general assembly of the Roundtable for Sustainable Palm
Oil in November 2005. They embody a commitment to long-term economic
and financial viability, the use of appropriate best management practices,
and an improvement of environmental and socially positive impacts whilst
reducing the negative ones. The planting of improved and adapted oil
palm planting material is a key input to achieve these commitments.
This article presents evidence of the effects of continuous improvement
of planting material on the profitability of the crop. Highlighted is
the widespread use of poor quality material, and the alternative value,
for example, of PT Socfindo planting materials enhanced by the cooperation
of Cirad – France and its network. The challenges to be faced
for the future by breeders and seed producers, as well as plantation
management are discussed.
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Effect
of New Palm Oil Mill Processes on the EFB and POME Utilization
New palm oil mill processes are characterized by advanced oil separation
technologies with zero dilution water (‘ECO-D’ for example
as a new system for oil recovery without dilution water) and continuous
sterilization of the fresh fruit bunch (FFB). These processes have a
deep impact on the amount and composition of waste water (POME). Compared
to conventional palm oil mills the total amount of palm oil mill effluent
(POME) can be reduced from 0.65 m3 t-1 FFB to 0.45 m3 t-1 (conventional
sterilization and zero dilution water) and 0.25 m3 t-1 (continuous sterilization
and zero dilution water). These changes influence the treatment processes
and its cost significantly. One process for the EFB and POME utilization
which can fulfil the demand of a sustainable palm oil production is
the co-composting of both of the materials. The composting process is
used also for biological drying of the POME. The final product of the
process is compost or mulch which unifies the nutrients of both in one
product. The POME can be used also for biogas production (in fixed bed
reactors for POME with low dry matter content and in totally mixed reactors
for ECO-D biomass) before composting. The investment cost and profitability
of the composting and fermentation process is calculated in detail based
on data from practise in Indonesia. The new developments of processes
in palm oil mills can reduce the cost for the waste and waste water
treatment up to 35%. The benefits from biogas production and composting
are the energy production, saved POME treatment cost in pond systems,
total utilization of the POME nutrients, reduced cost for the EFB transport
and utilization, higher empty fruit bunch (FFB) yields and from clean
development mechanism (CDM).
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Eco-friendly
Approaches to suintable Palm Oil Production
There have been many innovations in mill technologies, oil palm agronomy
and pest management over past decades that are increasingly meeting
the certification criteria of the Roundtable on Sustainable Palm Oil
(RSPO). In addition, because oil palm plantations may be functionally
analogous to forests, and remain undisturbed for several decades, they
can provide some essential ecosystem services to local/national stakeholders
in terms of direct use-values (products, economics) and indirect use-values
(carbon sequestration, biodegradation, hydrology); though the economic
value of indirect services, such as maintenance of water quality, have
not been recognized as national assets. On the other hand, option values
(gene pools) and existence values (biodiversity) for oil palm plantations
are low and loss of these values is contentious when natural systems
are converted. Negative perceptions of oil palm being ‘eco-friendly’
also reflect the extent to which forest and peatland conversion to oil
palm have resulted in off-site effects such as carbon mobilization,
damage to river systems from sedimentation and loss of biodiversity.
It is concluded that the industry could improve its image by adopting
mitigation measures, including better landscape design and documentation
of the areas under development, and by improving the visibility that
some sectors of the industry are making to address these environmental
issues.
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| Process
Development with Bifunctional Chiral Epoxides to Access Single Enantiomers
of Pharmaceutical
Intermediates Two selected case studies on process development
will be discussed: one is on the enantiocontrolled synthesis of (S)-3-hydroxytetradecanoic
acid (2), an intermediate of ONO-4007 (3) possessing anti-tumour activity,
which employs double homologation of (S)-epichlorohydrin (ECH) (1b)
with its termini being differentiated. The other is on the enantioselective
access to N-4-cyano-3-trifluoromethylphenyl-(S)-2,3-dihydroxy-2- methylpropanamide
(5a), an intermediate of (R)-bicultamide (5b) exhibiting potent anti-androgen
activity, which starts with enantioconvergent preparation of (R)-3-benzyloxy-2-methylpropane-1,2-diol
(4) from Obenzyl (±)-2-methylglycidol (1c) by the enantiocomplementary
hydrolysis using Bacillus subtilis epoxide hydrolase (BSEH) and H2SO4
in sequence. In each case study, emphasis will be placed on how to select
viable synthetic routes on the basis of availability of single enantiomers
of chiral starting materials and preparative methods thereof. In the
chemoenzymatic synthesis of (S)-5a, BSEH indispensable for building
its quaternary stereogenic centre is developed from scratch, which culminates
in successful overexpression of its gene from B. subtilis JCM 10629
under the influence of an amylase promoter and terminator of B. amyloliquefaciens
NBRC 15535 in an engineered strain of B. subtilis MT-2 deficient in
neutral protease. The discussion should help to develop process chemistry
in producing value-added fine chemicals from glycerol, one of its natural
sources being palm oil
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