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  1. Cavitation technology - a greener processing technique for the generation of pharmaceutical nanoemulsions
    Sivakumar M, Tang SY, Tan KW
    Ultrason Sonochem, 2014 Nov;21(6):2069-83.
    PMID: 24755340 DOI: 10.1016/j.ultsonch.2014.03.025
    Novel nanoemulsion-based drug delivery systems (DDS) have been proposed as alternative and effective approach for the delivery of various types of poorly water-soluble drugs in the last decade. This nanoformulation strategy significantly improves the cell uptake and bioavailability of numerous hydrophobic drugs by increasing their solubility and dissolution rate, maintaining drug concentration within the therapeutic range by controlling the drug release rate, and reducing systemic side effects by targeting to specific disease site, thus offering a better patient compliance. To date, cavitation technology has emerged to be an energy-efficient and promising technique to generate such nanoscale emulsions encapsulating a variety of highly potent pharmaceutical agents that are water-insoluble. The micro-turbulent implosions of cavitation bubbles tear-off primary giant oily emulsion droplets to nano-scale, spontaneously leading to the formation of highly uniform drug contained nanodroplets. A substantial body of recent literatures in the field of nanoemulsions suggests that cavitation is a facile, cost-reducing yet safer generation tool, remarkably highlighting its industrial commercial viability in the development of designing novel nanocarriers or enhancing the properties of existing pharmaceutical products. In this review, the fundamentals of nanoemulsion and the principles involved in their formation are presented. The underlying mechanisms in the generation of pharmaceutical nanoemulsion under acoustic field as well as the advantages of using cavitation compared to the conventional techniques are also highlighted. This review focuses on recent nanoemulsion-based DDS development and how cavitation through ultrasound and hydrodynamic means is useful to generate the pharmaceutical grade nanoemulsions including the complex double or submicron multiple emulsions.
  2. A computational and experimental study on acoustic pressure for ultrasonically formed oil-in-water emulsion
    Tiong TJ, Chu JK, Lim LY, Tan KW, Hong Yap Y, Asli UA
    Ultrason Sonochem, 2019 Sep;56:46-54.
    PMID: 31101285 DOI: 10.1016/j.ultsonch.2019.03.026
    In the field of ultrasonic emulsification, the formation and cavitation collapse is one major factor contributing to the formation of micro- and nano-sized emulsion droplets. In this work, a series of experiments were conducted to examine the effects of varying the ultrasonic horn's position to the sizes of emulsion droplets formed, in an attempt to compare the influence of the simulated acoustic pressure fields to the experimental results. Results showed that the intensity of the acoustic pressure played a vital role in the formation of smaller emulsion droplets. Larger areas with acoustic pressure above the cavitation threshold in the water phase have resulted in the formation of smaller emulsion droplets ca. 250 nm and with polydispersity index of 0.2-0.3. Placing the ultrasonic horn at the oil-water interface has hindered the formation of small emulsion droplets, due to the transfer of energy to overcome the interfacial surface tension of oil and water, resulting in a slight reduction in the maximum acoustic pressure, as well as the total area with acoustic pressures above the cavitation threshold. This work has demonstrated the influence of the position of the ultrasonic horn in the oil and water system on the final emulsion droplets formed and can conclude the importance of generating acoustic pressure above the cavitation threshold to achieve small and stable oil-in-water emulsion.
  3. Fulltext Ultrasonic cavitation: An effective cleaner and greener intensification technology in the extraction and surface modification of nanocellulose
    Hoo DY, Low ZL, Low DYS, Tang SY, Manickam S, Tan KW, et al.
    Ultrason Sonochem, 2022 Nov;90:106176.
    PMID: 36174272 DOI: 10.1016/j.ultsonch.2022.106176
    With rising consumer demand for natural products, a greener and cleaner technology, i.e., ultrasound-assisted extraction, has received immense attention given its effective and rapid isolation for nanocellulose compared to conventional methods. Nevertheless, the application of ultrasound on a commercial scale is limited due to the challenges associated with process optimization, high energy requirement, difficulty in equipment design and process scale-up, safety and regulatory issues. This review aims to narrow the research gap by placing the current research activities into perspectives and highlighting the diversified applications, significant roles, and potentials of ultrasound to ease future developments. In recent years, enhancements have been reported with ultrasound assistance, including a reduction in extraction duration, minimization of the reliance on harmful chemicals, and, most importantly, improved yield and properties of nanocellulose. An extensive review of the strengths and weaknesses of ultrasound-assisted treatments has also been considered. Essentially, the cavitation phenomena enhance the extraction efficiency through an increased mass transfer rate between the substrate and solvent due to the implosion of microbubbles. Optimization of process parameters such as ultrasonic intensity, duration, and frequency have indicated their significance for improved efficiency.
  4. Zinc (II) complex with a cationic Schiff base ligand: synthesis, characterization, and biological studies
    Lee SK, Tan KW, Ng SW, Ooi KK, Ang KP, Abdah MA
    Spectrochim Acta A Mol Biomol Spectrosc, 2014;121:101-8.
    PMID: 24231745 DOI: 10.1016/j.saa.2013.10.084
    A cationic Schiff base ligand, TSB (L) and its Zn (II) complex (1) were synthesized and characterized by using CHN, (1)H-NMR, FT-IR, UV, LC-MS, and X-ray methods. Their ability to inhibit topoisomerase I, DNA cleavage activities, and cytotoxicity were studied. X-ray diffraction study shows that the mononuclear complex 1 is four coordinated with distorted tetrahedral geometry. The singly deprotonated Schiff base ligand L acts as a bidentate ON-donor ligand. Complexation of L increases the inhibitory strength on topoisomerase I activity. Complex 1 could fully inhibit topoisomerase I activity at 250 μM, while L did not show any inhibitory effect on topoisomerase I activity. In addition, L and complex 1 could cleave pBR322 DNA in a concentration and time dependent profile. Surprisingly, L has better DNA cleavage activity than complex 1. The cleavage of DNA by complex 1 is altered in the presence of hydrogen peroxide. Furthermore, L and complex 1 are mildly cytotoxic towards human ovarian cancer A2780 and hepatocellular carcinoma HepG2.
  5. Synthesis of a DNA-targeting nickel (II) complex with testosterone thiosemicarbazone which exhibits selective cytotoxicity towards human prostate cancer cells (LNCaP)
    Heng MP, Sinniah SK, Teoh WY, Sim KS, Ng SW, Cheah YK, et al.
    Spectrochim Acta A Mol Biomol Spectrosc, 2015 Nov 5;150:360-72.
    PMID: 26057090 DOI: 10.1016/j.saa.2015.05.095
    Testosterone thiosemicarbazone, L and its nickel (II) complex 1 were synthesized and characterized by using FTIR, CHN, (1)H NMR, and X-ray crystallography. X-ray diffraction study confirmed the formation of L from condensation of testosterone and thiosemicarbazide. Mononuclear complex 1 is coordinated to two Schiff base ligands via two imine nitrogens and two tautomeric thiol sulfurs. The cytotoxicity of both compounds was investigated via MTT assay with cisplatin as positive reference standard. L is more potent towards androgen-dependent LNCaP (prostate) and HCT 116 (colon). On the other hand, complex 1, which is in a distorted square planar environment with L acting as a bidentate NS-donor ligand, is capable of inhibiting the growth of all the cancer cell lines tested, including PC-3 (prostate). It is noteworthy that both compounds are less toxic towards human colon cell CCD-18Co. The intrinsic DNA binding constant (Kb) of both compounds were evaluated via UV-Vis spectrophotometry. Both compounds showed Kb values which are comparable to the reported Kb value of typical classical intercalator such as ethidium bromide. The binding constant of the complex is almost double compared with ligand L. Both compounds were unable to inhibit the action topoisomerase I, which is the common target in cancer treatment (especially colon cancer). This suggest a topoisomerase I independent-cell death mechanism.
  6. A rhodamine based chemosensor for solvent dependent chromogenic sensing of cobalt (II) and copper (II) ions with good selectivity and sensitivity: Synthesis, filter paper test strip, DFT calculations and cytotoxicity
    Chan WC, Saad HM, Sim KS, Lee VS, Ang CW, Yeong KY, et al.
    Spectrochim Acta A Mol Biomol Spectrosc, 2021 Jun 23;262:120099.
    PMID: 34198119 DOI: 10.1016/j.saa.2021.120099
    A new chemosensor 1 was synthesized by reacting rhodamine B hydrazide and 2,3,4-trihydroxybenzaldehyde, which was then characterized by spectroscopic techniques and single crystal X-ray crystallography. Sensor 1 has the ability to sense Co2+/Cu2+ ions by "naked-eye" with an apparent colour change from colourless to pink in different solvent system, MeCN and DMF respectively. Furthermore, it can selectively detect Co2+/Cu2+ among wide range of different metal ions, and it exhibits low detection limit of 4.425 × 10-8 M and 1.398 × 10-7 M respectively. Binding mode of the two complexes were determined to be 1:1 stoichiometry for Co2+ complex and 1:2 stoichiometry for Cu2+ complex through Job's plot, IR spectroscopy, mass spectrometry and 1H NMR spectroscopy. Moreover, reversibility of the sensor 1 as copper (II) ion detector was determined by using EDTA and the results showed that sensor 1 can be reused for at least 6 cycles. Other than that, a low cost chemosensor test strips were fabricated for the convenient "naked-eye" detection of Co2+ and Cu2+ in pure aqueous media. The MTT assay was conducted in order to determine the cytotoxicity of sensor 1 towards human cell lines.
  7. Fulltext An outbreak of methicillin-resistant Staphylococcus aureus in a neonatal intensive care unit in Singapore: a 20-month study of clinical characteristics and control
    Tan KW, Tay L, Lim SH
    Singapore Med J, 1994 Jun;35(3):277-82.
    PMID: 7997904
    Methicillin resistant Staphylococcus aureus (MRSA) is a major infection control problem in many countries. There have been many reports of outbreaks in neonatal nurseries including, in our part of the world, Australia, Hong Kong and Malaysia. A recent outbreak of MRSA in the neonatal intensive care unit in the Kandang Kerbau Hospital, Singapore, presented us with the opportunity to study the clinical characteristics of the outbreak and the effects of infection control measures. Neonates admitted to the neonatal intensive care unit were studied over a 20-month period. They were all screened for nasal colonisation on admission and weekly thereafter. Infections were documented. Over this period there were altogether 2,576 admissions of which 85 infants had nasal colonisation with MRSA (3.3%) and 28 developed infections (1%). Although the majority of infants colonised by MRSA suffered no ill effects, 3 had septicaemia and 2 had septicaemia with osteomyelitis. There were no deaths. Standard infection control measures with barrier nursing and the use of mupirocin nasal ointment were ineffective, and control was achieved only after strict cohorting together with the use of mupirocin was instituted. This was done without additional costs to the department and without additional nurses or doctors.
  8. Fulltext Incidence of breast cancer attributable to breast density, modifiable and non-modifiable breast cancer risk factors in Singapore
    Ho PJ, Lau HSH, Ho WK, Wong FY, Yang Q, Tan KW, et al.
    Sci Rep, 2020 01 16;10(1):503.
    PMID: 31949192 DOI: 10.1038/s41598-019-57341-7
    Incidence of breast cancer is rising rapidly in Asia. Some breast cancer risk factors are modifiable. We examined the impact of known breast cancer risk factors, including body mass index (BMI), reproductive and hormonal risk factors, and breast density on the incidence of breast cancer, in Singapore. The study population was a population-based prospective trial of screening mammography - Singapore Breast Cancer Screening Project. Population attributable risk and absolute risks of breast cancer due to various risk factors were calculated. Among 28,130 women, 474 women (1.7%) developed breast cancer. The population attributable risk was highest for ethnicity (49.4%) and lowest for family history of breast cancer (3.8%). The proportion of breast cancers that is attributable to modifiable risk factor BMI was 16.2%. The proportion of breast cancers that is attributable to reproductive risk factors were low; 9.2% for age at menarche and 4.2% for number of live births. Up to 45.9% of all breast cancers could be avoided if all women had breast density <12% and BMI <25 kg/m2. Notably, sixty percent of women with the lowest risk based on non-modifiable risk factors will never reach the risk level recommended for mammography screening. A combination of easily assessable breast cancer risk factors can help to identify women at high risk of developing breast cancer for targeted screening. A large number of high-risk women could benefit from risk-reduction and risk stratification strategies.
  9. Fulltext Molecular Dynamics Simulation of Nanocellulose-Stabilized Pickering Emulsions
    Lee KK, Low DYS, Foo ML, Yu LJ, Choong TSY, Tang SY, et al.
    Polymers (Basel), 2021 Feb 23;13(4).
    PMID: 33672331 DOI: 10.3390/polym13040668
    While the economy is rapidly expanding in most emerging countries, issues coupled with a higher population has created foreseeable tension among food, water, and energy. It is crucial for more sustainable valorization of resources, for instance, nanocellulose, to address the core challenges in environmental sustainability. As the complexity of the system evolved, the timescale of project development has increased exponentially. However, research on the design and operation of integrated nanomaterials, along with energy supply, monitoring, and control infrastructure, has seriously lagged. The development cost of new materials can be significantly reduced by utilizing molecular simulation technology in the design of nanostructured materials. To realize its potential, nanocellulose, an amphiphilic biopolymer with the presence of rich -OH and -CH structural groups, was investigated via molecular dynamics simulation to reveal its full potential as Pickering emulsion stabilizer at the molecular level. This work has successfully quantified the Pickering stabilization mechanism profiles by nanocellulose, and the phenomenon could be visualized in three stages, namely the initial homogenous phase, rapid formation of micelles and coalescence, and lastly the thermodynamic equilibrium of the system. It was also observed that the high bead order was always coupled with a high volume of phase separation activities, through a coarse-grained model within 20,000 time steps. The outcome of this work would be helpful to provide an important perspective for the future design and development of nanocellulose-based emulsion products, which cater for food, cosmeceutical, and pharmaceutical industries.
  10. Fulltext Recent Developments in Nanocellulose-Reinforced Rubber Matrix Composites: A Review
    Low DYS, Supramaniam J, Soottitantawat A, Charinpanitkul T, Tanthapanichakoon W, Tan KW, et al.
    Polymers (Basel), 2021 Feb 12;13(4).
    PMID: 33673391 DOI: 10.3390/polym13040550
    Research and development of nanocellulose and nanocellulose-reinforced composite materials have garnered substantial interest in recent years. This is greatly attributed to its unique functionalities and properties, such as being renewable, sustainable, possessing high mechanical strengths, having low weight and cost. This review aims to highlight recent developments in incorporating nanocellulose into rubber matrices as a reinforcing filler material. It encompasses an introduction to natural and synthetic rubbers as a commodity at large and conventional fillers used today in rubber processing, such as carbon black and silica. Subsequently, different types of nanocellulose would be addressed, including its common sources, dimensions, and mechanical properties, followed by recent isolation techniques of nanocellulose from its resource and application in rubber reinforcement. The review also gathers recent studies and qualitative findings on the incorporation of a myriad of nanocellulose variants into various types of rubber matrices with the main goal of enhancing its mechanical integrity and potentially phasing out conventional rubber fillers. The mechanism of reinforcement and mechanical behaviors of these nanocomposites are highlighted. This article concludes with potential industrial applications of nanocellulose-reinforced rubber composites and the way forward with this technology.
  11. Fulltext Daily Consumption of a Fruit and Vegetable Smoothie Alters Facial Skin Color
    Tan KW, Graf BA, Mitra SR, Stephen ID
    PLoS One, 2015;10(7):e0133445.
    PMID: 26186449 DOI: 10.1371/journal.pone.0133445
    Consumption of dietary carotenoids or carotenoid supplements can alter the color (yellowness) of human skin through increased carotenoid deposition in the skin. As fruit and vegetables are the main dietary sources of carotenoids, skin yellowness may be a function of regular fruit and vegetable consumption. However, most previous studies have used tablets or capsules to supplement carotenoid intake, and less is known of the impact of increased fruit and vegetable consumption on skin color. Here, we examined skin color changes in an Asian population (Malaysian Chinese ethnicity) over a six week dietary intervention with a carotenoid-rich fruit smoothie. Eighty one university students (34 males, 47 females; mean age 20.48) were assigned randomly to consuming either a fruit smoothie (intervention group) or mineral water (control group) daily for six weeks. Participants' skin yellowness (CIELab b*), redness (a*) and luminance (L*) were measured at baseline, twice during the intervention period and at a two-week follow-up, using a handheld reflectance spectrophotometer. Results showed a large increment in skin yellowness (p<0.001) and slight increment in skin redness (p<0.001) after 4 weeks of intervention for participants in the intervention group. Skin yellowness and skin redness remained elevated at the two week follow up measurement. In conclusion, intervention with a carotenoid-rich fruit smoothie is associated with increased skin redness and yellowness in an Asian population. Changes in the reflectance spectrum of the skin suggest that this color change was caused by carotenoid deposition in the skin.
  12. Colour detection thresholds in faces and colour patches
    Tan KW, Stephen ID
    Perception, 2013;42(7):733-41.
    PMID: 24344549
    Human facial skin colour reflects individuals' underlying health (Stephen et al 2011 Evolution & Human Behavior 32 216-227); and enhanced facial skin CIELab b* (yellowness), a* (redness), and L* (lightness) are perceived as healthy (also Stephen et al 2009a International Journal of Primatology 30 845-857). Here, we examine Malaysian Chinese participants' detection thresholds for CIELab L* (lightness), a* (redness), and b* (yellowness) colour changes in Asian, African, and Caucasian faces and skin coloured patches. Twelve face photos and three skin coloured patches were transformed to produce four pairs of images of each individual face and colour patch with different amounts of red, yellow, or lightness, from very subtle (deltaE = 1.2) to quite large differences (deltaE = 9.6). Participants were asked to decide which of sequentially displayed, paired same-face images or colour patches were lighter, redder, or yellower. Changes in facial redness, followed by changes in yellowness, were more easily discriminated than changes in luminance. However, visual sensitivity was not greater for redness and yellowness in nonface stimuli, suggesting red facial skin colour special salience. Participants were also significantly better at recognizing colour differences in own-race (Asian) and Caucasian faces than in African faces, suggesting the existence of cross-race effect in discriminating facial colours. Humans' colour vision may have been selected for skin colour signalling (Changizi et al 2006 Biology Letters 2 217-221), enabling individuals to perceive subtle changes in skin colour, reflecting health and emotional status.
  13. International comparison of care for very low birth weight infants: parents' perceptions of counseling and decision-making
    Partridge JC, Martinez AM, Nishida H, Boo NY, Tan KW, Yeung CY, et al.
    Pediatrics, 2005 Aug;116(2):e263-71.
    PMID: 16061579
    To characterize parent perceptions and satisfaction with physician counseling and delivery-room resuscitation of very low birth weight infants in countries with neonatal intensive care capacity.
  14. Fulltext Estimating direct and spill-over impacts of political elections on COVID-19 transmission using synthetic control methods
    Lim JT, Maung K, Tan ST, Ong SE, Lim JM, Koo JR, et al.
    PLoS Comput Biol, 2021 May;17(5):e1008959.
    PMID: 34043622 DOI: 10.1371/journal.pcbi.1008959
    Mass gathering events have been identified as high-risk environments for community transmission of coronavirus disease 2019 (COVID-19). Empirical estimates of their direct and spill-over effects however remain challenging to identify. In this study, we propose the use of a novel synthetic control framework to obtain causal estimates for direct and spill-over impacts of these events. The Sabah state elections in Malaysia were used as an example for our proposed methodology and we investigate the event's spatial and temporal impacts on COVID-19 transmission. Results indicate an estimated (i) 70.0% of COVID-19 case counts within Sabah post-state election were attributable to the election's direct effect; (ii) 64.4% of COVID-19 cases in the rest of Malaysia post-state election were attributable to the election's spill-over effects. Sensitivity analysis was further conducted by examining epidemiological pre-trends, surveillance efforts, varying synthetic control matching characteristics and spill-over specifications. We demonstrate that our estimates are not due to pre-existing epidemiological trends, surveillance efforts, and/or preventive policies. These estimates highlight the potential of mass gatherings in one region to spill-over into an outbreak of national scale. Relaxations of mass gathering restrictions must therefore be carefully considered, even in the context of low community transmission and enforcement of safe distancing guidelines.
  15. To which world regions does the valence-dominance model of social perception apply?
    Jones BC, DeBruine LM, Flake JK, Liuzza MT, Antfolk J, Arinze NC, et al.
    Nat Hum Behav, 2021 01;5(1):159-169.
    PMID: 33398150 DOI: 10.1038/s41562-020-01007-2
    Over the past 10 years, Oosterhof and Todorov's valence-dominance model has emerged as the most prominent account of how people evaluate faces on social dimensions. In this model, two dimensions (valence and dominance) underpin social judgements of faces. Because this model has primarily been developed and tested in Western regions, it is unclear whether these findings apply to other regions. We addressed this question by replicating Oosterhof and Todorov's methodology across 11 world regions, 41 countries and 11,570 participants. When we used Oosterhof and Todorov's original analysis strategy, the valence-dominance model generalized across regions. When we used an alternative methodology to allow for correlated dimensions, we observed much less generalization. Collectively, these results suggest that, while the valence-dominance model generalizes very well across regions when dimensions are forced to be orthogonal, regional differences are revealed when we use different extraction methods and correlate and rotate the dimension reduction solution. PROTOCOL REGISTRATION: The stage 1 protocol for this Registered Report was accepted in principle on 5 November 2018. The protocol, as accepted by the journal, can be found at https://doi.org/10.6084/m9.figshare.7611443.v1 .
  16. Fulltext Dinuclear and mononuclear metal(II) polypyridyl complexes against drug-sensitive and drug-resistant Plasmodium falciparum and their mode of action
    Lai JW, Maah MJ, Tan KW, Sarip R, Lim YAL, Ganguly R, et al.
    Malar J, 2022 Dec 17;21(1):386.
    PMID: 36528584 DOI: 10.1186/s12936-022-04406-0
    BACKGROUND: Malaria remains one of the most virulent and deadliest parasitic disease in the world, particularly in Africa and Southeast Asia. Widespread occurrence of artemisinin-resistant Plasmodium falciparum strains from the Greater Mekong Subregion is alarming. This hinders the national economies, as well as being a major drawback in the effective control and elimination of malaria worldwide. Clearly, an effective anti-malarial drug is urgently needed.

    METHODS: The dinuclear and mononuclear copper(II) and zinc(II) complexes were synthesized in ethanolic solution and characterized by various physical measurements (FTIR, CHN elemental analysis, solubility, ESI-MS, UV-Visible, conductivity and magnetic moment, and NMR). X-ray crystal structure of the dicopper(II) complex was determined. The in vitro haemolytic activities of these metal complexes were evaluated spectroscopically on B+ blood while the anti-malarial potency was performed in vitro on blood stage drug-sensitive Plasmodium falciparum 3D7 (Pf3D7) and artemisinin-resistant Plasmodium falciparum IPC5202 (Pf5202) with fluorescence dye. Mode of action of metal complexes were conducted to determine the formation of reactive oxygen species using PNDA and DCFH-DA dyes, JC-1 depolarization of mitochondrial membrane potential, malarial 20S proteasome inhibition with parasite lysate, and morphological studies using Giemsa and Hoechst stains.

    RESULTS: Copper(II) complexes showed anti-malarial potency against both Pf3D7 and Pf5202 in sub-micromolar to micromolar range. The zinc(II) complexes were effective against Pf3D7 with excellent therapeutic index but encountered total resistance against Pf5202. Among the four, the dinuclear copper(II) complex was the most potent against both strains. The zinc(II) complexes caused no haemolysis of RBC while copper(II) complexes induced increased haemolysis with increasing concentration. Further mechanistic studies of both copper(II) complexes on both Pf3D7 and Pf5202 strains showed induction of ROS, 20S malarial proteasome inhibition, loss of mitochondrial membrane potential and morphological features indicative of apoptosis.

    CONCLUSION: The dinuclear [Cu(phen)-4,4'-bipy-Cu(phen)](NO3)4 is highly potent and can overcome the total drug-resistance of Pf5202 towards chloroquine and artemisinin. The other three copper(II) and zinc(II) complexes were only effective towards the drug-sensitive Pf3D7, with the latter causing no haemolysis of RBC. Their mode of action involves multiple targets.

  17. Nickel and zinc complexes of testosterone N4-substituted thiosemicarbazone: Selective cytotoxicity towards human colorectal carcinoma cell line HCT 116 and their cell death mechanisms
    Heng MP, Sim KS, Tan KW
    J Inorg Biochem, 2020 07;208:111097.
    PMID: 32438269 DOI: 10.1016/j.jinorgbio.2020.111097
    Two new Schiff base ligands (TE and TF) were prepared from conjugation of testosterone with 4-(4-ethylphenyl)-3-thiosemicarbazide and 4-(4-fluorophenyl)-3-thiosemicarbazide, respectively. Their nickel (NE and NF) and zinc (ZE and ZF) complexes were reported. X-ray crystallography revealed a distorted square planar geometry was adopted by NE. The compounds demonstrated excellent selectivity towards the colorectal carcinoma cell line HCT 116 despite their weak preferences towards the prostate cancer cell lines (PC-3 and LNCaP). Against HCT 116, all these compounds were able to arrest cell cycle at G0/G1 phase and induce apoptosis via mitochondria-dependent (TE, NE, and TF) and extrinsic apoptotic pathway (ZE, NF, and ZF). Moreover, only ZE was able to act as topoisomease I poison and halt its enzymatic reactions although all compounds presented excellent affinity towards DNA.
  18. Factors affecting nucleolytic efficiency of some ternary metal complexes with DNA binding and recognition domains. Crystal and molecular structure of Zn(phen)(edda)
    Seng HL, Ong HK, Rahman RN, Yamin BM, Tiekink ER, Tan KW, et al.
    J Inorg Biochem, 2008 Nov;102(11):1997-2011.
    PMID: 18778856 DOI: 10.1016/j.jinorgbio.2008.07.015
    The binding selectivity of the M(phen)(edda) (M=Cu, Co, Ni, Zn; phen=1,10-phenanthroline, edda=ethylenediaminediacetic acid) complexes towards ds(CG)(6), ds(AT)(6) and ds(CGCGAATTCGCG) B-form oligonucleotide duplexes were studied by CD spectroscopy and molecular modeling. The binding mode is intercalation and there is selectivity towards AT-sequence and stacking preference for A/A parallel or diagonal adjacent base steps in their intercalation. The nucleolytic properties of these complexes were investigated and the factors affecting the extent of cleavage were determined to be: concentration of complex, the nature of metal(II) ion, type of buffer, pH of buffer, incubation time, incubation temperature, and the presence of hydrogen peroxide or ascorbic acid as exogenous reagents. The fluorescence property of these complexes and its origin were also investigated. The crystal structure of the Zn(phen)(edda) complex is reported in which the zinc atom displays a distorted trans-N(4)O(2) octahedral geometry; the crystal packing features double layers of complex molecules held together by extensive hydrogen bonding that inter-digitate with adjacent double layers via pi...pi interactions between 1,10-phenanthroline residues. The structure is compared with that of the recently described copper(II) analogue and, with the latter, included in molecular modeling.
  19. Topoisomerase I inhibition and DNA cleavage by zinc, copper, and nickel derivatives of 2-[2-bromoethyliminomethyl]-4-[ethoxymethyl]phenol complexes exhibiting anti-proliferation and anti-metastasis activity
    Lee SK, Tan KW, Ng SW
    J Inorg Biochem, 2016 06;159:14-21.
    PMID: 26901628 DOI: 10.1016/j.jinorgbio.2016.02.010
    Three transition metal derivatives (Zn, Cu, and Ni) of 2-[2-bromoethyliminomethyl]-4-[ethoxymethyl]phenol (L) were synthesized by the reaction of the metal salts with the Schiff base ligand in one pot. In the crystal structure of [Zn(L)Br], the Schiff base ligand binds to the metal center through its phenolate oxygen and imine nitrogen, and adopts a distorted tetrahedral geometry. These compounds were found to inhibit topoisomerase I (topo I) activity, induce DNA cleavage and show DNA binding activity. Moreover, these compounds were found to be cytotoxic towards several cancer cell lines (A2780, MCF-7, HT29, HepG2, A549, PC3, LNCaP) and prevent metastasis of PC3. Collectively, Cu(II) complex 2 shows superior activity relative to its Zn(II) and Ni(II) analogs.
  20. Evaluation of carbon-based nanosorbents synthesised by ethylene decomposition on stainless steel substrates as potential sequestrating materials for nickel ions in aqueous solution
    Lee XJ, Lee LY, Foo LP, Tan KW, Hassell DG
    J Environ Sci (China), 2012;24(9):1559-68.
    PMID: 23520862
    The present work covers the preparation of carbon-based nanosorbents by ethylene decomposition on stainless steel mesh without the use of external catalyst for the treatment of water containing nickel ions (Ni2+). The reaction temperature was varied from 650 to 850 degrees C, while reaction time and ethylene to nitrogen flow ratio were maintained at 30 min and 1:1 cm3/min, respectively. Results show that nanosorbents synthesised at a reaction temperature of 650 degrees C had the smallest average diameter (75 nm), largest BET surface area (68.95 m2/g) and least amount of impurity (0.98 wt.% Fe). A series of batch-sorption tests were performed to evaluate the effects of initial pH, initial metal concentration and contact time on Ni2+ removal by the nanosorbents. The equilibrium data fitted well to Freundlich isotherm. The kinetic data were best correlated to a pseudo second-order model indicating that the process was of chemisorption type. Further analysis by the Boyd kinetic model revealed that boundary layer diffusion was the controlling step. This primary study suggests that the prepared material with Freundlich constants compared well with those in the literature, is a promising sorbent for the sequestration of Ni2+ in aqueous solutions.
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