The Biochemical Roles Of Transition Metals: Chm579: Advanced Inorganic Chemistry

THE BIOCHEMICAL ROLES OF TRANSITION METALS CHM579 : ADVANCED INORGANIC CHEMISTRY GROUP’S MEMBER

NUR AMIRAH BT AHMAD (M1) - 2018801966 NUR IZZAH LIYANA BT SAARI (M2) - 2018200164 NURUL ATIQAH BT AZIZAN (M1) – 2018226722 NURUL HUSNA BINTI IBRAHIM (M1) - 2018226626

PROGRAMME CODE

AS2224

COURSE CODE

CHM579

FACULTY

FACULTY OF APPLIED SCIENCE

LECTURER’S NAME

PM DR. KARIMAH BINTI KASSIM

DATE OF

12th JUNE 2020 (FRIDAY)

SUBMISSION

TABLE OF CONTENT PAGE

TITLE ACKNOWLEDGEMENT INTRODUCTION

N O 1. .2

2.1 Background of the issue 2.2 Objective of the report 2.3 Report problems 2.4 The scope of the report and sources 2.5 Personal Opinion of the particular issue LITERATURE REVIEW

.3

3.1 Literature on topic 3.2 Literature on Method of synthesis metal complexes 3.3 Theoretical approach (Understand the multivalency to the ability of transition metals to participate in formation of complex) CONCLUSION

.4

4.1 Contributions 4.2 Important REFERENCE

ACKNOWLEDGEMENT

.5

First of all, we would like to thank Allah SWT and HIS messenger, Prophet Muhammad SAW. It is because of HIS blessing; it is possible for us to finish this assignment. We had finally managed to finish up this group assignment with great enthusiasm and determination. All the time spent to search and discuss ideas as well as justifying theoretical clues to drive the output were worth our effort and time, Insya-Allah. This assignment had been done with all afford by our group members which are consist of Nur Amirah bt Ahmad, Nur Izzah Liyana bt Saari, Nurul Atiqah bt Azizan and Nurul Husna bt Ibrahim. We always work hard to produce a good assignment with our full commitment and responsibility. First and foremost, a big thank to our Advanced Inorganic Chemistry (CHM 579) lecturer’s, PM Dr. Karimah bt Kassim because without her guide, our assignment cannot be done properly like this. She always gives us supports and guide to us how to do assignments in purpose to produce a good outcome from theory that has been learned at class. Then, we would like to thanks to all our friends who had helped and shared ideas with us. They also gave us supports and advises. Lastly, we also want to thanks to our parents who always prayed well for us and giving their time to hear our problem. We hope our assignment is complete and will be receive. We had used our effort and acknowledgement to search information and ideas. Hoped our effort was worth it.

THE OBJECTIVE OF THE REPORT

The biological activity of these compounds was often believed to be caused by their ability to chelate ions of metal, present in the bio-system. In certain cases, the presence of metal ions exerts synergistic effects on the free ligand activity. Therefore, Schiff bases exhibit applicable biological activities. For examples anti-inflammatory, anaesthetic, antimicrobial, anticancer, antioxidant and antianxiety activities. In this report, firstly we propose general approaches to the Schiff base synthesis, a detailed review of Schiff bases’ numerous propriety biological applications and their metal complexes. its method and also the properties of it. Then, we also highlight the main significant examples of compounds belonging to this class which is antibacterial and also known as antimicrobial. And also the reaction of the Schiff base and its various of metals such as Copper(II), Cuprum(II) and Zinc(II), its theoretical approach and its contribution and uses were also present.

PERSONAL OPINION OF THE PARTICULAR ISSUE

Based on our opinion, Schiff bases are a common class compounds of interesting biological substances. Schiff bases are also versatile ligands of metal complexing and coordination of nearly all d-block metals as well as lanthanides was used. In therapeutics, Schiff bases and their metal complexes shows a broad variety of biological activities such as antifungal, antibacterial, anti-inflammatory, antimalarial and anticancer including DNA damage. We know that bacterial and fungal infectious diseases have risen significantly in recent years. Despite the considerable advances in antimicrobial therapy, the pervasive usage and abuse of antibiotics has contributed to the rise of antibiotic bacterial resistance, which is a significant public health danger. The development of new compounds to tackle resistant bacteria has therefore become one of the most important areas of antibacterial research today. Based on our findings through journal, Schiff bases nitro- and halo derivatives are documented to have antimicrobial and antitumor activity. Even antimicrobial and antifungal activities have been recorded from different Schiff bases. Some Schiff base and Beta- Lactam derivatives act as strong antimicrobial agents. Other than that, Sulphur and nitrogen Schiff bases ligand & metal complexes are such an effective antibacterial agent. Thus, the crown ethers of Schiff bases are often investigated to have an excellent ability to function as an antimicrobial agent. Besides, there some Schiff bases Copper(II) complexes with phenanthroline bipyridyl shows stronger antifungal action to combat human and plant fungal disease. In addition, Thiazole containing the bases of Schiff and their transition metal complexes also has been shown to be a vast range of biological activities.

LITERATURE ON METHOD OF SYNTHESIS METAL COMPLEXES Schiff bases Copper(II) complex:

Material and methods a) Conventional method 3 mmol of salicylaldehyde dissolved in 25cm 3 of ethanol is mixed with 3 mmol of hexamine dissolved in 25cm3 of ethanol. To this is added a few drops of acetic acid and mixture is refluxed for 1 to 1 and half hours. It is then cooled, filtered off, washed with water and vacuum-dried. The resulting crude product is recrystallised from ethanol.

b) Grinding method 3 mmol of salicylaldehyde was dissolved in 10 ml of ethanol (25cm 3) is mixed with 3 mmol of hexamine dissolved in 10 ml of ethanol (25cm3). To this is added a few drops of citric acid and grinding the mixture for 20 minutes. To attain the powdered form, pestle and mortar are used for grinding. And then cooled water is added. The precipitate was obtained.

c) Stirring method 3 mmol of hexamine in 10 ml of water is mixed with 3 mmol salicylaldehyde and then stirred for 10 minutes. The precipitate was obtained.

The above yields said three methods were compared and it was found that the traditional method is better method with greater yield. Since the yields of the two other methods are merger, they have not been used for further research.

Synthesis of metal complex

Add 1 gm of CuCl(H2O)6 complex to 10 ml ethanolic solution. In 10 ml ethanol, take 2 gm of Schiff base ligand. Heat the solution up. Add Schiff base ligand solution in CuCl(H2O)6 solution. There were several drops of ammonium solution added up to pH 6 to 8. And then the reaction mixture is stirred up to 1 hour at room temperature. The substance washed obtained was purified and washed with ethanol. Well dried and the base metal complex was formed by the Schiff. Greenish yellow complex has been obtained with a yield of 66.26%.

Schiff bases Cobalt(II) complex: Material and methods Both solvents and chemicals were commercially reagent-grade and used as Aldrich and Merck had provided. Elemental analysis was performed using an elemental analyser from Perkin-Elmer 2400II CHNS-O. Infrared spectra (KBr pellets) were registered on an instrument called the FT-IR JASCO 680. 1H NMR spectra was obtained on the 400spectrometer Bruker AVANCE III. The chemical changes of protons are recorded in ppm according to an internal Me4Si norm. they obtained electronic spectra on a spectrophotometer JASCO V-570. A Digital-Conductometer CG 855 instrument was used to measure the molar conductivity of the Co(II) complex freshly prepared 1.4 ~ 10-4M DMSO solution.

Synthesis of Schiff bases As stated in the literature H2L1 and HL were prepared. Elemental analysis and spectroscopic techniques characterized certain ligands. The melting points of the ligands are 248-250°C for H2L1 and 148-150°C for HL.

Synthesis of metal complex A solution of L (51.2 mg, 0.2 mmol) was added at room temperature in 15 ml CHCL 3 to a stirring solution of Co(CH3COO)2.4H2O (24.9 MG, 0.1 mmol) in 10 ml ethanol. 3.0 mmol of benzylamine was added to this solution drop-wise withing 3 hours. The final reaction mixture was drained out, leaving the filtrate untouched for three days at room temperature. The resulting yellowish-brown crystals of 1 suitable for X-ray crystallography were filtered off and washed and dried under vacuum with cold ethanol.

Schiff bases Cobalt(II) and Copper (II) complex: Material and methods Under the published protocols, analytical grade reagents were used to synthesize 7,8dihydroxy-4-methylcoumarin and 6-formyl-7,8-dihydroxy-4-methylcoumarin.

Synthesis of Schiff bases Schiff bases synthesis was performed by refluxing a reaction mixture of hot ethanol solution (30 ml) of o-toluidine/3-aminobenzotrifluoride (0.01 mol) and hot ethanol solution (30ml) of 6-formyl-7,8-dihydroxy-4-methylcoumarin (0.02 mol) for 6 hours with addition of 1-2 drops of glacial acetic acid. During reflux, the precipitate formed was filtered, washed with cold ethanol and recrystallized using acetic acid.

Synthesis of metal complex With 1 mmol of CoCl2.6H2O/CuCl2.2H2O an alcoholic solution of 2 mmol Schiff bases was refluxed into the water bath for 1 hour. Then, 1 mmol of sodium acetate trihydrate was added to the reaction mixture, and the reflux continued for 3 hours. The separated complex was drained, vigorously washed with water, ethanol and ether, and eventually dried

in vacuum over fused CaCl2. All the prepared complexes have a melting point of above 300°C.

Schiff bases Copper(II) and Zinc(II) complex: Material and methods Sigma-Aldrich (Munich, Germany) and Merck Co. (Darmstadt, Germany) purchased all the required chemicals and solvents and was used without further purification. FisherJohns blocks (Fisher Scientific, Germany) have determined the melting points and are uncorrected. In DMSO-d6, the NMR spectra were registered on a Bruker Avance 300 unit. Chemical changes are calculated on the scale of δ (ppm) using TMS (tetramethyl silane) as the internal standard. Infrared (IR) spectra, measured on a theoretical Pty FITR7600 Lambda. Ltd. to use KBr disk 4000-400cm-1. Mass spectra obtained on the spectrometer BRUKER ESQUIRE HCT. The study of TGA (Thermo gravimetric analysis) conducted on Universal V4.5A TA instrument.

Synthesis of Schiff bases 0.01 mol of the compound and 0.01 mol aldehyde derivatives in round bottom flask containing 10cm3 methanol, respectively. It refluxed the reaction mixture for 30 minutes. Reaction completion has been tested with TLC. Once the reaction mixture was drained, a solid liquid precipitated out, which was washed, dried and purified using ethanol recrystallization.

Synthesis of metal complex A solution of ZnCl2/CuCl2 in methanol was gradually added to Schiff base ligands stirred ethanolic solution in the molar ratio 1:2. At 78 °C, the reaction mixture was stirred

further for 2 hours. It was cooled down in the ice bath to ensure complete precipitation of the complexes formed. The precipitate solid complex was washed with water and filtered. Finally, the complex was washed with diethyl ether and dried over anhydrous CaCl 2 in vacuum desiccators.

Schiff bases Copper(II), Cobalt(II) and Zinc(II) complex: Material and reagents All chemicals used in this study were of the grade of analytical reagent and of the highest possible purity. They included Cu(II)Cl2.2H2O (Sigma), Co(II) and ZnCl2.2H2O (Ubichem). The other products included furan-2-carbaldehyde which propane-1,3-diamine, and were obtained respectively from Sigma and Aldrich. Organic solvents used included an absolute solution with ethyl alcohol, dimethyl formamide (DMF) and ammonia. Those solvents were BDH-pure spectroscopic. Bidistilled water was used in all preparations, collected from all the glass equipment.

Synthesis of Schiff bases The new bis Schiff base ligand is formed by condensing the furan-2-carboxaldehyde (2g, 0.02 mmol) and propane-1,3-diamine (1.5g, 0.02mmol) hot ethanolic solution. Instead,

to remove water and start the reaction, a few drops of sulphuric aced were added and the solution mixture was left under reflux for 5 hours. The yellow product formed was separated from ethanol by filtration, purified by crystallization, washed with diethyl ether and dried in vacuum over anhydrous calcium chloride. The base product yellow bis Schiff is produced in a yield of 89%.

Synthesis of metal complex The metal complexes were prepared by mixing hot solution in absolute ethanol (15 ml) of both the metal chloride salts and bis Schiff base ligand (0.3g) in mixture of ethanol and DMF (15 ml, 1:1 v/v). The resulting mixture was heated with a stirring for 3 hours under reflux. To bring the precipitation the solution was evaporated. The precipitate was washed with a small amount of ethanol-water mixture, diethyl ether, dried over anhydrous calcium chloride in vacuum, and weighed to calculate the yield of percentage.

SUMMARY OF REFERENCES YEAR 2015

AUTHOR

Anita Rani 1

*, Manoj Kumar 1

, Rajshree Khare 2

and Hardeep Singh Tuli 3

Anita Rani 1

*, Manoj

FINDINGS Metal complexes used: Cr(II), Co(II), Ni(II) and Cu(II) Method used: 1) Conventional method 2) Microwave

Kumar 1

, Rajshree Khare 2

and Hardeep Singh Tuli 3 2015

Anita Rani, Manoj Kumar, Rajshree Khare & Hardeep Singh Tuli Gehad G. Mohamed, Ehab M. Zayed, Ahmed M.M. Hindy

Metal complexes used: Zn(II), Co(II), Ni(II) and Cu(II) Method used: Reflux • Schiff base product produced is 89%

2015

yield. A.M.A. Alaghaz, M.E. Zayed, Metal complexes used: S.A. Alharbi, R.A.A. Ammar Co(II), Ni(II) and Cu(II) Method used: Reflux • Schiff base product produced is 88% yield.

2017

Darliane A. Martins,a Lucius F. Bomfim Filho,a Cleiton M. da Silva,a Ângelo de Fátima,a Sonia R. W. Louro,b Denise G. J. Batista,c Maria de Nazaré C. Soeiro,c João

Metal complexes used: Co(II) Method used: Microwave

2019

Ernesto de Carvalhod and Letícia R. Teixeira*,a

• Schiff base product produced is 84% yield

Yokeswari Nithya .P, Ananthi .P, & Shanmuga Priya D

Metal complexes used: Copper(II) and Nickel(II) Method used: 1) Conventional method 2) Grinding method 3) Stirring method • Conventional method was found to be a better method with maximum yield produced.

References

1. https://www.researchgate.net/publication/280774449_Schiff_bases_as_an_antimicrobi al_agent_A_review

2. https://www.researchgate.net/publication/333131733_Synthesis_Characterization_and _Biological_activities_of_Schiff_base_Ligands_and_its_Metal_Complexes

3. https://www.sci-hub.ren/https://doi.org/10.1016/j.saa.2015.01.129 4. http://static.sites.sbq.org.br/jbcs.sbq.org.br/pdf/160182AR.pdf 5. https://www.sci-hub.ren/https://doi.org/10.1016/j.molstruc.2015.01.035