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Trimm Inorganic Chemistry Reactions, Structure and Mechanisms Inorganic chemistry is the study of all chemical compounds except those containing carbon, which is the field of organic chemistry There is some overlap since both inorganic and organic chemists traditionally study organometallic compounds Inorganic chemistry has very important ramifications for industry Current research interests in inorganic chemistry include the discovery of new catalysts, superconductors, and drugs to combat disease This new volume covers a diverse collection of topics in the field, including new methods to detect unlabeled particles, measurement studies, and more He received his PhD in chemistry, with a minor in biology, from Clarkson University in 1981 for his work on fast reaction kinetics of biologically important molecules He then went on to Brunel University in England for a postdoctoral research fellowship in biophysics, where he studied the molecules involved with arthritis by electroptics He recently authored a textbook on forensic science titled Forensics the Easy Way (2005) Other Titles in the Series • Analytical Chemistry: Methods and Applications • Organic Chemistry: Structure and Mechanisms • Physical Chemistry: Chemical Kinetics and Reaction Mechanisms Related Titles of Interest • Environmental Chemistry: New Techniques and Data • Industrial Chemistry: New Applications, Processes and Systems • Recent Advances in Biochemistry ISBN 978-1-926692-59-3 00000 Apple Academic Press www.appleacademicpress.com 781926 692593 Reactions, Structure and Mechanisms Inorganic Chemistry Dr Harold H Trimm was born in 1955 in Brooklyn, New York Dr Trimm is the chairman of the Chemistry Department at Broome Community College in Binghamton, New York In addition, he is an Adjunct Analytical Professor, Binghamton University, State University of New York, Binghamton, New York Inorganic Chemistry Reactions, Structure and Mechanisms About the Editor Research Progress in Chemistry Harold H Trimm, PhD Editor Inorganic Chemistry Reactions, Structure and Mechanisms This page intentionally left blank Research Progress in Chemistry Inorganic Chemistry Reactions, Structure and Mechanisms Harold H Trimm, PhD, RSO Chairman, Chemistry Department, Broome Community College; Adjunct Analytical Professor, Binghamton University, Binghamton, New York, U.S.A Apple Academic Press CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 Apple Academic Press, Inc 3333 Mistwell Crescent Oakville, ON L6L 0A2 Canada © 2011 by Apple Academic Press, Inc Exclusive worldwide distribution by CRC Press an imprint of Taylor & Francis Group, an Informa business No claim to original U.S Government works Version Date: 20120813 International Standard Book Number-13: 978-1-4665-5977-6 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint Except as permitted under U.S Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400 CCC is a not-for-profit organization that provides licenses and registration for a variety of users For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com For information about Apple Academic Press product http://www.appleacademicpress.com Contents Introduction 9   Inorganic Polyphosphate Modulates TRPM8 Channels Eleonora Zakharian, Baskaran Thyagarajan, Robert J French, Evgeny Pavlov and Tibor Rohacs   On the Origin of Life in the Zinc World: Photosynthesizing, Porous Edifices Built of Hydrothermally Precipitated Zinc Sulfide as Cradles of Life on Earth 165 D T Hobbs, M Nyman, D G Medvedev, A Tripathi and A Clearfield   Origin of Selectivity in Tunnel Type Inorganic Ion Exchangers 103 A Y Mulkidjanian and M Y Galperin   Evaluation of New Inorganic Sorbents for Strontium and Actinide Removal from High-Level Nuclear Waste Solutions 36 A Y Mulkidjanian   On the Origin of Life in the Zinc World: Validation of the Hypothesis on the Photosynthesizing Zinc Sulfide Edifices as Cradles of Life on Earth 11 Abraham Clearfield, Akhilesh Tripathi, Dmitri Medvedev, Jose Delgado and May Nyman 170 6  Inorganic Chemistry: Reactions, Structure and Mechanisms   Development of Inorganic Membranes for Hydrogen Separation Brian L Bischoff and Roddie R Judkins   Nickel (II), Copper (II) and Zinc (II) Complexes of 9-[2- (Phosphonomethoxy)ethyl]-8-azaadenine (9,8aPMEA), the 8-Aza Derivative of the Antiviral Nucleotide Analogue 9-[2-(Phosphonomethoxy)ethyl]adenine (PMEA) Quantification of Four Isomeric Species in Aqueous Solution 273 Enrique J Baran 14 Mechanistic Aspects of Osmium(VIII) Catalyzed Oxidation of L-Tryptophan by Diperiodatocuprate(III) in Aqueous Alkaline Medium: A Kinetic Model 263 Awni Khatib, Fathi Aqra, David Deamer and Allen Oliver 13 Mean Amplitudes of Vibration of the IF8 − Anion 239 M Kuwata and Y Kondo 12 Crystal Structure of [Bis(L-Alaninato)Diaqua]Nickel(II) Dihydrate 234 M M Hoffmann, J L Fulton, J G Darab, E A Stern, N Sicron, B D Chapman and G Seidler 11 Measurements of Particle Masses of Inorganic Salt Particles for Calibration of Cloud Condensation Nuclei Counters 217 Cassandra E Deering, Soheyl Tadjiki, Shoeleh Assemi, Jan D Miller, Garold S Yost and John M Veranth 10 Chemical Speciation of Inorganic Compounds Under Hydrothermal Conditions 205 Robert H Byrne   A Novel Method to Detect Unlabeled Inorganic Nanoparticles and Submicron Particles in Tissue by Sedimentation Field-Flow Fractionation 183 Raquel B Gómez-Coca, Antonín Holy, Rosario A Vilaplana, Francisco González-Vilchez and Helmut Sigel   Inorganic Speciation of Dissolved Elements in Seawater: The Influence of Ph on Concentration Ratios 173 Nagaraj P Shetti, Ragunatharaddi R Hosamani and Sharanappa T Nandibewoor 278 Contents  15 Kinetic and Mechanistic Studies on the Reaction of DL-Methionine with [(H2O)(tap)2RuORu(tap)2(H2O)]2+ in Aqueous Medium at Physiological pH Tandra Das A K Datta and A K Ghosh 16 Molybdenum and Tungsten Tricarbonyl Complexes of Isatin with Triphenylphosphine 296 M M H Khalil and F A Al-Seif 17 Synthesis and Characterization of Biologically Active 10-Membered Tetraazamacrocyclic Complexes of Cr(III), Mn(III), and Fe(III) 286 303 Dharam Pal Singh, Vandna Malik and Ramesh Kumar 18 Antifungal and Spectral Studies of Cr(III) and Mn(II) Complexes Derived from 3,3'-Thiodipropionic Acid Derivative 312 Sulekh Chandra and Amit Kumar Sharma Index 321 This page intentionally left blank Introduction Chemistry is the science that studies atoms and molecules along with their properties All matter is composed of atoms and molecules, so chemistry is all encompassing and is referred to as the central science because all other scientific fields use its discoveries Since the science of chemistry is so broad, it is normally broken into fields or branches of specialization The five main branches of chemistry are analytical, inorganic, organic, physical, and biochemistry Chemistry is an experimental science that is constantly being advanced by new discoveries It is the intent of this collection to present the reader with a broad spectrum of articles in the various branches of chemistry that demonstrates key developments in these rapidly changing fields Inorganic chemistry is the study of all chemical compounds except those containing carbon, which is the field of organic chemistry There is some overlap, since both inorganic and organic chemists traditionally study organometallic compounds, such as the cancer fighting drug cisplatin Inorganic chemistry is very important in industry The size of a country’s manufacturing output is traditionally measured by its production of the inorganic chemical sulfuric acid, which is the basis for many industrial processes Current advances in inorganic chemistry include the discovery of new catalysts, superconductors, and drugs to combat disease Much of the green revolution in farming, which allows us to feed the earth’s population, is based on the inorganic chemist’s ability to produce fertilizer from cheap raw materials Synthesis and Characterization of Biologically  307 the complexes [12] The electronic spectra of chromium complexes show bands at ~9030–9250, 13020–13350, 17450–18320, 27435–27840, and 34820 cm−1 However, these spectral bands cannot be interpreted in terms of four or six coordinated environment around the metal atom In turn, the spectra are comparable to that of five coordinated Cr(III) complexes, whose structure has been confirmed with the help of X-ray measurements [13] Thus keeping in view, the analytical data and : ionic nature of these complexes, a five-coordinated square-pyramidal geometry may be assigned for these complexes Thus, assuming the symmetry C4V for these complexes [14], the various spectral bands may be assigned as B1→4Ea, 4B1→4B2, 4B1→4A2, and 4B1→4Eb The complexes not have idealized C4V symmetry but it is being used as approximation in order to try and assign the electronic absorption bands Manganese Complex The magnetic moment of manganese complex was found to be 4.85 B.M The electronic spectrum of manganese complex show three d-d bands at approximately 12.250, 16.045, and 35.435 cm−1 The higher energy band at 35465 cm−1 may be assigned due to charge transfer transitions The spectrum resembles those reported for five-coordinate square-pyramidal manganese porphyrins [14] This idea is further supported by the presence of the broad ligand field band at 20410 cm−1 diagnostic of C4V symmetry and thus the various bands may be assigned as follows: B1→5A1, 5B1→5B2, and 5B1→5E, respectively The band assignment in single electron transition may be made as d z → d x2 − y , d xy → d x2 − y and d xy , d yz → d x2 − y , respectively, in order of increasing energy However, the complexes not have idealized C4V symmetry Iron Complexes The magnetic moments of iron complexes lay in the range 5.82–5.90 B.M and are in accordance with proposed geometry of the complexes The electronic spectra of trivalent iron complexes show various bands 9825–9975, 15525–15570, 27635–27710 cm−1, and these bands not suggest the octahedral or tetrahedral geometry around the metal atom The spectral bands are consistent with the range of spectral bands reported for five coordinate square pyramidal iron (III) complexes [15] Assuming C4V symmetry for these complexes, the various bands can be assigned as d xy → d xz , d yz and d xy → d z Any attempt to make accurate assignment is difficult due to interactions of the metal-ligand pi-bond systems lifting the degeneracy of the dxz and dyz pair 308  Inorganic Chemistry: Reactions, Structure and Mechanisms Biological Assay The minimum inhibitory concentration (MIC) shown by the complexes against these bacterial strains was compared with MIC shown by standard antibiotics Linezolid and Cefaclor (Table 2) Complex showed an MIC of μg/mL against bacterial strain Escherichia coli (MTCC 739), which is equal to MIC shown by standard antibiotic Cefaclor against the same bacterial strain Complex registered an MIC of μg/mL, against bacterial strain Bacillus cereus (MTCC 1272), which is equal to MIC shown by standard antibiotic Cefaclor against the same bacterial strain Further complexes and showed a minimum inhibitory concentration of 32 μg/mL against bacterial strain Salmonella typhi (MTCC 733), which is equal to MIC shown by standard antibiotic Linezolid against the same bacterial strain The MIC of complex against Escherichia coli (MTCC 739) was found to be 16 μg/ml, which is equal to the MIC shown by standard antibiotic Linezolid against the same bacterial strain Complex registered an MIC of μg/ mL against bacterial strain Staphylococcus aureus (MTCC 1144) which is equal to MIC shown by standard antibiotic Linezolid against the same bacterial strain Among the series under test for determination of MIC, complexes and were found most potent as compared to other complexes However, complexes and showed poor antibacterial activity or no activity against all bacterial strains among the whole series (Table 2) Table Minimum Inhibitory Concentration (MIC) shown by complexes against test bacteria by using agar dilution assay (—) No activity, a: Bacillus cereus (MTCC 1272); b: Staphylococcus aureus (MTCC 1144); c: Escherichia coli (MTCC 739); d: Salmonella typhi (MTCC 733); Cefaclor and Linezolid are standard antibiotics Synthesis and Characterization of Biologically  309 Conclusions Chemistry Based on elemental analyses, conductivity and magnetic measurements, electronic IR, and far IR spectral studies, the structure as shown in Figure may be proposed for these complexes Figure Biological Assay It has been suggested that chelation/coordination reduces the polarity of the metal ion mainly because of partial sharing of its positive charge with donor group within the whole chelate ring system [16] This process of chelation thus increases the lipophilic nature of the central metal atom, which in turn, favors its permeation through the lipoid layer of the membrane thus causing the metal complex to cross the bacterial membrane more effectively thus increasing the activity of the complexes Abbreviations MIC: Minimum inhibitory concentration MTCC: Microbial type culture collection MHA: Muller Hinton Agar 310  Inorganic Chemistry: Reactions, Structure and Mechanisms CFU: Colony forming unit B.M.: Bohr Magneton DMF: N,N-dimethylformamide DMSO: Dimethylsulphoxide BHI: Brain heart infusion Acknowledgements D P Singh thanks the University Grants Commission, New Delhi for financial support in the form of Major Research Project Thanks are also due to authorities of N.I.T., Kurukshetra for providing necessary research facilities The authors are thankful to Dr Jitender Singh for carrying out the biological activity of the synthesized macrocyclic complexes References K Gloe, Ed., Current Trends and Future Perspectives, K Gloe, Ed., Springer, New York, NY, USA, 2005 L F Lindoy, Ed., The Chemistry of Macrocyclic Ligand Complexes, L F Lindoy, Ed., Cambridge University Press, Cambridge, UK, 1989 E C Constable, Ed., Coordination Chemistry of Macrocyclic Compounds, E C Constable, Ed., Oxford University Press, Oxford, UK, 1999 D P Singh, R Kumar, and J Singh, “Synthesis and spectroscopic studies of biologically active compounds derived from oxalyldihydrazide and benzil, and their Cr(III), Fe(III) and Mn(III) complexes,” European Journal of Medicinal Chemistry, vol 44, pp 1731–1736, 2009 R Kumar and R Singh, “Chromium(III) complexes with different chromospheres macrocyclic ligand, synthesis and spectroscopic studies,” Turkish Journal of Chemistry, vol 30, no 1, pp 77–87, 2006 Q Zeng, J Sun, S Gou, K Zhou, J Fang, and H Chen, “Synthesis and spectroscopic studies of dinuclear copper(II) complexes with new pendant-armed macrocyclic ligands,” Transition Metal Chemistry, vol 23, no 4, pp 371–373, 1998 L K Gupta and S Chandra, “Physicochemical and biological characterization of transition metal complexes with a nitrogen donor tetra-dentate novel macrocyclic ligand,” Transition Metal Chemistry, vol 31, no 3, pp 368–373, 2006 Synthesis and Characterization of Biologically  311 A K Mohamed, K S Islam, S S Hasan, and M Shakir, “Metal ion directed synthesis of 14–16 membered tetraimine macrocyclic complexes,” Transition Metal Chemistry, vol 24, no 2, pp 198–201, 1999 C Lodeiro, R Bastida, E Bértolo, A Macías, and A Rodríguez, “Synthesis and characterisation of four novel NxOy-Schiff-base macrocyclic ligands and their metal complexes,” Transition Metal Chemistry, vol 28, no 4, pp 388–394, 2003 10 D L Pavia, G M Lampman, and G S Kriz, Introduction to Spectroscopy, Harcourt College Publishers, New York, NY, USA, 2001 11 M Shakir, K S Islam, A K Mohamed, M Shagufta, and S S Hasan, “Macrocyclic complexes of transition metals with divalent polyaza units,” Transition Metal Chemistry, vol 24, no 5, pp 577–580, 1999 12 D P Singh and R Kumar, “Trivalent metal ion directed synthesis and characterization of macrocyclic complexes,” Journal of the Serbian Chemical Society, vol 72, no 11, pp 1069–1074, 2007 13 J S Wood, “Stereochemical electronic structural aspects of five-coordination,” Progress in Inorganic Chemistry, vol 16, p 227, 1972 14 D P Singh and V B Rana, “Binuclear chromium(III), manganese(III), iron(III) and cobalt(III) complexes bridged by diaminopyridine,” Polyhedron, vol 14, no 20-21, pp 2901–2906, 1995 15 A B P Lever, Inorganic Electronic Spectroscopy, Elsevier, Amsterdam, The Netherlands, 1984 16 Z H Chohan, C T Supuran, and A Scozzafava, “Metal binding and antibacterial activity of ciprofloxacin complexes,” Journal of Enzyme Inhibition and Medicinal Chemistry, vol 20, no 3, pp 303–307, 2005 Antifungal and Spectral Studies of Cr(III) and Mn(II) Complexes Derived from 3,3′-Thiodipropionic Acid Derivative Sulekh Chandra and Amit Kumar Sharma Abstract The Cr(III) and Mn(II) complexes with a ligand derived from 3,3′thiodipropionic acid have been synthesized and characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements, IR, UV, and EPR spectral studies The complexes are found to have [Cr(L)X]X2 and [Mn(L)X]X, compositions, where L = quinquedentate ligand and X=NO3−, Cl− and OAc− The complexes possess the six coordinated octahedral geometry with monomeric compositions The evaluated bonding Antifungal and Spectral Studies of Cr(III) and Mn(II)  313 parameters, Aiso and β, account for the covalent type metal-ligand bonding The fungicidal activity of the compounds was evaluated in vitro by employing Food Poison Technique Introduction The synthesis of the coordination compounds of the Schiff’s base ligands having N,S-donor binding sites has attracted a considerable attention because of their potential biological activities [1–3] The main features of these compounds are their preparative accessibility, diversity, structural variability and versatile coordinating properties These compounds have also been widely investigated to examine the effect of metallation on the antipathogenic activities of such ligand systems The studies of antipathogenic behavior of these chemically modified species are of paramount importance for designing the metal-based drugs These compounds have been found to be more effective when they are administered as metal complexes [4–6] In view of these aspects and our preceding work, we report here the synthesis, spectral, and antifungal studies of Cr(III) and Mn(II) complexes derived from ligand, 3,3′-thiodipropionic acid bis(4-amino-5-ethylimino-2,3-dimethyl-1-phenyl-3-pyrazoline) Experimental The ligand 3,3′-thiodipropionic acid bis(4-amino-5-ethylimino-2,3-dimethyl1-phenyl-3-pyrazoline) (Figure 1) was synthesized according to the literature method [7] The complexes were synthesized by refluxing mmol of the metal salt (nitrate, chloride, and acetate) with mmol of ligand in acetonitrile for 8–14 hours at 70–80°C The resulting mixture was kept in refrigerator overnight at 0°C The solid powder was filtered, washed with cold acetonitrile and dried under vacuum over P4O10 Figure Structure of ligand 314  Inorganic Chemistry: Reactions, Structure and Mechanisms The fungicidal activity of the compounds was screened in vitro by employing Food Poison Technique [7] against the plant pathogens viz Alternaria brassicae, Aspergillus niger, and Fusarium oxysporum Microanalytical analyses were performed on a Carlo-Erba 1106 analyzer IR spectra were recorded as KBr pellets in the region 4000–200 cm-1 on an FTIR spectrum BX-II spectrophotometer The electronic spectra were recorded on Shimadzu UV mini-1240 spectrophotometer using DMSO/DMF as a solvent EPR spectra were recorded in solid and solution forms on an E4-EPR spectrometer at room temperature and liquid nitrogen temperature operating in X-band region The molar conductance of complexes was measured in DMSO/DMF at room temperature on an ELICO (CM 82T) conductivity bridge The magnetic susceptibility was measured at room temperature on a Gouy balance using CuSO4.5H2O as callibrant Results and Discussion The microanalytical data, magnetic moments, and other physical properties of complexes are summarized in Table As we reported earlier [7], the ligand coordinates to the metal atom in the NNSNN fashion via five binding sites and forms the stable complexes having [Cr(L)X]X2 and [Mn(L)X]X compositions The molar conductance value accounts for the 1:2 and 1:1 electrolytic nature of Cr(III) and Mn(II) complexes, respectively, (Table 1) [8] The magnetic moments of these complexes lie in the range 3.78–3.89 (CrIII) and 5.89–5.98 B.M (MnII) Table Analytical data, magnetic moments, and physical properties of complexes The IR spectrum of the free ligand shows bands at 1647, 1621, 1532, 768 cm-1 due to ν(C=O) amide I, ν(C=N) azomethine, NH in-plane-bending (amide Antifungal and Spectral Studies of Cr(III) and Mn(II)  315 III) vibrations and ν(C–S), respectively On coordination, the position of ν(C=N), amide III and ν(C–S), bands is altered, which indicates that the nitrogen atoms of C=N and NH groups, and the sulphur atom of the C–S group are coordinated to the central metal atom Further, the IR spectrum of the ligand also shows a band at 3225 cm-1 due to the ν(NH) stretching vibration On coordination, this band shows a negative shift, which is in further support of coordination of the NH group through nitrogen However, the amide I band does not show any considerable change in its position on complexation, which suggests that the C=O group does not participate in coordination [7, 9, 10] The IR spectra of complexes also give the new bands at 407–497 and 312–328 cm-1 due to ν(M–N) and ν(M–S) stretching vibrations [7, 11] This discussion reveals that the ligand coordinates to metal atom in the NNSNN manner The complexes also show the IR bands due to coordinated anions [12] The electronic spectra of complexes were recorded in DMF/DMSO solution The electronic spectra of Cr(III) complexes exhibit the absorption bands in the range 13280–19231, 25028–27027, and 36764–37735 cm-1 due to the 4A2g → 4T2g(F)(ν1), 4A2g → 4T1g(F)(ν2), and 4A2g → 4T1g (P)(ν3) spin allowed d-d transitions, respectively These bands suggest an octahedral geometry for Cr(III) complexes (Figure 2) [13] Figure Structure of [Cr(L)X]X2 complexes, where X = NO3-, Cl- and OAc- The electronic spectra of Mn(II) complexes show the absorption bands in the range 16970–19540, 22280–24390, and 26109–27624 cm-1 These absorption bands may be assigned to the 6A1g → 4A1g (4G), 6A1g → 4A2g(4G), and 6A1g → 4Eg, 4A1g (4G) transitions, respectively These bands suggest that the complexes possess an octahedral geometry [13] The complexes also show the band in the region 34843–38022 cm-1 due to a charge transfer transition Different ligand field parameters have been evaluated for the complexes and the value of 316  Inorganic Chemistry: Reactions, Structure and Mechanisms covalency factor β (0.43–0.79) reflects the covalent nature of the L → M bond The covalency factor β was evaluated by using the expression β=Bcomplex/Bfree ion, where B is the Racah interelectronic repulsion parameter The value of B lies in the range 542–784 and 418–763 cm-1 for Cr(III) and Mn(II) complexes, respectively The X-band EPR spectra for Cr(III) complexes in solid form show a broad signal at giso= 1.9829–2.2870 The signal does not show hyperfine splitting due large line widths The EPR results of Cr(III) complexes are consistent with the presence of hexacoordinated Cr(III) centers [14] The EPR spectra for Mn(II) complexes in solid form give broad signal at giso= 1.9763–2.1351 both at room temperature and at liquid nitrogen temperature However, the EPR spectra of complexes in solution (RT and LNT) show the hyperfine splitting and give six lines at giso= 1.9835–2.5961 (55Mn, I=5/2) The hyperfine coupling constant Aiso was evaluated and its values (90.0–96.0) are consistent with the complexes having Mn(II) central metal atom in an octahedral field [15] The results of the antipathogenic activity of compounds are summarized in Table The fungal inhibition capacity of the compounds was compared with the standard fungicide Captan The data indicate that the complexes possess greater fungicidal activity in comparison to ligand which is due to their higher lipophilicity This modified fungicidal behaviour of the complexes is based on the Overtone’s Concept and Chelation Theory [7] Table Antifungal activity data of the compounds Conclusions The spectral analysis of the compounds reveals that the ligand acts as quinquedentate chelate and bound to the metal atoms through NNSNN-donor sites Antifungal and Spectral Studies of Cr(III) and Mn(II)  317 The bonding parameters account for the covalent nature of L → M bond The complexes are six coordinated with metal atom surrounded by an octahedral coordinating species The screening of fungicidal activity of compounds led to the conclusion that complexes possess moderate antipathogenic behavior than the free ligand Acknowledgements The authors sincerely express their thanks to DRDO, New Delhi financial support and Dr P Sharma, Principal Scientist, IARI, Pusa, New Delhi for providing laboratory facility for determining the fungicidal activity References M C Rodríguez-Argüelles, P Tourón-Touceda, R Cao, et al., “Complexes of 2-acetyl-γ-butyrolactone and 2-furancarbaldehyde thiosemicarbazones: antibacterial and antifungal activity,” Journal of Inorganic Biochemistry, vol 103, no 1, pp 35–42, 2009 H.-J Zhang, R.-H Gou, L Yan, and R.-D Yang, “Synthesis, characterization and luminescence property of N,N′-di(pyridine N-oxide-2-yl)pyridine-2,6dicarboxamide and corresponding lanthanide (III) complexes,” Spectrochimica Acta Part A, vol 66, no 2, pp 289–294, 2007 M Wang, L.-F Wang, Y.-Z Li, Q.-X Li, Z.-D Xu, and D.-M Qu, “Antitumour activity of transition metal complexes with the thiosemicarbazone derived from 3-acetylumbelliferone,” Transition Metal Chemistry, vol 26, no 3, pp 307–310, 2001 S Adsule, V Barve, D Chen, et al., “Novel Schiff base copper complexes of quinoline-2 carboxaldehyde as proteasome inhibitors in human prostate cancer cells,” Journal of Medicinal Chemistry, vol 49, no 24, pp 7242–7246, 2006 S Tardito, O Bussolati, M Maffini, et al., “Thioamido coordination in a thioxo-1,2,4-triazole copper(II) complex enhances nonapoptotic programmed cell death associated with copper accumulation and oxidative stress in human cancer cells,” Journal of Medicinal Chemistry, vol 50, no 8, pp 1916–1924, 2007 S Shahzadi, S Ali, S Jabeen, N Kanwal, U Rafique, and A N Khan, “Coordination chemistry of the transition metal carboxylates synthesized from the ligands containing peptide linkage,” Russian Journal of Coordination Chemistry, vol 34, no 1, pp 38–43, 2008 318  Inorganic Chemistry: Reactions, Structure and Mechanisms S Chandra, D Jain, A K Sharma, and P Sharma, “Coordination modes of a Schiff base pentadentate derivative of 4-aminoantipyrine with cobalt(II), nickel(II) and copper(II) metal ions: synthesis, spectroscopic and antimicrobial studies,” Molecules, vol 14, no 1, pp 174–190, 2009 W J Geary, “The use of conductivity measurements in organic solvents for the characterisation of coordination compounds,” Coordination Chemistry Reviews, vol 7, no 1, pp 81–122, 1971 S J Swamy and S Pola, “Spectroscopic studies on Co(II), Ni(II), Cu(II) and Zn(II) complexes with a N4-macrocylic ligands,” Spectrochimica Acta Part A, vol 70, no 4, pp 929–933, 2008 10 S J Swamy, B Veerapratap, D Nagaraju, K Suresh, and P Someshwar, “Nontemplate synthesis of ‘N4’ di- and tetra-amide macrocylic ligands with variable ring sizes,” Tetrahedron, vol 59, no 50, pp 10093–10096, 2003 11 S Chandra, D Jain, and A K Sharma, “EPR, mass, electronic, IR spectroscopic and thermal studies of bimetallic copper(II) complexes with tetradentate ligand, 1,4-diformyl piperazine bis(carbohydrazone),” Spectrochimica Acta Part A, vol 71, no 5, pp 1712–1719, 2009 12 K Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Wiley Interscience, New York, NY, USA, 3rd edition, 1978 13 A B P Lever, Inorganic Electronic Spectroscopy, Elsevier, Amsterdam, The Netherlands, 1st edition, 1978 14 A Abragam and B Bleaney, Electron Paramagnetic Resonance of Transition Ions, Clarendon Press, Oxford, UK, 11970 15 A Carrington and A D McLachlan, Introduction to Magnetic Resonance, Harper & Row, New York, NY, USA, 1969 Antifungal and Spectral Studies of Cr(III) and Mn(II)  319 Copyrights © 2009 Zakharian et al This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited © 2009 Mulkidjanian; licensee BioMed Central Ltd This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited © 2009 Mulkidjanian and Galperin; licensee BioMed Central Ltd This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited Public Domain Public Domain Public Domain Copyright © 2004 Raquel B Gómez-Coca et al This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited This journal is © The Royal Society of Chemistry and the Division of Geochemistry of the American Chemical Society 2002 © 2008 Deering et al; licensee BioMed Central Ltd This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited 10 Public Domain 11 © Author(s) 2009 This work is distributed under the Creative Commons Attribution 3.0 License 12 Copyright © 2009 Awni Khatib et al This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited 320  Inorganic Chemistry: Reactions, Structure and Mechanisms 13 Copyright © 2008 Enrique J Baran This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited 14 Copyright © 2008 Nagaraj P Shetti et al This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited 15 Copyright © 2009 Tandra Das et al This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited 16 Copyright © 2008 M M H Khalil and F A Al-Seif This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited 17 Copyright © 2009 Dharam Pal Singh et al This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited 18 Copyright © 2009 Sulekh Chandra and Amit Kumar Sharma This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited Trimm Inorganic Chemistry Reactions, Structure and Mechanisms Inorganic chemistry is the study of all chemical compounds except those containing carbon, which is the field of organic chemistry There is some overlap since both inorganic and organic chemists traditionally study organometallic compounds Inorganic chemistry has very important ramifications for industry Current research interests in inorganic chemistry include the discovery of new catalysts, superconductors, and drugs to combat disease This new volume covers a diverse collection of topics in the field, including new methods to detect unlabeled particles, measurement studies, and more He received his PhD in chemistry, with a minor in biology, from Clarkson University in 1981 for his work on fast reaction kinetics of biologically important molecules He then went on to Brunel University in England for a postdoctoral research fellowship in biophysics, where he studied the molecules involved with arthritis by electroptics He recently authored a textbook on forensic science titled Forensics the Easy Way (2005) Other Titles in the Series • Analytical Chemistry: Methods and Applications • Organic Chemistry: Structure and Mechanisms • Physical Chemistry: Chemical Kinetics and Reaction Mechanisms Related Titles of Interest • Environmental Chemistry: New Techniques and Data • Industrial Chemistry: New Applications, Processes and Systems • Recent Advances in Biochemistry ISBN 978-1-926692-59-3 00000 Apple Academic Press www.appleacademicpress.com 781926 692593 Reactions, Structure and Mechanisms Inorganic Chemistry Dr Harold H Trimm was born in 1955 in Brooklyn, New York Dr Trimm is the chairman of the Chemistry Department at Broome Community College in Binghamton, New York In addition, he is an Adjunct Analytical Professor, Binghamton University, State University of New York, Binghamton, New York Inorganic Chemistry Reactions, Structure and Mechanisms About the Editor Research Progress in Chemistry Harold H Trimm, PhD Editor ...Inorganic Chemistry Reactions, Structure and Mechanisms This page intentionally left blank Research Progress in Chemistry Inorganic Chemistry Reactions, Structure and Mechanisms Harold... Medvedev, Jose Delgado and May Nyman 170 6  Inorganic Chemistry: Reactions, Structure and Mechanisms   Development of Inorganic Membranes for Hydrogen Separation Brian L Bischoff and Roddie R Judkins... Inorganic Chemistry: Reactions, Structure and Mechanisms expressing GFP alone In controls, the values of menthol-induced currents obtained at −60 mV were 0.94±0.12 and 0.915±0.122 nA (n = 7) and

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  • Front Cover

  • Contents

  • Introduction

  • 1. Inorganic Polyphosphate Modulates TRPM8 Channels

  • 2. On the Origin of Life in the Zinc World: 1. Photosynthesizing, Porous Edifices Built of Hydrothermally Precipitated Zinc Sulfide as Cradles of Life on Earth

  • 3. On the Origin of Life in the Zinc World: 2. Validation of the Hypothesis on the Photosynthesizing Zinc Sulfide Edifices as Cradles of Life on Earth

  • 4. Evaluation of New Inorganic Sorbents for Strontium and Actinide Removal from High-Level Nuclear Waste Solutions

  • 5. Origin of Selectivity in Tunnel Type Inorganic Ion Exchangers

  • 6. Development of Inorganic Membranes for Hydrogen Separation

  • 7. Nickel (II), Copper (II) and Zinc (II) Complexes of 9-[2- (Phosphonomethoxy)ethyl]-8-azaadenine (9,8aPMEA), the 8-Aza Derivative of the Antiviral Nucleotide Analogue 9-[2-(Phosphonomethoxy)ethyl]adenine (PMEA). Quantification of Four Isomeric Species in Aqueous Solution

  • 8. Inorganic Speciation of Dissolved Elements in Seawater: The Influence of Ph on Concentration Ratios

  • 9. A Novel Method to Detect Unlabeled Inorganic Nanoparticles and Submicron Particles in Tissue by Sedimentation Field-Flow Fractionation

  • 10. Chemical Speciation of Inorganic Compounds Under Hydrothermal Conditions

  • 11. Measurements of Particle Masses of Inorganic Salt Particles for Calibration of Cloud Condensation Nuclei Counters

  • 12. Crystal Structure of [Bis(L-Alaninato)Diaqua]Nickel(II) Dihydrate

  • 13. Mean Amplitudes of Vibration of the IF8 – Anion

  • 14. Mechanistic Aspects of Osmium(VIII) Catalyzed Oxidation of L-Tryptophan by Diperiodatocuprate(III) in Aqueous Alkaline Medium: A Kinetic Model

  • 15. Kinetic and Mechanistic Studies on the Reaction of DL-Methionine with [(H2O)(tap)2RuORu(tap)2(H2O)]2+ in Aqueous Medium at Physiological pH

  • 16. Molybdenum and Tungsten Tricarbonyl Complexes of Isatin with Triphenylphosphine

  • 17. Synthesis and Characterization of Biologically Active 10-Membered Tetraazamacrocyclic Complexes of Cr(III), Mn(III), and Fe(III)

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