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    86 views22 pages

    Supramolecular Chemistry

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    Sachin ashok
    Supra

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    © All Rights Reserved
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    ‘Supramolecular Chemistry "Chemistry beyond the molecule” "Chemistry of the non covalent bond” In supramolecular chemistry the components are held together and organized by means of non-covalent binding interactions. ey Molecular Recognition > Basic component of supramolecular chemistry > Origin of molecular recognition is the lock and key model. > Specific interaction between the host and quest molecule. interactions are electrostatic interactions, Hydrogen bonding, Coordinate bonding, Vanderwaals interaction, hydrophobic interaction & pi-pi interaction. }To achieve high recognition host and guest be in contact over a large area. Static Molecular recognition Host and quest combine to form host guest complex a 3:2 complexation type. Interactions are H bo) electrostatic Bonding, Coordintebondinget. fe Dynamic Molecular recognition “Host molecule contain two binding site so it requires two guest molecules Two guest molecules not bindec at the sarn= ime Binding of one folidwed by other takes place og Two types, Positive allosteric modulation nding of the first quest increases the association constant ofthe second guest. Negative allosteric modulation Binding of first quest decreases the association constant of second guest. Dynamic molecular recognition enhance the ability to discriminate between several competing targets vis conformational proof reading mechanism, HOST GUEST COMPLEX FORMATION > Host : Larger organic molecule having complementary Guest: Molecule orion bind to the Rost. Itcan be organic molecules, is ions, metal ns etc Host quest complexformatioa involves a larger host molecule with a cavity in which guest molecule cw. Ye embedded. Complex formation can be proved by NMR technique. (iost Guest complex formatin isthe proces in which the host molecule recognize a sutable guest molecule and form Host Guest Molecule (complex) ” ) é mo SRC BAe fell weannee Be ea > When the host and guest molecules combine to form a single complex, an equilibrium exists between the bownde state and unbounded state pikes Hy Go HG tant < is defined a8 i. Mal Kotte ——— PRET TNERGY DIAGRAM OF HG FORMATION in the free energy diagram, x axis ~ Reaction coordinate “Vanis = Free energy ‘HG complex has lower energy than individual ones. Association constant is given by, _ Lal ayel Large value of Ka can be equated to small value of Kd indicating the strong complexation between hostand guest molecule to form HG complex. COMPLEMENTARITY It is defined as" the host must have a binding site which can be recognized to guest + Size complementarits + Electronic complements : Size complementarity ontain correct size of binding site which can be easily fitted to guest to form Host Guest complex. complementarity Negative host can only bind with positive guest and positive host can only bind with negative guest. FORCES INVOLVED IN MOLECULAR RECOGINITION % Gitnehy pote! ergy + ork cone FERCTROSTATIC INTERATION he ty ae fo a durfanu A apart b/w charged molecule veal - is fer away» i? Magnitude of this interaction is relatively, large compared to other non-covalant interactions Inelectrostatic interaction basically nog bonkis formed. «In soln, vom clurtey around the © Strength is inversely proportional to dielectric constant cloned wroluste f baw reduc tbe KY, S Ne Thera Frere Ft fone - on -ion interaction Electrostatic interaction occur interaction b/w ions KAtpole —Acpole a Bond energy 100-350 ki/mol eee K Av pot. -irdued ctipel - Eg: ionic solid NaCl b)lon-dipole interaction B Interaction b/w ion and chargeseparated polar molecule B Weaker than ionic interaction @ Strength 50-200 ki/mol th 50:200 Am Eg,alkaline metal cation with macro Hydrogen bonding 1 only when the functional group properly orien n occu ted 2 H-bonding interac a H-bonding is weaker than electronic interaction B Becatise of strong& high directional nature H- bonding interaction is called master key interaction -¥ [Wty 6oobb atom ) f tntra Cfamt Co-neephen 2) prolulan + Van der_waals interaction PMA, Ra & 2 it isthe interaction b/wnon polar molecule a itis the weakest interaction _ B energy 5-50kj/mol a ne al * pi -pi interaction seieceenetitonme ere 8 occur 6 /WaromatC TE & two type of interaction are possible ace to face imeraction SD styyory hed om grey Chalre-t), Bede to face interaction —Dlntantess lw E difrvent Hh atom orth E wel Ke Awd t orer ero mst mt CYCLODEXTRINS + most important compound used in host-guest chemistry + They provide a hydrophobic microenvironment in an aqueous phase. + obtained fro via certain en Sea + Starchsa polysaccharide with an a 1=< linkage of glucose “se changes this polysaccharide into cyclic oligomer with appropriate number of glycopyranoside units. L_ oligomers with six, seven and eight glycopyranoside units are the most common and are called +f andy -cyclodentein, respectively ‘OR ° SoH - °, nM, cocn, {On the basis of X-ray studies cyclodextrin is considered to have agigid truncated cone structures : Primary hydroxyl groups are located at the side of a narrow rim + Secondary hydroxy groups are found on the reverse side (atthe side ofa wide rim). +“ rsult the hydrony groups render polar character to the rime iv oc osidic oxygen ators Ting in @ plane and H3 and H5 hydrogen atoms “apolar character of the cavity “no hydroxyl groups exist on the wall, and the cavity of the cyclodextrin is hydrophobic { {Ds ave acavity in which other, mostly smaller, molecules (or fons or even radicals) may ese 1 The encapsulation of guest molecules by CDs is selective, forming the basis for their applications.” ~ [Ciclodestrinsdisaved in an aqueous phase can accommodate hydrophobic guests suchas aromatic Rydrocarbons in their cavities.» * ¢ iMorganicions and gas molecules can also be included.» + ‘naar important factor in the guest selectivity is that the gize ofthe cyclodextrin cavity matches that of the guest aa molecule. + For example{a benzene ring is a good fit to a-cyclodextrin * _ thi{cavity size depends-on the number of saccharide units thatthe cyclodextrin contains, he guests selected depend on the size of the cavity + B-cyclodextrin with two naphthyl groups was used as the host. * One of the naphthyl groups is included in the cavity of the B-cyclodextri mnlerstes ‘vhe> sppropriate guest molecule enters the cyclodextrin cavity the previously included naphthyl group is vat. form a dimer with the other naphthyl group. formation raciitcin strong emission ing inside the cavity secure the absence of external guest HYDROLYSIS OF PHENYL ACETATE BY CYCLODEXTRIN * _sxample of an artificial enzyme where a cyclodextrin cavity works as a hydrophobic binding site and hydroxyl groups play the role of a catalytic residue * When phenyl acetate is used as a substrate. * the phenyl ring is incorporated into the cyclodextrin cavity “the carbonyl group exposed to outer side is nucleephilcally attacked by the anionic form ofa secondary hydroxyl group. * The acetyl group is transferred to the hydroxyl group to form an ester, and subsequent hydrolysis of the ester completes the reaction + regenerating a hydroxyl anion on the cyclodextrin. + the substrate is hydrolyzed into phenol and acetate. /¢ interactions with two imidazolyl groups: of the hydrophobic substrate are phosphodiester is hydrolyzed through cooper ‘The relative positions of the imidazolyl groups and the inclusion geometry structurally well matched. «+, This artificial enzyme can be regarded as a model of ribonuclease A. PROPERTIES + (CD have the advantage of being entirely nontoxic over a wi le dosage range.) + cyclodextrins form ae coth series from ato y-CD in terms of their physical and chemical properties 1 Jery large cyclodextrins such as 6-CD are less rigid than the smaller hosts and ‘exhibit much poorer guest complexation ability + (water solubility is less for the odd-numbered B-CD than for a- and vs + intramolecular hydrogen Bonds on the secondary face of B-CO are responsible f for its low solubility ember of cose 6 ingste 30 8 0 Inernol cout cent meter so 62 80 ry Sobbityin water tg 12580) 14s 185 2 ‘ie sition metal aa 47 323 so sluton[K-Limo-2) 377 480 aa = commaavess Atenreneghevol phen, vanines Azvacen, own “ PREPARATION + Plant photosynthesis pro + Cellulose is insoluble , starct these cyclodextrins are prepared. «starch Comprises two glucose polymers amylose and amylopectin. «oth consisting of hundreds, or even thousands, of D-glucopyranoside residues + amylose contains only 1,4-glycosidic linkages + ramified amylopectin also contains 1,6-bonds. + Degradation of starch with enzymes in presenc: hydrolysis of glycosidic linkages. « arntrins ae degraded by glicosyltransferase enzyme, the primary product of the chain splitting undergoes intramolecular cyclisation without the involvement of water, to give the cyclodextrins «= indiigual cyclodextrins are isolated from the mixture by complexation with non-polar guests such as toluene which results in decrease in solubility. + industrially produced cyclodextrins are over 99 per cent pure. ,duces two main products: starch and cellulose this readily solubilised and converted into biochemically usable for -e of water gives rise to the dextrins, which result from the APPLICATIONS «About 80-80 pet cent of cyclodextrin production (mainly BCD) is forthe food industry, because of thei high _temperature stability during food processing, + “As 3 aid ntemoval of cholesterol from animal products such as eggs and dairy products. he chesioval ‘Hound a a guest in the cylodenti-cavity wich typically suceessulin emoving ca: $0 pes ces 4 ‘unwanted component. De + Complexation of Gxpensive flavour oils and spices, such as apple, citrus fruits, cinnamon garlic. ginger. me sO! spearmint and thyme, by cyclodextrins, Gan be Col 4 + Cor n by the cyclodextrin makes the flavorings much more re: degradation, thermal decomposition or loss by sublimation, — sistant to oxidation, photochemical y cyclodextrin complexation is known to relieve local irritation or drug-induced damage, and to mask unpleasant ee achitertastes, £1 meds Uvex the pharmaceuticals industry as drug-delivery. systems. * protecting agents, preventing premature drug metabolism |ser'in chromatographic methods such as thin-layer chromatography, gas chromatography, capillary lectrophoresis and high-pressure liquid chromatography (HPLC). a CROWN ETHERS, Cyclic chemical compounds that consist of a ring containing several ether groups. EIMost common crown ethers are oligomersof ethyl the repeating unit being ethyleneoxy(- nag “Tlmportant members of series are the tetramer(n=4), pentamer(n=5) & the hexamer(n=6) GiThe term crown ether is due to its resemblencebtw structure of crown ether bound to a cationé& a m.crown ether is du ssemblencebty crown sitting on.a persons head. GiThe first number in crown ether refers to number of atoms in the cycle. + GSecond number refers to number of Oxygen atoms. = CL7 a é 5 pe 7) a 2 tS \2¢4 \ocr Radii of Alkali metals crowul ete, ao Effective ton ‘2 Size/ Alkali ee best ai A lon s 076 : a Na* 1.02 ons totow: 6 : 1.34- Kt 1.38 rown- 128 6 ~ 1.67 1.7-2.1 cs pore ctrangly hind costain cationtorming complexes. gen atoms are well situated to coordinate with cationlocated at the interior of ring,, whereas exterior of ring is hydrophobic. erage ring is hydrophobic Ginterior of ca is waterlikewhereas exterior is hydrocarbon like GlVarying size sizeof crown ether varies cavity size & some metal ions fit better than others. 5 Seer oe ee caton) 15- (a) CRYPTANDS uk hor ‘= Considered tobe the three dimensional equivalents ofcrownethers butineorporaten as well as O atoms (somet mes S or P atoms also} to nae enti ‘ity than the Frown: ‘= Molecules are approbtiatéieross-inked with)Honefoms}-orrecty positionec(in the bridging group tw en.apse ste metal ions in cage-ke structures ‘PHighsclectveandevenstrongercomplexingagentsforalkalimetals afelietin f Sroyey lomp lrg gent fu ® Showhighcomplexingability ithalkalineearthcations,few Transitions and lanathanide ions also J. alteiMnial- Firstandmostimportantoftheseriesk 2 2jcryptand]222 denotes the no. of ethereal 0 atoms in each N-N bridge)} 4 ld mol rep hree dimensional moleculef€ the binding site for cations, tions through both nitrogeand Gxygen atoms ‘= The crypts show similar high selectivity towards the alkalies owns, For(2.2.2]_cryptand,for Sxample. K's appropriate to fit in the cavity but Lit, Na are too small and Rb=, Gs are foo big fo fom slatie complexes 122 "erniand is selective for Nat = 7 ela! cation binding abilty of cryptands over crown ethers is the pre-organised, three-dimensional i avty - =" degree of preorganisationryptands display peak selectivity ) Ssletdesiee of prearpanisation SYNTHESIS OF CRYPTANDS - The methods commonly employed for the synthesis of eryptands are: (igh dilution technique) f = Most extensively used technique ‘Addition of reactants into a large amount of solvents Jobe pla Indlte Solitons the formation of acl product byintramolecular eactionismoreitely and hence faster, than the formation of a polymer, which requires a collision between two separate reactants an intermolecular rection) ‘= Methodreduces the scope of forming undesired side products but takes a long time for completion of reaction Template synthesis, TP template organizes the respective reactants to achieve a particular inking to form the desired compound Template fect of a metal ion can be of kinetic or of thermodynamic origin or a combination of both oer the «netic template effect is operative, the geometrical arrangement of ligands within the eo-ordination sphere so se en ann provides constraints that can be used to control the structure of a product formed from the lunated ligands = Hhermodynamic template effect acts to stabilize a ligand structure that might otherwise be disfavored inthe pure organic chernical system at equilibrium APPLICATIONS Ove to their high selectivity and specificity, cryptands play major roles in recognition of cations, anions and neutral molecules "= They are applied in ion transportation studies : ‘= Polymersupported cryptands are widely used as stationary phases for the column chromatographic separation of cations, anions and also of isotopes. ‘SWiderange of eppiications are also found in redox active systems, for the study of photophysical iesjinnon- linearoptics.fordopingofsot-gelmaterials a+ for co ping ae Solgel mana Fyptands as cartiers in transportation 2 The ionic transpo i The ort of Nall), K(l) across monolein and lecithin bilayers usecryptands as carriers > riansportation of Agt), Cul in and lecthin b B strange uh up ted liquid membranes by taking cryptand [2.2.1] and cryptand yptand [2.2.2] displays high extractis d (2.2.2) di ion abilities and also acts as a good cé transportation of amino acid methyl esterhydrochlorides. ae through membranes for Cryptands as stationary phases ‘= Cryptands, due to their peak selectivity and stronger ability to bind cations, anions, and neural molecules ave oe widely used ry phases, ee ee ‘= Most of these stationary phases have been prepared by either dervatising comme ally available puvsvet eryptand or by adsorbing cryptands onto various polymeric supports ‘A novel pyrene based cryptandcontaining alkali metals in its cavity has been used as an anion-ex ‘The stationary phase thus developed has been utilized for analysis of environmental samples ~ nos ange separ Redox active cryptands Cryptands containing metallocenelikefedox active compounds are potentially useful as sen: ction and antitative estimation of metal cations, by electrochemical techniques as catalysts in a variety of reactionsand possibly as voltage-regulated optical switches, ‘= Redox active cryptandcalledraferrocene yihich{contans ferroceneyunits linked with a cryptand,has been used 3s.an etal regulatory system % Cryptands in non-linear optics ‘© Ciyptands displaying non-inear optical properties areapplicablein the emerging technologies of {optoelectronics and photonic devices = Non-symmietric cryptandshave been extensively studied for their linear and non-iinear optical properties Cryptanddopedsol-gels ‘Doping of sol-gel materials with metal cryptatesigives: hybrid materials [iseful in the field of optical and electrochemical sensing, catalysis, gas separation etc, “ SPHERANDS + spherands are the most preorganised of the macrocyclic ligands and are ver tala «Spherands are complex crystands having an almost spherical structure, and are able to fprmcomplexes by enveloping the metal cations. «+ The third ofthe host-guest species is that of the spherands developed by Donald James Cram The spherands differ to the former crown ethers and cryptands as they are designed to be inflexible and ridin structure. be cause & + By creating this Pid frashewack the eation binding of oxygen atoms are preorganised and selectivity © v eae ‘ a on eee Mer O ee or Their extreme preorganisation is demonstrated by the binding constant of spherand-6 (2.15) for Lit and Na+, which are in excess of 16 and 14 log units, respectively, in water-saturated chloroform. ‘This afinity represent aa remarkably trong interaction with these highly labile ions. J ‘nll the crown ethers and even the cryptands, the binding activation energy (the energy required for a metal ‘ice its way ita the cavitl is extremely high asa consequence of the rigid nature of th spherand. ‘ov? tunding netics, for spheraplexes (complexes of spherands) ae 10 "than for the crown ethers scomlenation of metal ons from spheraplexes is also extremely sow at 25 degree cafaur fay awe been many derivatives of spherands prepared and these include hybids of spherands with crown “thers nodands and ryptands, to form hegnspherands(2.26) and cryptaspherands(2.27) MOLECULAR TWEEZERS The term "molecular tweezers" was first used by Whitlock. Molecular tweezers and molecular clips are host molecules with open cavities capable of binding guest molecules, The open cavity of the molecular tweezers may bind guests using non co\ nding which includes H -bonding, metal coordination hydrophobic forces, Vanderwaal forces, Tem intefaction and or electrostatic effects, 1s Complexes are a subset of macrocyclic molecular receptors and their btructure is ba\ the two “arms " that bind the guest molecule between themjare only connected to The end leading to Certain flexibility of these receptor molecule. Prue Lee wonnss 4 uo adeeb heey qued mebusle ger betel. EXAMPLES Water soluble phosphate - substituted molecular tweezers and norborenyl substituents bind to positively amino acids such as lysine and argine . The mee xclusive binding models make these compounds valuable tools for “¢ probing titical biclogical inteFactions of basic amino acid side chains in peptides and Proteins,as well as of NAD(P) +and similar cofactors. RCE eT Ea Molecular tweezers may be developed as drugs against diseases caused by abnor al protein aggregation. They also shown to destroy the membranes of and hepatitis C, which’make them good candidates z made of alternatively phenyl ed aliphatic side chains of basic. loped viruses such as HIV, herps, for development of microbicidies. 6 Pypiecebiows x DRA ree Reo A Metet phic as : 4 top anton we SA * nei mab bb ot 4 ve Law oy ‘ K nportts com be ured be maith dhe qiurt meolanils kine prevent a Bors fovthey oractions yf Prog da livang & Sonureg acourdchey CARCERANDS Acarcerand is a host molecule that €ompletely entraps its guest so th: i escape even at high temperatures, “This type of molecule was first described by Donald J. Cram in 1985 and is derived fromthe Latin carcer,or@rison ) The€omplexes formed by a carcerand with permanently imprisoned guests@re called carceplexes. ) Hemicarcerands allow guests to enter and exit the cavity at iiigh temperatures bu! form stable complexes at ambient temperatures The complexes formed by a hemicarcerand and a guest are called hemicarc Reactivity of bound guest Cram described the interior of the container compound as the inner phase in which radically different reactivity was observed. He used a hemicarcerand to isolate highly unstable, antiaromatic cylobutadiene at room temperature. Thelhemicarcerand stabilizes guests within its cavity by preventing their reaction with gther molecules » The first generation carcerands are based on calixarene hemicarcerands with 4 alkyl substituents on the upper rim and 4 reactive substituents on the lower rim. The coupling of both hemicarcerands takes place through a spacer group, Herd two different hemicarcerands react, one with chloromethyl reactive groups « one with thiomethyl reactive groups in a nucleophilic displace muvit and the resultise the spacer group is a dimethylsulfide (CHzSCH,). In another configuration the 4 lower rim functional groups are aldehydes which condense with O-Phenylenediamine to the corresponding di- imines. The 4 spacer groups connecting the two spheres are now much longer and consequently the internal cavity is much larger. Compounds rapped the salty are said to be held there by constrictive binding. They can be introdliced by simply heating in neat solvent like hexachlorobutadiene (a fungicide). The half-life of the reverse process is 3.2 hours at 25 °C in CDCI; by NMR analysis. Ferrocene can be introduced by heating with the hemicarcerand in a large bulky solvent such as tripiperidylphosphine oxide. The half-life for ferrocene liberation is 19.6 hours at 112 °C. The internal cavity of a carcerand can be as large as 1700 A’ (1.7 nm*) when six hemicarcerands form a single octahedral compound. This is accomplished by dynamic covalent chemistry in a one-pot condensation of 6 equivalents of a tetraformyl calixarene and 12 equivalents of ethylene diamine_with trifluoroacetic acid catalyst in chloroform at room temperature followed by reduction of the imine bonds with sodium borohydride. plexes. CYCLOPHANES ‘ cyclophane is a hydrocarbon consisting of an aromatic unit (typically a benzene ring) an aliphatic chain that forms a bridge between two non-a ijacent positions of the “aromatic ring) More complex derivatives with multiple aromatic units and bridges forming cage like structures are also known, Basic cyclophane types are [nJmetacyclophanes (I) 1 [n]paracyclophanes (I!) and [n.n'Jeyclophanes (Il). The prefixes meta and Para correspond to the usual arene Substitution patterns and n refers to the number of carbon atoms making up the bridge. fa Pt () eg eo) Schty 7 (CH), JZ i. LS “| ae = oy Mase cc ong et whe orge distribution in a benzene ring is characterized b moment equal to zero and a large quadruple effect | charge above and below the ring plane and to a rin ‘coinciding with the hydrogen atom positions, Thus cyclophanes are capable of binding not only neutral molecules but also cations, * _In the gas phase the binding of K+ to benzene is stronger than to the water molecule in spite of the big dipole moment of the latter molecule. * The binding by cyclophanes is strongly influenced t by the hydrophobic effect, thus solvent effects play an important role in such binding. The Kog? group synthesized the cyclophane water-soluble at pH<2dueto - protonation of the nitrogen atoms. Cyciophane as molecular receptors 'o~* cuest complexation behavior of various functionalized cyclophanes has been isccissed in view of their efficiency as artificial receptors and enaymes. rophobic cavities of simple and monocyclic cyclophanes are too small an effective inclusion offhydrophobic guests of various bulki ess even though the primary hydrophobic binding interaction is further enhanced by electrostatic and charge-transfer interactions 'n order to improve molecular recognition ability of cyclophanes, modifications of macro cyclic skeletons are required to give three-dimensionally extended hydrophobic cavities. One approach to create such sizable internal cavities is to construct cage-type macro cycles, e.g, Cubic cyclophanes, which are capable of incorporating guest molecules through the lock-and-key mechanism.| + Another is tolintroduce multiple hydrocarbon chains into macrocyclic skeletons, e.g., octepus cyclophanes, so that the induced-fit binding is exercised. Toe y a permanent dipole Ponce L, leading to the regions of negative" 7] 8 Of positive charge roughly id shallow to alloy do v As regards simulation of coenzyme-dependent ‘enzymatic reactions, coenzyme factors must be introduced into cyclophanes covatently or noncovalently Under cooperation of an effective substrate-activation process that can be performed with vanadium trichloride and molecular oxygen, a real artificial holoenzyme system has been composed with an octopus cyclophane and a hydrophobic vitamin B12 The holoenzyme model system catalyzes various carbon-skeleton rearrangement reactions ina manner as observed for the naturally occurring enzymes Endoacidic cyclophanes Endoacidic cyclophanes contains cavities with functional group they are acidic: and hence they have the potential fo bind cation guest such as metal ions, quaternary ammonium salts,positivly charged species and hydrogen binding solvents. In general definition we can also include cyclophane structures that are n-acidic (electron accepting) and use intimate donor acceptor interaction to drive binding. Cyclophane receptor (1) featuring 3 endo-carboxylic acid groups + Itact as an efficient transporter of highly charged hard metal ions of matching size including divalent alkaline earth metals (e.g. Ca2+Sr2+) and trivalent lanthanide earth metals (Yb3+) + The cyclophane is also referred to as Stoddart's blue box because its inventor, J Fraser Stoddart, illustrates the[electron-poor areas of molecules shade CALIXARENES © Acalixarene is 2 macrocycle ox cyclic oligomer)based ong hydroxyalkylation product of a phenol and an aldehyde. > © The word calixarene is derived from calix or chalice because this type of molecule resembles a vase and from the word arene that refers to ‘the aromatic building block. © They come ina variety of ring sizes but theompounds containing 4,6 or 8 phenol rings within the macrocycle are the easiest to synthesise and the most widely studied, \ ae ia © generally adopt a bi wl or vase shaped conformation, It is this structural shape that has lead to the name ‘calixarene’ and act as a major contributor to the properties and applications of these compounds. © The bow! shapes and the presence of the hydroxyl groups allow this family of compounds to interact with a wide variety of guests by a combination of hydrogen bonding and aromatic ring-based int teractions, © Galivarenes are usually thermally and chemically robust, can be made in large quantities from inexpensive preciirsors and can be easil 'y derivatised at the hydroxy groups or on the aromatic rings to give a wide range of materials with highly specific purposes and potential commercial applications, © The characteristic advantages of calix{4larenes for the c lowed Onstructing of receptors are vr mucostand accessibility of parent macrocycles by one-pot synthesis; calixarenes can incorporate the small hydrophobic organic molecules into their molecular cavities with the formation of the stable host-guest complexes; - 7 the existence of variety of calixarene conformations: cone, partial cone, 1,2-alternate, 1,3-alternate etc; * calix{4Jarene conformations are rath orientation of binding centers; 7 _nontoxicity of calixarene platforms. 7 “calixarene platform gives an unique possibility to decorate Macrocycle by the suitable heteroatom Possessing the several binding centers; er rigid and are able to fix the required spatial the upper and lower rim of Broups and to form the molecular system SYNTHESIS The somatic components are derived from phenol, resorcinol or pyrogallol, For phenol, ine aldehyde most often used is simply formaldehyde, while larger aldehydes (acetaldehyde, or larger) are generally required in condensation reaction, with resorcinol and pyrogallol. 7 The chemical reaction ranks under electrophilic aromati tit elimination of water and then a second aromatic substitution. 7 The reaction is acid catalyzed or base catalyzed, > Calixarenes are difficult to produce becaus: tions followed by an jad celled oy bane totelyeed Stun bi wr Ihe aldaty de 4 pleco! > CALIXARENES Practical Application “Reprocessing of spent nuclear fuel: recovery cesium anienwi)) *Chemo(bio)sensors: electioie nuse anu jue “Separation & Purification: membranes, civomatography, tullerenes separation “Catalysis: phase transfer, metallocomplexing, organocatalysts *Microelectronics: electron beam lithography, noninear optics niaterials *Gases storage: H2, CH4, COx, Nox -Pharmaceuticals & Nanomedicine: diagnostics, delivery systems. crug desian Calixarenes in the Nanoworld: Springer (2007) ‘Application of Calixarene > > Calixarenes are applied in enzyme mimetics, ion-selective electrodes or sensors, selective membranes and optic sensors. Calixarenes are used in commercial applications as sodium selective electrodes for the measurement of sodium levelis in blood. Calixarenes are often used as mobile phase additives for HPLC and chemically bonded stationary phase for both GC and HPLC in chromatography. Biological applications ~ Carriers through membranes (amphiphilic) + Avimiaet Targets & mobilization proteins DNA chips (HPV detection) Cancer and winor prevention enone editing ~ Invivo & in vitro experiments Carbon nanocapsules Nanoscale shelKfnade from a nontoxic polymer They are vesicular systems Made up of polymeric membrane Used as mri guided nano robots Size_10- 1000n: Depending on preparation & use size will be specific Nano vesicular system in the core shell Shel! made up of polymeric membrane Sioraradable polyesters ,chitosan,gelatin,albumin,polysacchrides & sacchrides are u sed.as polymers The,core contains oil surfactant that will coordinate with drug ~Oil must be highly soluble with drug & nontoxic Oil drug emulsion must have low solubility with polymer ! Preparation 1. Nanoprecipitation 2. Emulsion diffusion 3. Solvent extraction Nanoprecipitation / solvent displacement * Creating a colloidal suspension b/w 2 separate phases * Organic phase : solution & mixture of organic solvents. * Aqueous phase: mixture of non solvents. © Organic phase is slowly injected to aqueous phase «Agitated to form eallotal suspension * Agitated thoroughly until it form nanocapsules Emulsion - diffusion © Organic aqueous & dilutiin phase * Organic phase added to aquoeus phase under high agitation Forming an emulsion. et ; . Water is added to the emulsion That the solvent diffuse * Nanocapsule is formed See Solvent evaporation Single or double emulsions are formed From solvents and Are used to formulate sormed From solvents cused to formulate nanoparticle suspension High speed homogenization or ultras {0 produce small particle size When the suspension is stable solvents are evaporated Propel Absorbability It depends on aspect ratio Low ratio tend to penetrate cells easily than with high aspect ratio Drug delivery 1. Hydration and diffusion — In this release nie@chanism the nanocapsule will swell duc to the effects of hydration. Once the to thefeftect=|2! nce the Ranocapsule has swollen to a point where poce ese \t stretches, the polymeric membrane wil aliow for diffusion of the drug through the panei polymeric mem biological sys 2. Enzymatic reaction — The polymer shell must be first selected to coordinate with the énzymes roduced by the huiiati body an, boaly ar to produce and endymatid reaction. [his reaction will cause a rupture in the polymeric membrane which allows the drug to be dispersed into the system Dissociation of the drug Near-infrared light: Drug release is triggered from heat. The infrared technology can lx _absorbed deep in the body, turn t. The heat-sensitive material, particularly a polymer shell that swells upon heating, collapses The upon Neatine action of deflating is what reidases the drug.!”! Magnetic fields: Magnetic bars of millimeter- Scale are embedded in poly(vinyl alcohol). The Magnetic field within the bats is alternated, nich results in the ¢ iangeief shape and ultimate collapse of the nanocapsules. The oo Shape of tne nanocapsule: Sed to change in the structure then triggers the drug release. 4 ‘ | pe Ways sf oreo ee Some other ways include oral, which is the most active, nasal, transder, and through > Nasal, transderma tne lung. Oralis the most commen, and the host challenging, De nands for consistent lease gy althouah developments ING Marte for drugs te to bloadhere to the unal tract. Bioadne considered for nas Ns also being al delivery, to prolong the life of the drug within the nose. Drugs can also be transferred through the skin transdermal) oA tnnalers are als of interest, as for example, wr erest, as for exam) asthma drugs consist of macromoleculcs Applications In cancer treatment Used in food as neutraceuticals 1 in food as neutraceutical Used as self healing materials Explain the importance of molecular recognition in biological systems like DNA and proteins. The term molecular recognition refers to the specific interaction between two or more molecules through noncovalent bonding such as hydrogen bonding, metal coordination, hydrophobic forces, van der Wa “elec als forces, n-n interactions, ha gen electrostatic logen bonding, electrostati and/or electromagnetic effects. | + _ In the formation of double hi structure, the paired DNA strands are complementary toeach other and molecular Fecognition is established through 1) H-bonding between 5 be pecific base pairs 2) stacking interaction: bet een the hydrophobic bases +” Replication and tran BB Conplawe hrs palyruriec en wie, DU Marg ) Recognition of Proteins Protein folding: Proteins are synthesized in cells in a linear fashion (on ribosomes) and have to fold into a.native, active conformation (tertiary or quaternary structure). This conformation is largely determined by the amino acid sequence and Particularly by the distribution pattern of hydrophilic and hydrophobic amino acid residues. as » cid general rule, hydrophobic residues are buried inside the:protein core during the folding process, driven by the hydrophobic effect. The folding process is temperature sensitive and promoted by the molecular crowding , ligand binding events on receptors, an analogous enhanced interaction between protein and ligand is found. Here, the initial binding inge, which increases the molecular closeness DNA binding molecules rugs affecting gene ex ression inhibit the action of hormone re: ulated nuclear receptors. p inhibit the action of hormone reg Ptor ce hese are DNA binding proteins which either activate or suppress the trancan ional actjvity » So called transcription factors are regulated by dimerization induced by ligand binding. Transcription factor inhibitors either block agonist binding, or prevent dimerization, Examples include the nuclear receptors for estrogen, thyroxin, slucocorticoids, and the morphogen ic acid. in plants the ripening process of ste expression of a gene involved in ethylene productio drugs affecting gene expression either directly bind to DNA (non ify DNA by cross-linking or strand cleavage. Non- molecules is mediated by base intercalation, Aromatic fi; lecules integrate themselves between the base pair stacks changing the conf tmation of the double helis. Examples include the antibi oth erotics actinomycin D and proflavin. Cross linking agents form lent bonds mostly to nitrogen groups on guanine bases changing the surface structure of DNA and thus blocking protein binding — = - cc i Ane me mun bE elar engi 7 bed “4 ite Plove how Dhose hor hy ev agent eat ene addee| eo hontpart & veagend ts Speuke byehiont whet “Cl (an reat OU efley ataqenh, + OO Nat namycin PA Gatsbroticn poli Cleetrvely, fenepeat es Hhevegt teu umincnt . “_0 tomplened 5 0 ah of vebnomy Cun, t One HY ememulated (4 Carn efcrerctly bent be a= 5 Sane

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