Fully Uncomplexed Cyclodextrin in Mixed Systems of Vesicle-Cyclodextrin- Solvolysis of

Fully Uncomplexed Cyclodextrin in Mixed Systems of Vesicle -Cyclodextrin:Solvolysis of Benzoyl Chlorides

C.Cabaleiro-Lago,?L.García-R?′o,?P.Herve ′s,*,?and J.Pe ′rez-Juste ?

Department of Physical Chemistry,Faculty of Chemistry,Uni V ersity of Vigo,36310Vigo,Spain,and Department of Physical Chemistry,Faculty of Chemistry,Uni V ersity of Santiago de Compostela,15782Santiago de Compostela,Spain

Recei V ed:February 4,2009;Re V ised Manuscript Recei V ed:March 11,2009

In this contribution the in?uence of -cyclodextrin (CD)on the behavior of aqueous systems containing vesicles of dipalmitoyl phosphatidyl choline (DPPC)has been studied by determining the kinetics of the solvolysis reaction of substituted benzoyl chlorides whose solvolysis reactivity entails a high sensitivity on media properties.The application of the pseudophase formalism allowed us to obtain the thermodynamic and kinetic coef?cients characteristic of the reaction,which are essentially independent of the concentration of CD.We were able to determine the percentages of uncomplexed cyclodextrin in equilibrium with the vesicular system which were in all cases compatible with 100%.The obtained results led us to conclude that the properties of DPPC vesicles are not affected by the presence of CD in the medium and there is no type of interaction between the CD and the vesicular surfactant monomers and,therefore,all cyclodextrin is present in the mixed system as uncomplexed cyclodextrin.

Introduction

There is increasing interest in investigating surfactant ag-gregates that mimic biological membranes,such as phospho-lipidic,liposomes or synthetic amphiphile vesicles,because the architecture of these arti?cial membranes is considerably simpler than that of cell membranes.1,2Membrane mimetic agents have been used in reactivity control,photochemical reactions,and provided unique environments for substrates and enzymes.Liposomes are useful as both biomembrane models and potential drug carriers.3Since liposomes are closed vesicles consisting of unilamellar or multilamellar membranes,they can encapsulate various molecules in their internal aqueous phase or their phospholipid membranes.4In fact,liposomes carrying antibodies or oligosaccharide chains have also been reported as effective and speci?c reagents in antibacterial,antitumor,5and antihuman inmmunode?ciency virus (HIV)therapies.6Kinetically,vesicles make a highly appealing reaction medium.Because of their physical and chemical characteristics,they can inhibit chemical reactions 7-9or they can catalyze reactions acting as micro-reactors.7-15

Cyclodextrins (CD)also have the ability to alter chemical reactivity.The most studied cyclodextrins are R -, -,and γ-cyclodextrins,which consist in six,seven,and eight glucose units,respectively.16Regardless of the ?ner details of their structure,the most important feature of CDs is their cavity,because this enables them to form inclusion complexes with a great variety of substrates.16-18Increasingly,the native CDs now serve as scaffolds on which multiple functional groups can be assembled with controlled geometry opening new areas of supramolecular chemistry.19-22

Cyclodextrins as drug complexing agents have been the object of intense interest for both fundamental aspects and practical

purposes for a long time.22-24Recently,this attention has turned to the problem of biological photosensitization of drugs.25Indeed,despite their excellent therapeutic activity,many pharmacologically important chemicals such as antibacterials,antimicotics,and nonsteroidal anti-in?ammatory drugs can induce phototoxic,photoallergic,and photomutagenic phenom-ena strictly related to the drug photochemical reactivity.26It has been reported that in some cases such effects can be substantially decreased in the presence of CDs with model cellular systems.27-29Application of CDs was,therefore,suggested as a useful strategy to minimize the biological damage induced by drugs and increase drug photostability.However,it should be stressed that drug -CD complexes usually dissociate once introduced into the body,where there is also exposure to a wide range of endogenous species.29,30

In the work described in this article we studied the in?uence of -cyclodextrin (CD)on the behavior of aqueous systems containing vesicles of dipalmitoyl phosphatidyl choline (DPPC)by determining the kinetics,in these media,of the solvolysis reaction of substituted benzoyl chlorides (see Scheme 1).Benzoyl chlorides’geometry and polarity give rise to the formation of an inclusion complex with CD,31and their solvolysis reactivity entails a high sensitivity on media properties.32-34It is known that the addition of enough amounts of cyclodextrins to micellar systems causes their destruction due to the formation of CD -surfactant monomer complexes.Previ-

*To whom correspondence should be addressed.E-mail:jherves@uvigo.es.?

University of Vigo.?

University of Santiago de Compostela.

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10.1021/jp901028k CCC:$40.75 2009American Chemical Society

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ous studies carried out in our group have shown that,at the micellization point,appreciable concentrations of uncomplexed CD exist.35Furthermore,the increase of the hydrophobic character of the micellar surfactant monomers leads to an increase in the percentage of uncomplexed CD.36The aim of the present work was to study a mixed system composed by cyclodextrins and vesicles (more hydrophobic than micelles and also more realistic models for biological membranes),in which it is possible that the presence of cyclodextrins neither destroys nor alters the properties of the vesicles.Experimental Section

All the reagents (from Sigma)were of the highest available grade and used without further puri?cation.The stock solutions of benzoyl chlorides were prepared in acetonitrile to prevent them from decomposing too rapidly.CD solutions were made taking into account that commercial CD has a H 2O content of 8mol mol -1.For aqueous solutions double-distilled and deionized water was used.All experiments were carried out at 25.0(0.1°C.

Vesicle Preparation.DPPC stock solutions were prepared by weighing the required amount of solute,adding water,and keeping the solution for 30min in a water bath at 65°C.Then the solution was sonicated with a tip sonicator (Bandelin UW 2200)for 30min at 65°C (in some cases,DPPC solutions were cosonicated in presence of cyclodextrin).After those samples were equilibrated to room temperature and ?ltered through a 0.45μm pore size ?lter twice,the stock solution was diluted to the desired concentrations to prepare samples for kinetic measurements.Although the vesicles were assumed to be stable,we always used dispersions within 3h after preparation.

Dynamic Light Scattering Measurements.Samples were irradiated with an Ar +laser at λ)514.5nm,and data were recorded at three different angles (60°,90°,and 120°).Scattering data were analyzed by means of a Malvern autosizer 4700digital correlator.Correlation functions were ?tted by using the CONTIN and cumulants methods.

Transmision Electron Microscopy (TEM).Vesicles were imaged with a JEOL JEM-1010transmission electron micro-

scope using the negative-staining method.A drop of vesicle solution was spread on a 200mesh copper grid coated with a Formvar ?lm,and the extra droplet was instantly wiped off by ?lter paper.After being naturally desiccated,a drop of 2%uranyl acetate in ethanol solution was dripped on the copper grid for about 60s and the extra droplet was also removed.Then the grid was dried naturally for about 3h before TEM observation.Kinetic Measurements.Solvolysis reactions were carried out in an Applied Photophysics SX-18MV stopped-?ow reaction analyzer thermostatted with a Polyscience water bath.All kinetic experiments were performed using a 1:25asymmetric mixing kit so that the percentage of acetonitrile in the reaction mixture was always less than 4%by volume.Kinetic pro?les were followed by monitoring the decrease in absorbance of benzoyl chlorides.The wavelengths used for the kinetic studies ranged between 250and 300nm for 4-MeO,4-Cl,and 4-CF 3.The concentration range was between 6and 9×10-4M.Kinetic data were always satisfactorily ?tted by the ?rst-order integrated rate equations,and therefore,in what follows,k obs denotes the pseudo-?rst-order rate constant.Experiments were reproducible to within 5%.

Results

1.Characterization of Vesicles and CD -Vesicle Systems.The size and shape of vesicles depends on the sonication time and temperature at which they are prepared.37Sonication above the transition phase temperature (42°C)38leads to larger,multicompartment vesicles that gradually become single-compartment vesicles as the sonication time is extended.We prepared vesicles by sonicating the DPPC dispersions (in some cases in presence of CD)at 65°C for 30min.We have characterized our DPPC vesicles at 25°C in the absence and presence of cyclodextrin using TEM and dynamic light scat-tering (DLS)techniques.In Figure 1TEM micrographs are shown for DPPC vesicles in the absence and in the presence of 3mM CD.The pictures show small unilamellar vesicles with a nearly spherical shape,low polydispersity,and an average diameter of 65nm.The size and shape of the vesicles is not modi?ed by the presence of cyclodextrin.This result

suggests

Figure 1.Representative TEM images of DPPC vesicles prepared in the absence (left)and in the presence (right)of 3mM CD.

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to us the coexistence of vesicles and CD without mutual interactions that lead to destroy the vesicular aggregates.We have also determined the size of the vesicles from DLS measurements.A hydrodynamic diameter of D h )69(5nm was obtained,in good agreement with that determined by TEM.The hydrodynamic diameter of the vesicles prepared cosoni-cating DPPC in the presence of cyclodextrin ([CD])3mM)was D h )70(2nm (similar to that in the absence of CD),suggesting again no interactions between DPPC monomers and CDs.

2.In?uence of CD on the Solvolysis of Substituted Benzoyl Chlorides.Although the hydrolysis of benzoyl chlo-rides in the presence of CDs has been recently studied,31we examined the in?uence of the CD concentration on the solvolysis reaction of substituted benzoyl chlorides to ensure good consistency in the evaluations of the experimental results.In the presence of CD,the apolar inner cavity of the CD provides a solubilization site for the benzoyl chloride with a reversible formation of a 1:1inclusion complex,as shown in Scheme 2.From this kinetic scheme we can obtain the following rate equation:

k obs )

k w +k CD K CD [CD]1+K CD [CD]

(1)

where k w and k CD are the rate constants of the solvolysis of the benzoyl chlorides in bulk water and in the inclusion complex with the cyclodextrin.K CD is the equilibrium constant of the cyclodextrin -benzoyl chloride complex.

Depending on the nature of each benzoyl chloride,the kinetic behavior obtained differs (Figure 2),and this is due to the different mechanisms whereby the reaction takes place.Benzoyl chlorides with electron-withdrawing groups (4-CF 3)favor an associative mechanism,and therefore the inclusion complex is reactive (Figure 2A).On the other hand,benzoyl chlorides with electron-donating substituents (4-MeO and 4-Cl)favor a dis-sociative mechanism that implies the formation of a nonreactive complex (Figure 2B).31

Equation 1can be ?tted to experimental data giving values in good agreement with literature.31(K CD )200(23M -1and k CD )(9.2(0.3)×10-2s -1for 4-CF 3,K CD )391(15M -1for 4-MeO,and K CD )225(21M -1for 4-Cl.)

3.In?uence of DPPC Vesicles on the Solvolysis of Substituted Benzoyl Chlorides.The study of the solvolysis reaction of substituted benzoyl chlorides in the presence of zwitterionic vesicles of DPPC has been recently carried out in our research group.39

Figure 3shows the in?uence of the vesicular aggregates on the solvolysis reactions for the different benzoyl chlorides.The observed kinetic behavior will depend on the substituent of the

aromatic ring.In general,the kinetic effects of the vesicles on the pseudo-?rst-order rate constant can be analyzed on basis of the pseudophase model,40,41assuming a two-pseudophase system in which the reaction is treated as occurring in both a vesicular pseudophase,representing the DPPC bilayer,and an aqueous pseudophase,representing both the bulk medium and the intravesicular compartment (see Scheme 3).The substrate would be distributed between the two regions,and therefore the reaction can take place in either of them.

The overall reaction rate will be the sum of the rates in both pseudophases.This model leads to the following equation:

k obs )

k w +k ves K V [DPPC]1+K V [DPPC]

(2)

where k ves and k w are the ?rst-order rate constants for the vesicular and aqueous pseudophases,respectively,and K V is the association constant or constant of benzoyl chloride distribu-tion between the two pseudophases.

Table 1shows the values of rate constants in the vesicular interface and in water,as well as the distribution constant for the three substituted benzoyl chlorides studied obtained from the ?t of eq 2to experimental data.

4.Solvolysis of Substituted Benzoyl Chlorides in the Presence of the Mixed CD -Vesicle System.To study the CD -vesicles mixed system we carried out sets of experiments in which the [CD]was kept constant,and we observed the effect of increasing the vesicles concentration.

4.1.Sol W olysis of 4-MeO and 4-Cl Benzoyl Chlorides.To study the effect of DPPC vesicles on the solvolysis of 4-MeO benzoyl chloride containing CD,we conducted experiments at constant CD concentration (1.0×10-3,3.0×10-3,

5.0×10-3,and 9.0×10-3M)and variable DPPC concentrations (see Figure 3A).In all cases,the reaction rate decreased with increasing DPPC vesicles concentration.The k obs values obtain-ing by extrapolating to a zero DPPC concentration at each CD concentration are consistent with the k obs values obtained in the presence of CD and in the absence of DPPC (see Figure 2B).The decrease in k obs with increasing [CD]is due to the formation of a nonreactive complex between CD and 4-MeO benzoyl chloride,as we mentioned in section 2.Benzoyl chlorides with electron-donating substituents favor a dissociative pathway in which the departure of the leaving group is the slow step of the reaction.32Taking into account that the solvation ability of the interior of the cyclodextrin is minimal,16,17,42it is expected a negligible or very low reactivity of the inclusion complex formed between these benzoyl chlorides and the CD,then an increase in CD concentration will lead to a decrease in the reaction rate.At a constant [CD],an inhibitory effect of DPPC vesicles on solvolysis of 4-MeO benzoyl chloride is observed.Vesicular and substituent effects can be explained in terms of a duality of reaction paths (associative and dissociative).The dissociative mechanism is strongly affected by the properties of the medium.32,43Vesicles provide a more apolar medium for solvolysis of benzoyl chlorides,with a lower ability to solvate the leaving group,the slow step of the reaction.The inhibition observed in Figure 3A can be attributed to the association of the substrates to the vesicles.The association prevents the access of the substrate to the bulk water reducing the observed reaction rate.Although reaction in the vesicular pseudophase is taking place,the rate constant (k ves )is much smaller than that in water.39In Figure 3A also it can be also observed that the inhibitory effect of vesicles is reduced as the concentration of CD increases due to the competitive association of 4-MeO benzoyl chloride

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to the CD that reduces the amount of substrate available to reacts in the vesicular interface.

Similar results were obtained in the study of the in?uence of DPPC vesicles on the solvolysis of 4-Cl benzoyl chloride containing CD (see Figure 3B).The observed rate constant decreases as the vesicle concentration increases.As for the

4-MeO substituent,the solvolysis of 4-Cl benzoyl chloride occurs through the dissociative channel,with the departure of the leaving group as rate-limiting step.This behavior,as occurs in the absence of cyclodextrin,is due to the association of the substrate to the vesicles and the smaller reactivity in the vesicular interface than in water,leading to a decrease in the reaction rate.We mentioned in section 2that 4-Cl benzoyl chloride forms a nonreactive complex with cyclodextrin;therefore,the observed rate constant in presence of the mixed system CD -vesicles is smaller than in presence of DPPC vesicles.

4.2.Sol W olysis of 4-CF 3Benzoyl Chloride.Figure 3C shows the in?uence of vesicle concentration on k obs for the solvolysis of 4-CF 3benzoyl chloride in the presence of a constant concentration of CD,[CD])1×10-3M.The observed

rate

Figure 2.In?uence of cyclodextrin concentration on k obs for (A)solvolysis of 4-CF 3benzoyl chloride and (B)4-MeO benzoyl chloride,(O )in the absence of DPPC vesicles and (b )in the presence of [DPPC])5×10-4

M.

Figure 3.(A)In?uence of DPPC concentration on k obs for solvolysis of 4-MeO benzoyl chloride in the presence of different cyclodextrin concentrations:(O )0.00,(b )1×10-3,(0)3×10-3,(9)5×10-3,and (?)9×10-3M.(B)In?uence of DPPC concentration on observed rate constant for solvolysis of 4-Cl benzoyl chloride in (O )absence and (b )[CD])1×10-3M.(C)In?uence of DPPC concentration on k obs for solvolysis of 4-CF 3benzoyl chloride in (O )absence and (b )[CD])1×10-3M.

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TABLE 1:Percentage of the Free Cyclodextrin and Results of Fitting Eq 3or 4to the Experimental Data for the Solvolysis of Benzoyl Chlorides in CD -Vesicle Mixed

Systems Keeping Constant the Cyclodextrin Concentration a

substrate [CD]/mM

%[CD]f k ves /s -1b K V /M -1b 4-MeO 0335(74-MeO 1100(4300(134-MeO 399(3342(134-MeO c 396(3317(144-MeO 5102(4304(214-MeO 9109(12292(514-Cl 00.064(0.005518(404-Cl 1105(140.053(0.007445(554-CF 300.16(0.01107(174-CF 3

1

99(38

0.16(0.03

102(34

a

k w )57s -1(4-MeO),k w )0.195s -1(4-Cl),k w )0.037s -1(4-CF 3),k CD )0.092s -1(4-CF 3),K CD )391M -1(4-MeO),K CD )225M -1(4-Cl),K CD )200M -1(4-CF 3).b Values obtained from ?tting eqs 3and 4to the experimental data.c DPPC and CD were cosonicated,vide infra.

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constant,k obs,increases with increasing DPPC vesicles concen-tration,as occurs in the absence of cyclodextrin.Solvolysis of benzoyl chlorides with electron-withdrawing groups(as4-CF3) goes through an associative channel,with the formation of a tetrahedral intermediate that develops a negative charge as rate-limiting step.32The observed catalysis in Figure3C is because of the enhanced stabilization of the associative intermediate due to favorable interactions of cationic head groups of the DPPC vesicles with the developing negative charge at the reaction center.39The presence of CD in the mixed system also leads to an increase in the reaction rate due to the formation of a reactive 1:1complex between CD and4-CF3benzoyl chloride.The primary hydroxyl groups of the cyclodextrin are nucleophilic and react with benzoyl chlorides with electron-withdrawing groups.It can be observed that the value of the observed rate constant extrapolated to zero DPPC concentration is in agree-ment with the values obtained in the absence of vesicular surfactant(see Figure2A).

Discussion

A quantitative interpretation of the experimental behavior observed can be carried out by means of the formalism of the pseudophase model.In the solvolysis of substituted benzoyl chlorides we must consider the existence of three simultaneous reaction paths:the reaction of the free substrate in aqueous medium,the reaction of the complexed substrate with the CD, and the reaction of the substrate in the vesicular surface(see Scheme3).

On the basis of this mechanism we can obtain the following general expression for the observed rate constant:

k obs )

k

w

+k

ves

K

V

[DPPC]+k

CD

K

CD

[CD]

f

1+K

V

[DPPC]+K

CD

[CD]

f

(3)

where[CD]f is the concentration of uncomplexed cyclodextrin that is available to form an inclusion complex with the benzoyl chloride.

In order to apply this kinetic model to our system we need to know the concentration of free cyclodextrin([CD]f)present in the system.Our group has developed a kinetic model that accounts for reactivity in mixed micellar surfactant-CD sys-tems,35allowing us to indicate some characteristics of mixed CD-surfactant systems:(i)for surfactant concentrations lower than the micellization point complexation equilibrium between the surfactant and the cyclodextrin is established.As the surfactant concentration increases we reach a situation in which the concentration of uncomplexed surfactant monomers in equilibrium with the CD is enough for the micellization process to begin.(ii)At the micellization point an appreciable concen-tration of uncomplexed CD exists.36This conclusion was contradictory with the traditional view44that considers that only when all the available cavities of the CD are occupied,the monomers can aggregate to form the micelles,and(iii)the results obtained con?rm that the percentage of uncomplexed CD increases with the hydrophobic character of the surfactant. Therefore,by modulating the hydrophobicity of cationic sur-factants we have found changes in the percentage of uncom-plexed CD in equilibrium with the micellar system between5% and30%.45Moreover,using nonionic surfactant with lower critical micelle concentration(cmc)than cationic ones,46the percentage of uncomplexed CD can increase to almost93%. DPPC vesicles supply a more hydrophobic environment than micelles due to the much lower critical vesicle concentration, as compared to the cmc.Then,we would be able to obtain a vesicle-CD mixed system in which all cyclodextrin would be free and available to bind the organic substrate,as we propose in Scheme3.It is well-known that the addition of CDs to micellar systems produces changes in its physicochemical properties,due to the formation of inclusion complexes CD-surfactant monomer,and if the[CD]is high enough,this complexation process can lead to destroy the micellar ag-gregates.To take this interaction into account,the concentration of free or uncomplexed CD(CD not associated to surfactant molecules)was calculated by using the information obtained from the experiments in systems where the benzoyl chlorides are in presence of a single association entity,CD or vesicles. As pointed out before for the substituted benzoyl chlorides with dissociative mechanism,4-MeO and4-Cl,the reactivity of the substrate complexed with the cyclodextrin is negligible, and then in these cases,eq3can be rewritten as

k

obs

)

k

w

+k

ves

K

V

[DPPC]

1+K

V

[DPPC]+K

CD

[CD]

f

(4)

For any vesicle concentration it is possible to obtain the concentration of free cyclodextrin([CD]f),from the following equation derived from eq4.

[CD]

f

)

k

w

-k

obs

+K

V

(k

ves

-k

obs

)[DPPC]

k

obs

K

CD

(5)

The combination of the curves for the systems with only CD or DPPC(Figure2B and Figure3,parts A and B)can be used as calibration curves and let us obtain the concentration of uncomplexed cyclodextrin in the mixed system formed by CD and a vesicular surfactant.This requires that we assume that the kinetics and equilibrium constants in the individual system are not modi?ed in the mixed system.For each constant concentration of CD of Figure3,parts A and B,we can obtain the value[CD]f from the k obs value of each DPPC concentration. In Table1are shown the obtained mean values of[CD]f.The percentages of free cyclodextrin are compatible with100%and are independent of the cyclodextrin concentration of the medium. This result is in accordance with previous results obtained in our research group45,46that showed that the percentage of uncomplexed CD increases with the hydrophobic character of the micellar surfactant.DPPC provides a more hydrophobic environment than micelles,or at least its critical vesicle concentration is lower than the cmc of micelles.

On the other hand for the4-CF3-substituted benzoyl chloride (with and associative mechanism and therefore a reactive CD-substrate inclusion complex)it is possible to calculate the uncomplexed or free cyclodextrin concentration from eq6, which is obtained from eq3.

[CD]

f

)

k

w

-k

obs

+K

V

(k

ves

-k

obs

)[DPPC]

k

obs

K

CD

-k

CD

K

CD

(6)

The Figure2A values(in absence of DPPC)and Figure3C (in absence of CD)were used as calibration curves and allow us to obtain the concentration of uncomplexed cyclodextrin.As before,the percentage of free cyclodextrin in the mixed system is compatible with100%(see Table1).

The experimental data together with the percentages of free cyclodextrin obtained from eqs5and6allow us to propose the lack of interaction between cyclodextrin and the vesicular surfactant.Therefore,the concentration of DPPC in eqs3and 4corresponds to the total concentration of vesicular surfactant (we are taking into account the very low critical aggregation concentration of vesicles),47and[CD]f is the total cyclodextrin concentration which is available to react with benzoyl chlorides.

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Taking into account the above considerations(that is,the DPPC and CD f concentrations correspond to the total concentra-tions)eqs4and3can be?tted to the experimental data for the 4-MeO/4-Cl and4-CF3,respectively.The curves traced in Figure 3,parts A and B,correspond with the?t of eq4to the experimental values of k obs.In the case of Figure3C we?t eq 3to the observed rate constant.To simplify the?tting procedure, we have only optimized the parameters corresponding with the reaction in the vesicular pseudophase,k ves and K V(using the values for k w,k CD,and K CD obtained in the absence of vesicles). The value of k ves for the solvolysis of4-MeO is much smaller than that in water and compatible with zero.For this reason and to make easier the?tting procedure we have considered these values negligible in the CD-vesicle mixed system.In Table1are shown the obtained?tting parameters,and es-sentially these parameters are independent of[CD]and agree satisfactorily with the values obtained in the absence of CD. These results indicate the validity of the model being applied. Besides,the constancy in the K V values indicates to us that the properties of DPPC vesicles themselves are not affected by the presence of CD in the medium.

In order to check the validity of the proposed model,we study the effect CD concentration on the solvolysis of substituted benzoyl chloride in the presence of a constant concentration of vesicles,[DPPC])5×10-4M.Figure2A shows the results for4-CF3benzoyl chloride.The observed rate constant increased with increasing CD concentration,as happened in the absence of vesicles,due to the formation of a reactive complex between benzoyl chloride with electron-withdrawing groups and CD.The increase in k obs values in the presence of DPPC vesicles is due the fact of4-CF3benzoyl chloride reacts through an associative channel,which is favored by the vesicles,39as we mentioned in the Results section.Figure2B shows the effect of increasing [CD]on k obs for the solvolysis of4-MeO in the presence of vesicles.The reaction rate shows inhibition behavior with increasing[CD],due the formation of an unreactive inclusion complex between benzoyl chloride with electron-donating groups and CD.The reaction rate decreases in the presence of DPPC vesicles,which provide a more apolar medium,leading to an inhibition of reaction that goes through the dissociative mechanism,as was commented in the Results section.Similar results were found to4-Cl benzoyl chloride(see the Supporting Information).The solid lines in Figure2,parts A and B, represent the best?t of eqs3and4,respectively,to the experimental data.In this case,we optimized the parameters corresponding with the reaction in the presence of cyclodextrins, k CD and K CD(and using the values for k w,k ves,and K V obtained in the absence of cyclodextrin).In Table2are shown the optimized values for these parameters in cyclodextrin and mixed CD-vesicle systems.As we can observe there is a good agreement between the values of k CD and K CD obtained in the absence and presence of DPPC vesicles.These results support the proposed model.

The results obtained and shown in Tables1and2let us conclude that(a)the properties of DPPC vesicles themselves are not affected by the presence of CD in the medium and(b) there is no type of interaction between the CD and the vesicular surfactant monomers,and then all cyclodextrin is present in the mixed system as uncomplexed cyclodextrin.

In our model we considered that properties of DPPC vesicles themselves were not affected by the presence of CD in the medium.The characterization of the mixed system and the kinetic result obtained supports this assumption.Previous kinetic studies have shown that there is no interaction between CD and sodium dodecyl sulfate(SDS)or tetradecyltrimethylammonium bromide(TTABr)micelles.48,49In the other hand,the results obtained from the study of the enthalpy of transfer of cyclo-dextrin from water to the aqueous surfactant solutions suggest the existence of interactions between micelles and cyclodextrins by using?uorinated alkanoates.50However,the existence of these interactions has been questioned recently,51using the self-diffusion NMR technique to study the host-guest interactions between CD and micelles of cationic,anionic,and nonionic surfactants.

As we mentioned,previous studies carried out in our group and by others52showed that,rather than being two competitive processes,the association to the cyclodextrin and the autoas-sociation of surfactant are simultaneous processes,and from the competition between them derives the existence of free cyclodextrin.Our results show that an increase in the hydrophobic-character of the surfactant favors more the autoassociation45,46 rather the association to the cyclodextrin.With the use of a provesicular surfactant,it is possible to obtain a surfactant-CD mixed system in which all cyclodextrin is free and available to react with the organic substrate.Another explanation for the absence of interactions between DPPC vesicles and cyclodex-trins is the high robustness of the vesicles comparing to micelles. Although there is a surfactant concentration threshold below which vesicles do not form,47this threshold is not the result of a dynamic equilibrium between free and vesicular surfactant, like the cmc of micellar media.Once formed,vesicles are not destroyed by dilution.The stability of the vesicles is,in this sense,higher than the micelles.

As a last con?rmation of our results,we have studied the in?uence of DPPC on solvolysis of4-MeO in mixed systems of CD-vesicle,but in this case the vesicular surfactant was cosonicated in presence of[CD])3×10-3M.The hydro-dynamic diameter of the vesicles prepared in this way was D h )70(2nm(similar to that in the absence of CD).The values of k obs obtained increasing the vesicles concentration were similar(see the Supporting Information)to that obtained,at the same starting reactant concentrations,in the mixed system in which the cyclodextrin is added to the previous formed vesicles, leading to a similar values of K V(see Table1).These results reassert our assumption of there is no type of interaction between the CD and the vesicular surfactant monomers.Opposite to what happens with micellar surfactant,the additions of cyclodextrin to the vesicular systems neither destroy nor alter the properties of the vesicles.The results summarized in this work highlight the complexity of CD-vesicle systems,and we consider them of great importance since cyclodextrins and DPPC(or others surfactants)aggregates are potential drug complexing agents. Therefore,formulations that contain both species should take

TABLE2:Results of Fitting Eq3or4to the Experimental

Data for the Solvolysis of Benzoyl Chlorides in CD-Vesicle

Mixed Systems Keeping Constant the DPPC Concentration a

substrate[DPPC]/M k CD/s-1K CD/M-1

4-MeO0391(15

4-MeO5×10-4411(7

4-Cl0225(2

4-Cl5×10-4212(11

4-CF300.092(0.003200(23

4-CF35×10-40.085(0.006268(85

a k w)57s-1(4-MeO),k w)0.195s-1(4-Cl),k w)0.037s-1

(4-CF3),k ves)0.064s-1(4-Cl),k ves)0.16s-1(4-CF3),K v)335

M-1(4-MeO),K v)518M-1(4-Cl),K CD)107M-1(4-CF3).

6754J.Phys.Chem.B,Vol.113,No.19,2009Cabaleiro-Lago et al.

into deep consideration the possible interaction between both species and the consequences on this interaction on its function. Conclusions

A study has been carried out on the solvolysis of substituted benzoyl chlorides in cyclodextrins-DPPC vesicle mixed sys-tems.The reaction takes place simultaneously through dissocia-tive and associative mechanisms.A quantitative interpretation of the experimental behavior observed can be carried out by means of the formalism of the pseudophase model,which allowed us to obtain the thermodynamic and kinetic coef?cients characteristic of the reaction.

The kinetic proposed model lets us determine the percentages of uncomplexed cyclodextrin in equilibrium with the vesicular system which are compatible with100%and are independent of the cyclodextrin concentration in the medium.Transmission electron microscopy and DLS measurements showed that the size and shape of the vesicles are not modi?ed by the pres-ence of cyclodextrin.The results obtained let us conclude that the properties of DPPC vesicles themselves are not affected by the presence of CD in the medium,and there is no type of interaction between the CD and the vesicular surfactant mono-mers,and then all cyclodextrin is present in the mixed system as uncomplexed cyclodextrin.Opposite to what happens with micellar surfactant,the addition of cyclodextrin to the vesicular system neither destroys nor alters the properties of the vesicles. Acknowledgment.Financial support from the Ministerio de Educacio′n y Ciencia(Project CTQ2007-64758),Programa de Recursos Humanos do Plan Galego de Innovacions,Desen-volvemento e Teccnoloxia-INCITE Isidro Parga Pondal(C.C.-L.),and Programa Nacional de Contratacio′n e Incorporacio′n de Recursos Humanos de Investigacio′n,Subprograma Ramo′n y Cajal(J.P.-J.)is acknowledged.

Supporting Information Available:Graphs for the sol-volysis of4-Cl in the presence of CD and solvolysis of4-MeO in the cosonicated CD-vesicles system.This material is available free of charge via the Internet at https://www.wendangku.net/doc/1d9808691.html,. References and Notes

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c语言试题及答案

《C语言》课程综合复习资料 一、单选题 1. 在C语言中，字符型数据在存中的存储形式是 A）原码 B）补码 C）反码 D）ASCII码 2. 在C语言中，十进制数47可等价地表示为 A) 2f B) 02f C) 57 D) 057 3. 设有定义：int x=12,n=5; 则表达式 x%=(n%2) 的值为 A) 0 B) 1 C) 2 D) 3 4. 设有定义语句：char str[][20]={,"Beijing"，"中国石油大学"},*p=str; 则printf("%d\n",strlen(p+20)); 输出结果是 A）10 B） 6 C） 0 D） 20 5. 已定义以下函数: fun(int *p) { return *p; } 该函数的返回值是 A）不确定的值 B）形参p所指存储单元中的值 C）形参p中存放的值 D）形参p的地址值 6. C语言中,函数返回值的类型是由 A）return语句中的表达式类型决定 B）调用函数的主调函数类型决定 C）调用函数时的临时类型决定 D）定义函数时所指定的函数类型决定 7. 有以下函数定义： void fun( int n , double x ) { …… } 若以下选项中的变量都已正确定义并赋值，则对函数fun的正确调用语句是 A） fun( int y , double m )； B） k=fun( 10 , 12.5 )； C） fun( 10 , 12.5 )； D） void fun( 10 , 12.5 )； 8. 以下选项中不能正确赋值的是 A） char b[]={′H′，′e′，′l′，′l′，′o′，′！′}； B） char b[10]；b="Hello！"；

适合娶亲婚礼上唱的歌最全版本

1.《水晶》（新人对唱的） 2.《真想见到你》（李汶的歌，新娘独唱的哦，实力派！） 3.《月亮代表我的心》（比较悠久啦） 4.《深情相拥》（对新人的唱功要求颇高啊） 5.《很爱很爱你》（也是新娘独唱哦，不过改了歌词，例如”看着她走向你，那幅画面多美丽”改成“我现在走向你，那幅画面多美丽”） 6.《第一次》（光良的歌，不用我多说了吧） 7.《love,love,love》（八错，调动现场气氛满灵的，新娘唱的也八错滴好象唱歌的新娘居多，我们的男士们很害羞呢） 8.《明明很爱你》（马来西亚的歌手唱的歌满受JMS的欢迎，大概是曲风比较明快吧） 9.《神话》（成龙大哥的版本比较通俗，八过对MM的要求高些，韩红的版本实力派的JMS挑战一下啊！） 10.《选择》（内敛型的JMS可以考虑的一种） 11.《最浪漫的事》（经典的歌曲，用在婚礼上再合适不过。） 12.《宁静的夏天》（节奏轻快，简洁，个人满喜欢，夏天结婚的可以试试） 13.《牵手》（应该是满老的歌了，有空我去听下再发表意见恩，听了个开头就知道了，应该是满苦情的歌，婚礼上就需要考虑是否适合了额．跟年龄有关吧） 14.《你最珍贵》（又一个对唱功有要求的） 15.《恋爱达人》（利用歌词可以搞些小剧情，效果应该不错。） 16.《恋爱频率》（看来是对流行音乐把握很敏锐的MM，） 17.《我只在乎你》（大家帮忙改改歌词吧） 18.《明明白白我的心》（简单的情歌，不太唱歌的JMS也可以小试身手了） 19.《你是我最深爱的人》（应该是男士发挥的时候了吧） 20.《屋顶》（个人还是喜欢杰伦的版本） 21.《在我生命中的每一天》（对唱的、抒情的慢歌永远是大家的最爱+首选） 22.《小夫妻》（一般用来做背景音乐较多的歌，可能太通俗了些，唱的人八多啊，不过还 是赞一个） 23.《不得不爱》（） 24.《爱你一万年》（LG唱给LP听，记住表情,一定要深情!迷倒一大片。。。。。掌声鼓励一下） 25.《让我取暖》（很适合年轻夫妻对唱的情歌，有Young的气息） 26.《明天我要嫁给你了》 27.《你是我的老婆》（好歌啊，好歌。。。，终于又有适合GG们独唱的好歌了。） 28.《大城小爱》（） 29.《你是我的幸福吗》（MM们独唱之作，不要害羞，大胆的唱给GG们听吧！） 30.《出嫁》（zhangning_she MM真是需要再表扬一下，提供了这么多歌，而且首首都这么经典，不错的情歌，可对唱） 31.《我愿意》（可独唱，也可双人合唱的佳作） 32.《你是我心底的烙印》（一人一句，配合默契啊） 33.《甜蜜蜜》（邓JJ的怀旧老歌，永远最好听） 34.《北极雪》（旋律很容易上口，不只冬天适合唱，夏天唱可以带来一丝凉意） 35.《被风吹过的夏天》（如果是在夏天相恋的JMS注意了额，这里就有一首适合你们对唱 的歌曲了）

12年高考湖北文言文《家有名士》详细注解家有名士

2012年高考湖北卷 家有名士 1 南朝2 刘义庆 3 ?王湛4 既除所生服5 ，遂停墓所6 。兄王浑7 之子济 8 每来拜墓9，略不过叔10，叔亦不候。济脱时过11，止 12 寒温13而已。后聊14试问近事15，答对甚有音辞16，出 济意外，济极惋愕17。仍与语，转造18清微19 。济先略无20子侄之敬21，既闻其言，不觉懔然22，心形23俱肃24。 遂留共语，弥日累夜25。济虽俊爽26，自视缺然27 ，乃喟然28 叹曰：“家有名士，三十年而不知！” ?济去，叔送至门。济从骑1 有一马，绝．2 难乘，少3 能骑者。济聊4问叔：“好5骑乘不？”曰：“亦好尔。”济 又使骑难乘马，叔姿形6既妙，回策如萦7，名骑8无以 9 过之。济益10叹其11难测，非复12 一事。 ?【邓粲1 《晋纪》曰：“王湛字处冲，太原人。隐德，人莫之知，虽兄弟宗族，亦以为痴，唯父昶异焉。昶丧，居 墓次2，兄子济往省3湛，见床头有《周易》4 ，谓湛曰：‘叔 父用此何为？颇5曾看不？’湛笑曰：‘体中6 不佳时，脱 复看耳7。今日当与汝言。’因8 共谈《易》，剖析入微，济 所未闻，叹不能测9 。 ?济性好马，而所乘马骏驶1 ，意甚爱之。湛曰：‘此虽小驶2，然力薄不堪3 苦。近见督邮马，当胜此，但养不至 耳。’济取督邮马，谷食4 十数日，与湛试之。湛未尝乘马，卒5然便驰骋，步骤不异于济，而马不相胜6 。湛曰：‘今直 行车路7，何以别马胜不8？唯当就．9蚁封10 耳。’于是就蚁封盘马11，果倒踣12，其俊识13天才14乃尔15。”】 ?既还，浑问济：“何以暂行累日1 ？”济曰：“始2 得 一叔。”浑问其故，济具3叹述4如此。浑曰：“何如5 我？”济曰：“济以上人。”武帝每见济，辄以湛调之，曰：“卿家痴叔死未？”济常无以答。既而得叔，后武帝又问如前，济 曰：“臣叔不痴。”称其实美6。帝曰：“谁比7 ？”济曰：“山涛8以下，魏舒9以上。”【《晋阳秋》曰：“济有人伦鉴识10， 见湛，叹服其德宇11 。时人谓湛上方山涛不足，下比魏舒有余。”】 【注】正文选自南朝刘义庆的《世说新语》，【】内的文字是南朝刘孝标的注解。有删改。 ①【名士míng shì】：（1）指已出名而未出仕的人。郑玄注：“名 士，不仕者。”（2）泛指有名的人。杜甫《陪李北海宴历下亭》诗：“海 内此亭古，济南名士多。”（3）特指恃才放达、不拘小节的人。”清 袁赋诚《睢阳尚书袁氏家谱》：“袁可立爱书，不事生产。所与游皆名士”（4）指刑名之士（崇尚法家之士）。《史记·律书》：“自是以后，名士迭兴，晋用咎犯，而齐用王子，吴用孙武，申明军约，赏罚必信。” 【名士】一词，源于我国古代魏晋时期 。魏晋多名士 ，他们的特点： 多隐居，峨冠博带，说怪话但博学多才，形貌潇洒，偶尔也有放浪形骸的。有云：从来圣贤皆寂寞，是真名士自风流 ②【南朝】：南朝（420—公元589，共170年）是东晋之后建 立于南方的四个朝代（宋、齐、梁、陈）的简称。自公元420年刘裕灭亡东晋王朝建立宋，接着是齐、梁、陈，而陈朝最终于589年被隋灭。 它们存在的时间都相对较短，南朝宋（420年—479年，共60年）；南朝齐（479年—502年，共24年）；南朝梁（502年—557年，共56年）；南朝陈（557年—589年，共33年）；其中最长的不过60年，最短的仅有24年，是我国历史上朝代更迭较快的一段时间。此时，中国正处于南北分治的时期，在我国历史上南朝与北方政权北魏、东魏、西魏、北齐、北周并称南北朝。 秦汉三国两晋南北朝隋唐五代十国宋元明清 ③【刘义庆】（403—444），字季伯，汉族，原籍南朝宋彭城（今 江苏徐州）人，文学家，南朝刘宋文学家。刘宋武帝刘裕之侄，在诸王 中颇为出色，十分被看重。刘义庆是这本书的编者，并不为作者。《世说新语》是魏晋南北朝时期“志人小说”的代表作。依内容可分为“德行”“言语”“政事”“文学”“方正”等三十六类，每类收有 若干则，全书共一千多则，每则文字长短不一，有的数行，有的三言两语，从此可见笔记小说“随手而记”的诉求及特性。《世说新语》主要记述世人的生活和思想，及统治阶级的情况，反映了魏晋时期文人想言行，和上层社会的生活面貌，记载颇为丰富真实，描述了当时士人所处的时代状况及政治社会环境，展示了“魏晋清谈”的风貌。京尹时期（15-30岁）。刘义庆15岁一路来平步青云，其中任秘书监一职，掌管国家的图书著作，有机会接触与博览皇家典籍，对《世说新语》的编撰奠定了良好的基础，17岁升任尚书左仆射（相当于副宰相），可惜的是，《世说新语》一书刚刚撰成，刘义庆就因病离开扬州，回到京城不久便英年早逝，时年仅41岁，宋文帝哀痛不已，赠其谥号为“康王”。 ④【王湛zhàn 】：（249～295年），字处冲，西晋太原晋阳（今山 西太原）人，官至西晋汝南内史，又称王汝南，王昶之子，王浑之弟，儿子是王承。少有识度，身长七尺八寸，龙额大鼻，少言语。服完父丧后，闭门不交宾客，冲素简淡，沉静和顺。晚成，被同族认为痴，起初只有父亲王昶欣赏他。后来被侄子王济称赏，在应答晋武帝时说王湛人材在“山涛以下，魏舒以上”，由此渐而知名。二十八岁方出仕，历任秦王文学、太子洗马、尚书郎、太子中庶子、汝南内史。元康五年（295年）去世，时为四十七岁。 【湛zhàn 】1、深：精～。～恩（深恩）。～蓝。湛深 深湛；精深 湛深的艺术功力。2. 清澈：清～。澄～。1.湛蓝 zhànlán 晴天的蓝色；湖海等的深蓝色。.湛清 清澈 天空湛清如水。 【冲素chōn ɡ sù】 亦作“冲素”。冲淡纯朴。 【冲淡chōng dàn 】冲和、淡泊，叫做冲淡。 冲淡和纤秾不同。纤秾用的是浓彩，冲淡施的是淡墨。 冲淡并非淡而无味，而是冲而不薄，淡而有味。 魏晋文人濯足清流，不染尘俗，同封建权贵不合作的精神，对安静、美好的理想境界的憧憬，是形成冲淡的一个重要原因。 ⑤【除所生服】：为父母守丧完毕。 【所生suǒ shēng 】： 1.生 身父母。： 注：“所生，指亲母。” 南朝 宋 刘义庆 《世说新语·赏誉》：“ 王汝南既除所生服，遂停墓所。 【除服】：亦称“除丧”、“脱服”。除去、脱去丧服。谓守孝三年完毕。 ⑥【墓所】：1.墓地，坟地、墓次。 【墓 mù】 埋葬死人的地方：墓穴。墓地。墓园。墓道。墓碑。坟墓。墓志铭。 【所 suǒ】 处，地方：住所。哨所。场所。处所。 机关或其他办事的地方的名称：研究所。派出所。 ⑦【王浑】（223－297），字玄冲，太原晋阳（今山西太原）人。三国曹魏后期至西晋初期的大臣，东汉代郡太守王泽之孙，曹魏司空王昶之子。承袭父亲京陵侯之位，属魏大将军曹爽部下。嘉平元年（249），曹爽被杀，王浑随之免职。后来又被起用为怀县（今河南沁阳）县令，参司马昭的安东将军军事，任散骑黄门侍郎、散骑常侍。咸熙年间（264－265），为越骑校尉。王浑曾辅佐晋武帝和晋惠帝两代君主，在晋初的军事和政治上作出了一定贡献。特别是在平吴作战方面功绩显著，因此官职累累升迁。 ⑧【王济】（246～291），字武子，太原晋阳（今山西太原）人，名士。西晋大将军王浑的次子。王济才华横溢，风姿英爽，气盖一时，被晋武帝司马炎选为女婿，配常山公主。王济爱好弓马，勇力超人，又善《易经》、《老子》、《庄子》等。文词俊茂，名于当世，与姐夫和峤及裴楷齐名。王济年四十六岁，先其父王浑而亡，追赠骠骑将军。 ⑨【拜墓】：拜扫坟墓。拜扫baì sǎo ：在墓前祭奠；扫墓。《南史·梁 纪中·武帝下》：“拜扫山陵，涕泪所洒，松草变色。” 白雪遗音·马头调·雷峰塔》：“清明拜扫，搭船借伞，前世恩人来相见。”⑨【】又如：略等（大约相等，差不多）；略绰（阔大；大略）；略订（约略计算）；略约（约略） ⑩【略不过叔】：基本上、几乎不拜访他的叔叔。 略lüè本义: 封疆土地；天子经略土地,定城国,制诸侯。——《左传·昭公七年》1、基本上，几乎，稍稍，全，皆，都 敬亭丧失其资略尽。—— 清· 黄宗羲《柳敬亭传》 略无慕艳意。——明· 宋濂《送东阳马生序》2 稍稍，稍微；略懂一点，略识文字（初识文字，认字不多）3通“掠”。抢劫;夺取 “属盗起于境，资产略尽，迫寒馁而无忧叹。”---《郝逢传》4、谋略：móu lüè，雄才大略： xióng cái dà lüè：非常杰出的才智和谋略。才，才能。略，计谋。 ?【脱时tuō】：结合上下文，应做有时、偶尔的意思来讲。偏义副词，重点由“时”字联想。脱字确实不知道作什么讲。 脱tuō 肉去骨曰脱。——《尔雅》 1. 离开，落掉：～产。～发（fà）。～节。～离。～落。～贫（摆脱贫困）。～稿（完成著作）。～手。摆～。挣～。临阵逃～。 2. 遗漏：～漏。～误。～文（因抄刊古书而误脱的字。亦称“夺文”）。3. 取下，除去：～下。～帽。～氧。～脂。～胎换骨。4. 倘若，或许：～有不测。5. 轻慢：～略（放任，不拘束）。～易（轻率，不讲究礼貌）。轻～（轻率，不持重，放荡）。 脱产学习就是参加工作后再去校内进行全日制学习的方式，其管理模式与普通高校一样，学习期间不在原单位工作，不占用周六和周日的工休时间，对学生有正常的、相对固定的授课教室和管理要求，有稳定的寒暑假期安排。 ?【止zh ǐ 】： 1. 仅，只：～有此数。不～一回。2. 停住不动：～ 步。截～。3. 拦阻，使停住：～痛。禁～。4. 古同“趾”，脚；脚趾头。 ? 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