material in a preformed monolithic conformation, [12] sug- gests its potential use in the development of optical sensing applications. Experimental PreparationofSolid 1: In a typical synthesis, mesoporous MCM-41 solid was first dried at 110C, suspended in dry toluene (1 g of solid in 30 mL) and then an excess of 3-aminopropyltriethoxysilane (3.0 mL, 13.0 mM) was added under aninertatmosphere.Themixturewasstirred,at110C,foroneday.Theresult- ing solid was filtered and washed with dichloromethane and then with ethanol, anddriedat70Cfor2h.Then,anewsuspensionwaspreparedwith1gofthe amino-functionalized solid suspended in 30 mL of ethanol. 0.5 g (2.42 mM) of 9-anthraldehydewasthenadded,andthemixturewaskeptat45Cforoneday. After that, an excess of NaBH 4 (110 mg, 2.91 mM) was added and the mixture was stirred at RT for 10±12 h. The resulting solid was filtered and washed with HCl (10 ±2 M) and then with water until the pH was 5±6. Finally, any residual reactants in the solid were removed by Soxhlet extraction over ethanol for at least 24 h. Preparation of L 1 : The synthesis of L 1 (97% yield) was carried out by con- densing 9-anthraldehyde with N-octylamine in absolute ethanol at 45C, in or- dertoobtainthecorrespondingiminethatwasreducedtothesecondaryamine after hydrogenation with sodium borohydride, in ethanol, at RT. The resulting mixturewaschromatographedonsilicagel(hexane/ethylacetate7:3). Received:February28,2002 Finalversion:April4,2002 ± [1] For some recent references see: a) P. D. Beer, P. A. Gale, Angew. Chem. Int. Ed. 2001, 40, 486. b) P. A. Gale, Coord. Chem. Rev . 2001, 213, 79. c) J. J. Lavigne, E. V. Anslyn, Angew. Chem. Int. Ed. 2001, 40, 3119. d) M. M. G. Antonisse, B. H. M. Snellink-Rul, I. Yigit, J. F. J. Eng- bersen, D. N. Reidhoudt, J . Org. Chem. 1997, 62, 9034. e) L. Fabrizzi, M. Licchelli, G. Rabaioli, A. Taglietti, Coord. Chem. Rev . 2000, 205, 85. f) P. D. Beer, J. Cadman, Coord. Chem. Rev . 2000, 205,131.g)D.H.Lee, H.Y.Lee,K.H.Lee,J.I.Hong, Chem. Commun. 2001,1188.h)H.Miya- ji, W. Sato, J. L. Sessler, Angew. Chem. Int. Ed. 2000, 39, 1777. i) C. B. Black, B. Andrioletti, A. C. Try, C. Ruiperez, J. L. Sessler, J . Am. Chem. Soc. 1999, 121, 10438. j) J. J. Lavigne, E. V. Anslyn, Angew. Chem. Int. Ed. 1999, 38,3666. [2] C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli, J. S. Beck, Nature 1992, 359,710. [3] a) S. Cabrera, J. El Haskouri, C. Guillem, J. Latorre, A. Beltrµn-Porter, D. Beltrµn-Porter, M. D. Marcos, P. Amorós, Solid State Sci. 2000, 2, 405. b)J.El Haskouri,S.Cabrera,M.CaldØs,J.Alamo,A.Beltrµn-Porter,M. D. Marcos,P.Amorós,D.Beltrµn-Porter, Int. J . Inorg. Mater. 2001, 13,192. [4] G.Wirnsberger,B. J.Scott,G. D.Stucky, Chem. Commun. 2001,119. [5] a) H. S. Zhou, I. Honma, Adv . Mater. 1999, 11, 683. b) B. Lebeau, C. E. Fowler,S.Mann,C.Farcet,B.Charleux,C.Sanchez, J . Mater. Chem. 2000, 10, 2105. c) M. Ganschow, M. Wark, D. Wöhrle, G. Schulz-Ekloff, Angew. Chem. Int. Ed. 2000, 39,161. [6] During the development of this work, a reference dealing with the use of MCM-41 functionalized solids for the determination of neutral amines was reported: V. S.-Y. Lin, C.-Y. Lai, J. Huang, S.-A. Song, S. Xu, J . Am. Chem. Soc. 2001, 123,11510. [7] The fluoride anion could not be used in this study because HFattacks the silica matrix at this pH. In fact, we have recently used this effect for the development of fluoride sensors in aqueous environments: A. B. Descal- zo, D. JimØnez, J. El Haskouri, D. Beltrµn, P. Amorós, M.D. Marcos, R.Martínez-Mµæez,J.Soto, Chem. Commun. 2002,562. [8] For a detailed study on the quenching on aminoanthracene derivatives see, for instance: a) M. E. Huston, E. U. Akkaya, A. W. Czarnik, J . Am. Chem. Soc. 1989, 111,8735.b)M.Ayadim,J.L.HabibJiwan,A.P.daSil- va, J. P. Soumillion, Tetrahedron Lett. 1996, 37, 7039. c) M. T. Albelda, M. A.Bernardo,E.García-Espaæa,M. L.Godino-Salido,S. V.Luis,M. J. Meb, F. Pina, C. Soriano, J . Chem. Soc., Perkin Trans. 2 1999, 11, 2545. d) F. Sancenón, A. Benito, J.M. Lloris, R. Martínez-Mµæez, T. Pardo, J.Soto, Helv . Chim. Acta,inpress. [9] Supramolecular Chemistry of Anions (Eds: A. Bianchi, K. Bowman- James,E.García-Espaæa),Wiley-VCH,Weinheim 1997. [10] J.Bourson,J.Pouget,B.Valeur, J . Phys. Chem. 1993, 97,4552. [11] The titration curve of the functionalized MCM-41 solid with ATP was fittedusinganequationderivedfromtheLangmuirisotherm: I  I L I LA  I L  K ATP   1K ATP   ; ATP    1 K  C M  C 0 f g   1 K  C M  C 0   2  4C 0 K q 2 (1) where K is the adsorption constant; I L and I LA are the emission fluores- cence intensities for the polyammonium-functionalized MCM-41 material inwateratpH3,andupontheadditionofalargeexcessofanion,respec- tively (Fig. 2); C 0 =added ATP (M)/solution volume (L); and C M =ad- sorbedATP (M)/solutionvolume(L). [12] J. El Haskouri, D. Ortiz de Zarate, C. Guillem, J. La Torre, M. CaldØs, A.Beltrµn,D.Beltrµn,A.B.Descalzo,G.Rodríguez-López,R.Martínez- Mµæez,M.D.Marcos,P.Amorós, Chem.Commun. 2002,330. Morphosynthesis of Organoclay Microspheres with Sponge-like or Hollow Interiors** By Eswaramoorthy Muthusamy , Dominic Walsh, and Stephen Mann* The ability to manipulate the morphogenesis of inorganic materials through chemical synthesis is an important require- ment for the control and design of complex architectures across many length scales. [1] An important strategy in mor- phosynthesis involves the inorganic replication of organized COMMUNICATIONS Adv.Mater. 2002, 14,No.13±14,July4 Ó WILEY-VCHVerlagGmbH,D-69469Weinheim,2002 0935-9648/02/1307-0969$17.50+.50/0 969 Fig. 4. a) Schematic view of the surface of solid 1, where the 30  diameter holes filled by aminoanthracene molecules have been represented (ovals repre- sent ATP anions). b) A schematic representation of the surface of solid 2, for comparison. ± [*] Prof. S. Mann,Dr. E. Muthusamy,Dr. D. Walsh SchoolofChemistry,UniversityofBristol BristolBS81TS(UK) E-mail:s.mann@bristol.ac.uk [**] We thank the EPSRC for financial support, and A. Patil for help with X-raydiffraction.