Liquid-phase epitaxial layer by layer brushing fabrication of metalorganic frameworks films

Development of metal-organic framework(MOF)films is of great importance to expand their applications.Herein,we report a facile and universal method of liquid-phase epitaxial(LPE)layer by layer(LBL)brushing approach for fabricating MOF films on various substrates in a high-throughput fashion.This MOF films preparation method offers a great prospective to cost-effectively construct films with short preparation time and little reagent consumption.Moreover,this LBL brushing approach has been implemented successfully to assemble various MOF films,including HKUST-1,zeolitic imidazolate framework-8(ZIF-8),Cu(bdc),and Cu_(2)(L)_(2)P(L=bdc,ndc,and cam;P=dabco and bipy).Afterwards,the classic MOF HKUST-1 and ZIF-8 films were grown on sensor chip electrode and porous fiber support for good volatile organic compounds(VOCs)selective sensing and water purification applications.This study demonstrates that this LBL brushing preparation method can be employed to synthesize various MOF films with a variety of characteristics to realize their sensing and separation applications.

Breaking Mirror Circularly Polarized Luminescence of Chiral Metal-Organic Frameworks by High-Pressure Stimulation

Understanding high-pressure-stimulated circularly polarized luminescence(CPL)of enantiomers remains a challenging but significant task in fundamental research and optical applications.Here,we combined in situ high-pressure photoluminescence with circularly polarized light to study how high pressure stimulated the CPL of crystalline enantiomers.Chiral lanthanide(Ln)-tartrate(Tar)metal-organic frameworks(MOFs;Ln=Eu,Tb)were synthesized to study their CPL from atmospheric pressure to 10 GPa.Under atmospheric pressure,D-and L-Eu(Tar)showed strong andmirror CPL.CPL intensity changes,emission wavelength shifts,and signal inversions were induced by increasing pressure.Note that the D-Eu(Tar)enantiomer showed strong CPL with a maximal dissymmetric factor(g_(lum))of 0.69 under 3 GPa,which is much higher than that under atmospheric pressure and of other reported MOF-based CPL materials.More interestingly,D-and L-Ln(Tar)enantiomers display obvious asymmetric CPL signals with increasing pressure,demonstrating that high pressure can break the mirror CPL of the MOF enantiomers.Our findings provide a critical understanding on in situ high-pressure CPL of chiral materials and establish a new optical phenomenon where high pressure can break the mirror CPL of enantiomers.

Surface-Oriented Assembly of Cyclodextrin Metal-Organic Framework Film for Enhanced Peptide-Enantiomers Sensing

Oriented metal-organic framework(MOF)films are attracting great attention due to their fascinating physicochemical properties and unique functionalities.Here,we report an[110]-oriented biomolecularγ-cyclodextrin(γCD)MOF film with arrayed CD channels running perpendicular to the substrate surface.This sophisticated architecturewas realized by combining liquid phase epitaxial layer-by-layer(lbl)methods with aγCD-based thiol self-assembled monolayer(SAM)functionalized surface.This first demonstration of the lbl method for MOF growth from aqueous conditions yielded oriented,highly homogeneous,and chiralγCD-SURMOFs(surfacecoordinated MOFs)with tunable thickness.Using a quartz crystal microbalance(QCM)to monitor adsorption of biomolecules,we demonstrated thatγCD-SURMOF provides highly-efficient recognition of tripeptide enantiomers(Tyr-(L-Ala)-Phe vs Tyr-(D-Ala)-Phe),clearly outperformingγCD(SH)_(8) SAMs as well as polycrystalline,mixed-orientationsγCDMOF film.The presence of well-alignedγCD-channels enables highly efficient transport channels with large adsorption capacity and fast loading,along with high enantioselectivity.In addition,the fast and highly specific loading rates allow for the realization of highly specific sensors for biomolecules with short response times.