Magnetic and Transparent Composites by Linking Liquid Crystals to Ferrite Nanoparticles through Covalent Networks

The fabrication of transparent, flexible, and optically homogeneous magnetic composites containing ferrite (Fe₃O₄) nanoparticles, liquid crystals (LCs), and siloxane backbones is reported. The transparent magnets are achieved by covalently bonding LCs to the siloxane backbones and then linking them to dopamine‐functionalized ferrite nanocrystals. They exhibit simultaneous high transparency and strong magnetic properties. A remarkable feature of these films is that the surface morphology of the LC‐attached ferrite films can be tuned by an external magnetic field, demonstrating a striped surface in the direction of the field. We show that the LC‐attached film can act as an alignment layer to orient LCs, enabling the development of LC alignment surfaces on the basis of these nanomagnet–LC polymer composites.     

Photo‐ and Rubbing‐Alignable Brush Polyimides Bearing Three Different Chromophores

Three new photoreactive brush polyimides (PSPIs), each bearing a different type of chromophore (cinnamoyl (CA), 3‐(2‐furyl)acryloyl (FA), and methacryloyl (MA)) in their bristles (i.e., side groups), are successfully synthesized, and are found to produce good‐quality films with smooth surfaces through conventional spin‐casting and drying processes. These PSPI polymers are thermally stable up to 320 °C. This is the first quantitative investigation of the photoaligning and rubbing‐aligning processabilities of PSPI polymer films, and of the abilities of the resultant films to control the orientation and anchoring of liquid‐crystal (LC) molecules. The chromophores of both poly(1‐cinnamoyloxy‐2,4‐phenylene hexafluoroisopropylidenediphthalimide) (6F‐DAP‐CA) and poly(1‐3‐(2‐furyl)acryloyloxy‐2,4‐phenylene hexafluoroisopropylidenediphthalimide) (6F‐DAP‐FA) PSPIs are found to undergo photodimerization in thin films and, to a lesser extent, photoisomerization, resulting in insoluble, crosslinked films. The MA chromophores of 6F‐DAP‐MA PSPI are found to undergo photopolymerization in thin films, which might include photodimerization to a lesser extent, resulting in insoluble, crosslinked films. Thin films of the PSPI polymer chains are found to have excellent unidirectional orientation ability as a result of either photoexposure with linearly polarized UV light (LPUVL) or rubbing. Both the photoaligned and the rubbing‐aligned polymer chains in the PSPI films are demonstrated to effectively induce the alignment of nematic LCs along their orientation directors by anisotropic interactions between the preferentially oriented polymer chain segments and the LCs. The contribution to LC alignment of the microgrooves developed in the rubbed films is found to be very low. The anchoring energies of the LCs on the photoaligned film surfaces are comparable to those on the rubbing‐aligned film surfaces; the anchoring energies are found to be in the range 0.45–2.25 × 10^–5 J m^–2, and to depend on which film treatment process is used and which chromophore bristle is present. In summary, the new PSPIs reported in this paper are promising LC alignment‐layer candidates with rubbing‐free processing for the production of advanced LC‐display (LCD) devices, including LCD televisions with large display areas.     

Porous Silicon Films Micropatterned with Bioelements as Supports for Mammalian Cells

Porous silicon (pSi) surfaces have been chemically patterned via a UV initiated hydrosilylation reaction of an alkene through a photomask, introducing chemical functionality in the exposed surface areas. A secondary, UV initiated hydrosilylation reaction with a second alkene of different functionality is performed to backfill the silicon hydride terminated regions on the surface, thereby affording patterned porous films with dual, surface chemistry. UV initiated hydrosilylations were performed using the alkene undecylenic acid N‐hydroxysuccinimide (NHS) ester, and the pSi surfaces were stabilized by a second hydrosilylation reaction with a polyethylene glycol (PEG) appended alkene. NHS ester and PEG functionalized surfaces were used for the selective immobilization of the cell adhesion mediator protein fibronectin (FN), in the NHS‐functional regions. Matrix‐assisted laser desorption/ionization mass spectrometry imaging on the protein functionalized pSi surface confirmed the patterned conjugation of the FN to the NHS functionalized regions. Mammalian cells cultured on these surfaces showed attachment that was confined to the patterned areas of FN on the pSi surface.     

Real‐Time Liquid Crystal pH Sensor for Monitoring Enzymatic Activities of Penicillinase

A liquid crystal (LC)‐based pH sensor for real‐time monitoring of changes in localized pH values near a solid surface is reported, along with its application for the detection of enzymatic activities. It is found that 4‐cyano‐4′‐pentylbiphenyl (5CB), when doped with 4′‐pentyl‐biphenyl‐4‐carboxylic acid (PBA), shows a bright‐to‐dark optical response to a very small change in pH (from 6.9 to 7.0). The pH‐driven optical response can be explained by using orientational transitions of 5CB induced by the protonation and deprotonation of PBA at the aqueous/LC interface. Because of its high pH sensitivity, the LC‐based sensor is further exploited for monitoring local pH changes resulting from enzymatic reactions. As a proof of concept, the hydrolysis of penicillin G by surface‐immobilized penicillinase is monitored using the system, even when the concentration of penicillin G is as low as 1 nM . This type of LC‐based sensor may find potential utilities in high‐throughput screening of enzyme substrates and enzyme inhibitors.     

Chiroptical Resolution and Thermal Switching of Chirality in Conjugated Polymer Luminescence via Selective Reflection using a Double‐Layered Cell of Chiral Nematic Liquid Crystal

An optically resolvable and thermally chiral‐switchable device for circularly polarized luminescence (CPL) is first constructed using a light‐emitting conjugated polymer film and a double‐layered chiral nematic liquid crystal (N*‐LC) cell. The double‐layered N*‐LC cell with opposite handedness at each layer is fabricated by adding each of two types of N*‐LCs into each of the cells, and the N*‐LCs consist of nematic LCs and chiral dopants with opposite chirality and different mole concentrations. The selective reflection band due to the N*‐LC is thermally shifted so that the band wavelength is close to the luminescence band of the racemic conjugated polymer, such as disubstituted polyacetylene (diPA), yielding CPL with opposite handedness and high dissymmetry factor values (|g_lum|) of 1.1–1.6 at low and high temperatures. The double‐layered N*‐LC cell bearing the temperature‐controlled selective reflection is useful for generating CPLs from racemic fluorescent materials and for allowing thermal chirality‐switching in CPLs, which present new possibilities for optoelectronic and photochemical applications.     

Cell Adhesion and Cellular Patterning on a Self‐Assembled Monolayer of Zeolite L Crystals

Chemically functionalized self‐assembled monolayers made by disk‐shaped zeolite L nanocrystals are used as models for biocompatible surfaces to study cell‐adhesion behavior. Different chemical groups lead to different cellular behavior and fluorescent‐molecule‐loaded zeolites allow the position of the cells to be determined. Furthermore, a patterned monolayer of asymmetrically functionalized zeolite L obtained by microcontact chemistry is used to grow cells. A spatial recognition of the cells, which proliferate only on the bioactive‐molecule‐functionalized stripes, is possible.     

Highly Oriented Nanofibrils of Regioregular Poly(3‐hexylthiophene) Formed via Block Copolymer Self‐Assembly in Liquid Crystals

A novel method making use of block copolymer self‐assembly in nematic liquid crystals (LCs) is described for preparing macroscopically oriented nanofibrils of π‐conjugated semiconducting polymers. Upon cooling, a diblock copolymer composed of regioregular poly(3‐hexylthiophene) (P3HT) and a liquid crystalline polymer (LCP) in a block‐selective LC solvent can self‐assemble into oriented nanofibrils exhibiting highly anisotropic absorption and polarized photoluminescence emission. An unusual feature of the nanofibrils is that P3HT chains are oriented along the fibrils' long axis. This general method makes it possible to use LCs as an anisotropic medium to grow oriented nanofibrils of many semiconducting polymers insoluble in LCs.     

Spatially Selective Nucleation of Metal Clusters on the Tobacco Mosaic Virus

Tobacco mosaic virus (TMV) is a very stable nanotube complex of a helical RNA and 2130 coat proteins. The special shape makes it an interesting nano‐object, especially as a template for chemical reactions. Here we use TMV as a chemically functionalized template for binding metal ions. Different chemical groups of the coat protein can be used as ligands or to electrostatically bind metal ions. Following this activation step, chemical reduction and electroless plating produces metal clusters of several nanometers in diameter. The clusters are attached to the virion without destroying its structure. Gold clusters generated from an ascorbic acid bath bind to the exterior surface as well as to the central channel of the hollow tube. Very high selectivity is reached by tuning Pd^II and Pt^II activations with phosphate: When TMV is first activated with Pd^II, and thereafter metallized with a nickel–phosphinate bath, 3 nm nickel clusters grow in the central channel; when TMV from phosphate‐buffered suspensions is employed, larger nickel clusters grow on the exterior surface. Phosphate buffers have to be avoided when 3 nm nickel and cobalt wires of several 100 nm in length are synthesized from borane‐based baths inside the TMV channel. The results are discussed with respect to the inorganic complex chemistry of precursor molecules and the distribution of binding sites in TMV.     

Inside Front Cover: Unprecedented Dual Alignment Mode and Freedericksz Transition in Planar Nematic Liquid Crystal Cells Doped with Gold Nanoclusters (Adv. Funct. Mater. 2/2008)

On p. 212, Torsten Hegmann and co‐workers describe nematic liquid crystals (N‐LCs) confined in planar liquid crystal cells after doping with small quantities of gold nanoclusters. These give rise to a dual alignment mode and electro‐optic response (Freedericksz transition). By fine‐tuning of experimental conditions, N‐LCs doped with gold nanoclusters can be electrically reoriented and aligned either like N‐LCs with a positive dielectric anisotropy (used in twisted nematic displays) in a planar cell or alternatively as N‐LCs with a negative dielectric anisotropy (used in large LCD TVs based on the vertical alignment mode). We demonstrate that alkylthiol‐capped gold nanoclusters doped into nematic liquid crystals (N‐LCs) with positive dielectric anisotropy give rise to an unprecedented dual alignment mode and electro‐optical response, which has a potential impact on current liquid crystal (LC) display technologies and N‐LC optical‐biosensor design. By fine‐tuning experimental conditions (temperature, electric field, and alignment), N‐LCs doped with gold nanoclusters can be aligned and electrically reoriented either like N‐LCs with a positive dielectric anisotropy in a planar cell or, alternatively, as N‐LCs with a negative dielectric anisotropy in a homeotropic cell, both at lower threshold voltages than the pure N‐LC.     

Towards Efficient Dispersion of Carbon Nanotubes in Thermotropic Liquid Crystals

Motivated by numerous recent reports indicating attractive properties of composite materials of carbon nanotubes (CNTs) and liquid crystals (LCs) and a lack of research aimed at optimizing such composites, the process of dispersing CNTs in thermotropic LCs is systematically studied. LC hosts can perform comparably or even better than the best known organic solvents for CNTs such as N‐methyl pyrrolidone (NMP), provided that the dispersion process and choice of LC material are optimized. The chemical structure of the molecules in the LC is very important; variations in core as well as in terminal alkyl chain influence the result. Several observations moreover indicate that the anisotropic nematic phase, aligning the nanotubes in the matrix, per se stabilizes the dispersion compared to a host that is isotropic and thus yields random tube orientation. The chemical and physical phenomena governing the preparation of the dispersion and its stability are identified, taking into account enthalpic, entropic, as well as kinetic factors. This allows a guideline on how to best design and prepare CNT–LC composites to be sketched, following which tailored development of new LCs may take the advanced functional material that CNT–LC composites comprise to the stage of commercial application.     

Nanosensor Design Packages: A Smart and Compact Development for Metal Ions Sensing Responses

With recent advances in mesostructured materials and nanotechnologies, new methods are emerging to design optical sensors and biosensors, and to develop highly sensitive solid sensors. Here, highly sensitive, low cost, simple nanosensor designs for naked‐eye detection of toxic metal ions are successfully developed by the immobilization of commercially available α,β,γ,δ‐tetrakis(1‐methylpyridinium‐4‐yl)porphine p‐toluenesulfonate (TMPyP) and diphenylcarbazide (DPC), and chemically synthesized 4‐n‐dodecyl‐6‐(2‐thiazolylazo) resorcinol (DTAR) and 4‐n‐dodecyl‐6‐(2‐pyridylazo) phenol (DPAP) chromophore molecules into spherical nanosized cavities and surfaces. A rational strategy was crucial to develop optical nanosensors that can be used to control accurate recognition and signaling abilities of analyte species for ion‐sensing purposes. This is the first reported evidence of the significant key factors of the development of receptors as ‘indicator dyes' and surface‐confinement materials as ‘carriers' to broadening the applicability of optical chemical sensors for selective discrimination of trace levels of toxic analytes. In all the nanosensor design techniques presented here, a dense pattern of immobilized hydrophobic ‘neutral' and hydrophilic ‘charged' chromophores with intrinsic mobility, as a result of extremely robust constructed sequences on nanoscale structures, is a key to enhancing the sensing functionality of optical nanosensors. These nanosensor designs can be used as cage probe sinks with reliable control, for the first time, over the colorimetric recognition of cadmium ions to low levels of concentration in the range of 10^–9 to 10^–10 M . Optimization of control sensing conditions is established to achieve enhanced signal response and color intensities. These chemical nanosensors are reversible and have the potential to serve effectively in on‐site field analysis of environmental samples, which eliminates the necessity for instrument‐dependent analysis. Moreover, these new classes of optical cage sensors exhibit long‐term stability of signaling and recognition functionalities that in general provide extraordinary sensitivity, selectivity, reusability, and fast kinetic detection and quantification of various deleterious metal ions in our environment.     

Optical Nanoscale Pool‐on‐Surface Design for Control Sensing Recognition of Multiple Cations

General design of optical chemical nanosensors is needed to develop efficient sensing systems with high flexibility, and low capital cost for control recognition of toxic analytes. Here, we designed optical chemical nanosensors for simple, high‐speed detection of multiple toxic metal ions. The systematic design of the nanosensors was based on densely patterned chromophores with intrinsic mobility, namely, “building‐blocks” onto three‐dimensional (3D) nanoscale structures. The ability to precisely modify the nanoscale pore surfaces by using a broad range of chromophores that have different molecular sizes and characteristics enables detection of multiple toxic ions. A key feature of this building‐blocks design strategy is that the surface functionality and good adsorption characteristics of the fabricated nanosensor arrays enabled the development of “pool‐on‐surface” sensing systems in which high flux of the metal analytes across the probe molecules was achieved without significant kinetic hindrance. Such a sensing design enabled sensitive recognition of metal ions up to sub‐picomolar detection limits (～10^?11 mol dm^?3), for first time, with rapid response time within few seconds. Moreover, because these sensing pools exhibited long‐term stability, reversibility and selectivity in detecting most pollutant cations, for example, Cr(VI), Pb(II), Co(II), and Pd(II) ions, they are practical and inexpensive. The key result in our study is that the pool‐on‐surface design for optical nanosensors exhibited significant ion‐selective ability of these target ions from environmental samples and waste disposals.     

Synthesis and Characterization of Bifunctionalized Ordered Mesoporous Materials

Direct synthesis (co‐condensation reaction) and post‐synthesis reaction (grafting) are combined for the first time to efficiently fabricate bifunctionalized ordered mesoporous materials (OMMs). Ethylenediamine‐containing OMMs (ED‐MCM‐41) were first synthesized via direct synthesis and then further modified by the phenyl (PH) group in a supercritical fluid (SCF) medium via grafting reaction, resulting in OMMs with ED and PH groups (PH‐ED‐MCM‐41). X‐ray diffraction (XRD) patterns, N₂ sorption properties, transmission electron microscopy (TEM), ²⁹Si and ¹³C magic angle spinning (MAS) NMR, chemical analysis, and hydrothermal treatment were used to characterize the bifunctionalized materials. Experiments show that bifunctionalized OMMs can be efficiently prepared by modifying the directly synthesized monofunctionalized OMMs via grafting reaction in a supercritical fluid medium. Both functional groups are distributed uniformly at the surfaces. The advantage of bifunctionalized OMMs over monofunctionalized OMMs was illustrated by introducing thiol groups into ED‐MCM‐41 materials and the subsequent formation of CdS nanocrystals inside thiol‐ and ED‐functionalized MCM‐41 (HS‐ED‐MC‐41). Because of the variety of the functional groups that can be introduced into OMMs by direct synthesis or post‐synthesis reaction, it is expected that the present strategy could provide a generally applicable approach to the design of OMMs with two functional groups.     

Surface Chemistry of Vitamin: Pyridoxal 5′‐Phosphate (Vitamin B6) as a Multifunctional Compound for Surface Functionalization

Vitamins are non‐toxic compounds that perform a variety of biological functions and also available in a large quantity. Other than the usage as food supplements, few attempts have been made to use them as functional materials. In this study, we report that vitamin B6, pyridoxal 5′‐phosphate (PLP), is a multi‐functional molecule for oxide surface chemistry. PLP‐immobilized surfaces exhibit superhydrophilicity and even hemophilicity, enhancing proliferation, migration, and differentiation of mammalian cells. Unlike existing molecules used so far in surface modification, PLP has an intrinsic chemical reactivity toward biomacromolecules due to the presence of the aldehyde group. In fact, RGD peptide is covalently tethered onto PLP surfaces directly in one step without any chemical activation. Furthermore, PLP‐functionalized implant device showed rapid bone healing. As vitamin B6 is a FDA approved molecule for human usage, the surface chemistry of vitamin B6 potentially allows a fast route for surface functionalized medical devices into clinic.     

Functionalized Cellulose for Water Purification,Antimicrobial Applications,and Sensors

As the most abundant natural polymer, cellulose presents a unique advantage for large‐scale applications. To fully unlock its potential, the introduction of desired functional groups onto the cellulose backbone is required, which can be realized by either chemical bonding or physical surface interactions. This review gives an overview of the chemistry behind the state‐of‐the‐art functionalization methods (e.g., oxidation, esterification, grafting) for cellulose in its various forms, from nanocrystals to bacterial cellulose. The existing and foreseeable applications of the obtained products are presented in detail, spanning from water purification and antibacterial action, to sensing, energy harvesting, and catalysis. A special emphasis is put on the interactions of functionalized cellulose with heavy metals, focusing on copper as a prime example. For the latter, its toxicity can either have a harmful influence on aquatic life, or it can be conveniently employed for microbial disinfection. The reader is further introduced to recent sensing technologies based on functionalized cellulose, which are becoming crucial for the near future especially with the emergence of the internet of things. By revealing the potential of water filters and conductive clothing for mass implementation, the near future of cellulose‐based technologies is also discussed.     

Organosilica Materials with Bridging Phenyl Derivatives Incorporated into the Surfaces of Mesoporous Solids

An interesting class of materials is mesoporous organosilica materials containing a bridging, organic group along the pore‐surface. Such materials are prepared from silsesquioxane precursors of the type (R′O)₃Si‐R‐Si(OR′)₃ where R is the bridging organic group of interest, in combination with a lyotropic phase as a template for the generation of the pores. A new silsesquioxane precursor, 1,3‐bis‐(trialkoxysilyl)‐5‐bromobenzene, and the related mesoporous organosilica material containing bromobenzene groups located at the pore walls are presented in the current publication. The latter precursor allows access to the derivatization reactions known for halogenated aromatic compounds. Materials containing phenyl derivatives can be obtained either by chemical modifications starting from the mentioned precursor on the molecular scale, or the modifications can be performed directly at the surfaces of the porous material. Materials with surfaces containing benzoic acid, styrene, and phenylphosphonic acid are described.     

Titania and Mixed Titania/Aluminum,Gallium, or Indium Oxide Spheres: Sol–Gel/Template Synthesis and Photocatalytic Properties

Porous polymer beads have been used as templates in which sol–gel chemistry was conducted for the formation of porous titanium dioxide and titania/aluminum, gallium, or indium oxide spheres. The addition of 5, 10, and 15 wt.‐% of the second metal oxide to titania was studied, resulting in little variation in the final porous‐sphere diameter, but in a decreased titania nanocrystal size and an increased specific surface area of the material. The crystallinity of the samples was observed after heating at 550, 750, and 950 °C as anatase to rutile phase transitions became apparent and peaks from the added metal oxide were observed with the increase in temperature. Photocatalytic decomposition of 2‐chlorophenol was monitored in the presence of the titania and titania/metal‐oxide spheres showing that a 5 wt.‐% addition of the second metal oxide gave best photocatalytic results for all the metal oxides studied. At a pH of 6 the pure titania spheres were less photocatalytically active than the Degussa P25 titania, however the mixed titania/5 wt.‐% metal‐oxide samples were more active than the standard in the order In (least active), Ga, then Al (most active). Variation of the solution pH (between pH 2 and 10) had little influence on the photocatalytic activity of the titania/5 wt.‐% aluminum oxide material, more effect on the titanium/5 wt. % gallium oxide, and the most pronounced effect on the titanium/5 wt.‐% indium oxide, with increased activity at higher pH values. The adsorption of pyridine to the titania samples containing the second metal oxide indicated the presence of Lewis‐acid sites.     

Enhanced Osteoblast Adhesion to Epoxide‐Functionalized Surfaces

As an alternative to expensive extracellular matrix (ECM) proteins generally applied as coatings in Petri dishes used for cell binding, an innovative system based on epoxide‐functionalized monolayers capable of protein binding is proposed. Since cells bind to material surfaces through proteins, protein‐binding surfaces should also promote cell binding. Here we investigate how the cell‐binding properties of an epoxide‐functionalized surface compares with ECM protein gel coated surfaces and tissue culture polystyrene control surfaces. Glass surfaces are functionalized with glycidoxypropyltriethoxysilane (GOPS), which results in an epoxide‐functionalized surface capable of binding proteins through an epoxide–amine reaction. Advancing contact angle measurements and atomic force microscopy measurements confirm the formation of a homogeneous GOPS monolayer. This monolayer is micropatterned with fluorescein‐labeled ECM protein gel by microcontact printing (µCP). Confocal laser scanning microscopy (CLSM) shows accurately transferred ECM protein gel micropatterns. Osteoblasts that are seeded on these micropatterned substrates show a clear preference for adhering to the epoxide‐functionalized areas. The morphology of these cultured osteoblasts is needle‐like with high aspect ratios. As controls, osteoblasts are cultured on GOPS‐functionalized surfaces, unstructured ECM protein gel surfaces, and tissue culture polystyrene (TCPS). The GOPS surfaces demonstrate a drastic increase in cell adhesion after 2 h, whilst the other tests show no adverse effects of this surface on the osteoblasts as compared to ECM and TCPS. CLSM shows healthy cell morphologies on each surface. It is demonstrated for the first time that epoxide groups outperform ECM protein gel in cell adhesion, thereby providing new routes for cost‐effective coatings that improve biocompatibility as well as exciting, new methodologies to control and direct cell adhesion.     

Selective Zinc(II)‐Ion Fluorescence Sensing by a Functionalized Mesoporous Material Covalently Grafted with a Fluorescent Chromophore and Consequent Biological Applications

A highly ordered 2D‐hexagonal mesoporous silica material is functionalized with 3‐aminopropyltriethoxysilane. This organically modified mesoporous material is grafted with a dialdehyde fluorescent chromophore, 4‐methyl‐2,6‐diformyl phenol. Powder X‐ray diffraction, transmission electron microscopy, N₂ sorption, Fourier transform infrared spectroscopy, and UV‐visible absorption and emission have been employed to characterize the material. This material shows excellent selective Zn²⁺ sensing, which is due to the fluorophore moiety present at its surface. Fluorescence measurements reveal that the emission intensity of the Zn²⁺‐bound mesoporous material increases significantly upon addition of various concentrations of Zn²⁺, while the introduction of other biologically relevant (Ca²⁺, Mg²⁺, Na⁺, and K⁺) and environmentally hazardous transition‐metal ions results in either unchanged or weakened intensity. The enhancement of fluorescence is attributed to the strong covalent binding of Zn²⁺, evident from the large binding constant value (0.87 × 10⁴ M ^?1). Thus, this functionalized mesoporous material grafted with the fluorescent chromophore could monitor or recognize Zn²⁺ from a mixture of ions that contains Zn²⁺ even in trace amounts and can be considered as a selective fluorescent probe. We have examined the application of this mesoporous zinc(II) sensor to cultured living cells (A375 human melanoma and human cervical cancer cell, HeLa) by fluorescence microscopy.     

Spray‐Layer‐by‐Layer Carbon Nanotube/Electrospun Fiber Electrodes for Flexible Chemiresistive Sensor Applications

Development of a versatile method for incorporating conductive materials into textiles could enable advances in wearable electronics and smart textiles. One area of critical importance is the detection of chemicals in the environment for security and industrial process monitoring. Here, the fabrication of a flexible, sensor material based on functionalized multi‐walled carbon nanotube (MWNT) films on a porous electrospun fiber mat for real‐time detection of a nerve agent simulant is reported. The material is constructed by layer‐by‐layer (LbL) assembly of MWNTs with opposite charges, creating multilayer films of MWNTs without binder. The vacuum‐assisted spray‐LbL process enables conformal coatings of nanostructured MWNT films on individual electrospun fibers throughout the bulk of the mat with controlled loading and electrical conductivity. A thiourea‐based receptor is covalently attached to the primary amine groups on the MWNT films to enhance the sensing response to dimethyl methylphosphonate (DMMP), a simulant for sarin nerve agent. Chemiresistive sensors based on the engineered textiles display reversible responses and detection limits for DMMP as low as 10 ppb in the aqueous phase and 5 ppm in the vapor phase. This fabrication technique provides a versatile and easily scalable strategy for incorporating conformal MWNT films into three‐dimensional substrates for numerous applications.