Stimuli-Responsive Dendritic Macromolecules for Optical Detection of Metal Ions and Acidic Vapors by the Photoinduced Electron Transfer Mechanism: Paper-Based Indicator for Food Spoilage Sensing.

Visual detection of analytes has been a significant challenge in the design and development of optical chemosensors. Sensing of analytes in aqueous solution by organic molecules has encountered some issues, such as poor water solubility and quenching of optical properties. In this study, a new category of smart dendritic macromolecules was designed and synthesized by functionalization of the poly(amidoamine) (PAMAM) dendrimer with spiropyran molecules to afford a photoluminescent dendritic structure (SP-PAMAM). Smart optical sensors were prepared by physical incorporation of four different oxazolidine derivatives containing hydroxyl and nitro substituted groups into the SP-PAMAM structure. Investigation of optical properties demonstrated photoinduced electron transfer (PET) between the spiropyran end group of SP-PAMAM and oxazolidine derivatives (in a concentration of about 0.0002 M), which can result in quenching of fluorescence emission of spiropyran photoswitch in the form of merocyanine (MC). Treatment of the oxazolidine-doped SP-PAMAM samples with metal ions resulted in changes in the PET mechanism (switching on or off), as observed in the case of Fe3+, Pb2+, Cu2+, Zn2+, Cd2+, Co2+, and Ni2+ by different oxazolidine derivatives through various mechanisms (increase or decrease of fluorescence emission). These smart photoluminescent dendritic macromolecules have potential applications for photodetection of metal ions in aqueous media as optical chemosensors. In addition, the smart macromolecules displayed disconnection of PET between MC and oxazolidine and also showed red fluorescence emission under acidic conditions (pH 1-5). It is due to the protonation of the MC to MCH form and demonstrates a remarkable red shift in fluorescence spectra. The pH-responsivity of smart macromolecules was used for designing a paper-based pH indicator for visual detection of spoilage in the food industry, especially in the case of milk. The prepared papers applied on cap of the milk bottles did not show any fluorescence emission in the case of fresh milk; however, a red fluorescence emission was observed after milk spoilage as a result of adsorption of acidic volatile components generated by bacterial degradation and oxidation process on the paper surface. The reported smart papers can serve as optical portable pH indicators for timely detection of spoilage in food materials, which are usable in food packaging as smart indicator tags.

Rewritable acidochromic papers based on oxazolidine for anticounterfeiting and photosensing of polarity and pH of aqueous media.

Oxazolidine is a new category of stimuli-chromic organic compounds with unique characteristics in response to polarity, pH changes, water, light, and metal ions that were well-known as solvatochromism, acidochromism, hydrochromism, photochromism, and ionochromism, respectively. Therefore, oxazolidine derivatives have been developed for their potential applications in chemosensors, anticounterfeiting, and rewritable hydrochromic papers. In this study, various oxazolidine derivatives containing hydroxyl and naphthalene substituted groups were synthesized by using two different indolenine compounds. The synthesized oxazolidine derivatives were used for investigation of solvatochromism in different solvents, and also acidochromism in various pHs by using UV-Vis and fluorescence spectroscopies. In addition, the oxazolidine derivatives were coated on cellulosic papers using a layer-by-layer strategy to develop rewritable acidochromic papers for printing of security tags on cellulosic papers by using acidic and alkaline solutions as water-based inks. Therefore, the developed rewritable acidochromic papers could be used as security papers.

Development of highly sensitive metal-ion chemosensor and key-lock anticounterfeiting technology based on oxazolidine.

Optical chemosensors and ionochromic cellulosic papers based on oxazolidine chromophores were developed for selective photosensing of metal ions and information encryption as security tags, respectively. The oxazolidine molecules have been displayed highly intense fluorescent emission and coloration characteristics that are usable in sensing and anticounterfeiting applications. Obtained results indicated that oxazolidine molecules can be used for selective detection of pb2+ (0.01 M), and photosensing of Fe3+, Co2+ and Ag+ metal ion solutions by colorimetric and fluorometric mechanisms with higher intensity and sensitivity. Also, oxazolidine derivatives were coated on cellulosic papers via layer-by-layer method to prepare ionochromic papers. Prepared ionochromic papers were used for printing and handwriting of optical security tags by using of metal ion solutions as a new class of anticounterfeiting inks with dual-mode fluorometric and colorimetric securities. The ionochromic cellulosic papers can be used for photodetection of metal ions in a fast and facile manner that presence of metal ions is detectable by naked eyes. Also, key-lock anticounterfeiting technology based on ionochromic papers and metal ion solution as ink is the most significant strategy for encryption of information to optical tags with higher security.

Photoluminescent and Chromic Nanomaterials for Anticounterfeiting Technologies: Recent Advances and Future Challenges.

Counterfeiting and inverse engineering of security and confidential documents, such as banknotes, passports, national cards, certificates, and valuable products, has significantly been increased, which is a major challenge for governments, companies, and customers. From recent global reports published in 2017, the counterfeiting market was evaluated to be $107.26 billion in 2016 and forecasted to reach $206.57 billion by 2021 at a compound annual growth rate of 14.0%. Development of anticounterfeiting and authentication technologies with multilevel securities is a powerful solution to overcome this challenge. Stimuli-chromic (photochromic, hydrochromic, and thermochromic) and photoluminescent (fluorescent and phosphorescent) compounds are the most significant and applicable materials for development of complex anticounterfeiting inks with a high-security level and fast authentication. Highly efficient anticounterfeiting and authentication technologies have been developed to reach high security and efficiency. Applicable materials for anticounterfeiting applications are generally based on photochromic and photoluminescent compounds, for which hydrochromic and thermochromic materials have extensively been used in recent decades. A wide range of materials, such as organic and inorganic metal complexes, polymer nanoparticles, quantum dots, polymer dots, carbon dots, upconverting nanoparticles, and supramolecular structures, could display all of these phenomena depending on their physical and chemical characteristics. The polymeric anticounterfeiting inks have recently received significant attention because of their high stability for printing on confidential documents. In addition, the printing technologies including hand-writing, stamping, inkjet printing, screen printing, and anticounterfeiting labels are discussed for introduction of the most efficient methods for application of different anticounterfeiting inks. This review would help scientists to design and develop the most applicable encryption, authentication, and anticounterfeiting technologies with high security, fast detection, and potential applications in security marking and information encryption on various substrates.

Encryption and authentication of security patterns by ecofriendly multi-color photoluminescent inks containing oxazolidine-functionalized nanoparticles.

Counterfeiting of confidential documents has been a costly challenge for banks, companies, and customers. Encryption of invisible security marks, such as barcodes, quick response codes, and logos, in national or international confidential documents by high-security anticounterfeiting inks is the most significant solution for counterfeiting problems. Ecofriendly multi-color photoluminescent anticounterfeiting inks based on highly-fluorescent polymer nanoparticles functionalized with new oxazolidine derivatives were developed for the fast and facile encryption of security labels on cellulosic documents, such as paper currency, passport, and certificate. Depending on the polarity of functionalized polymer nanoparticles, a wide range of colors and fluorescence emissions were observed as a result of polar-polar interactions between the oxazolidine molecules and surface functional groups of the nanoparticles. The fluorescent polymer nanoparticles showed spherical, vesicular, and cauliflower-like morphologies resulted from different surface functional groups. Functional polymer nanoparticles displayed high stability and printability on cellulosic substrates due to hydrogen bonding interactions. The highly-fluorescent polymer nanoparticles were also used to prepare anticounterfeiting inks with different colors and fluorescence emissions. All the ecofriendly polymeric anticounterfeiting inks were loaded to stamps with specific marks, and then applied to different confidential documents. Printed labels displayed highly intense fluorescence emission in different colors (green, orange, pink, and purple depending on the matrix polarity) under UV irradiation (365 nm). These water-based multi-color fluorescent anticounterfeiting inks with highly intense, bright, and sensitive fluorescence emission have potential applications in encryption and authentication of security patterns.

Encryption and optical authentication of confidential cellulosic papers by ecofriendly multi-color photoluminescent inks.

Photodetection of originality and authentication of security documents such as money, passport, bank note, and national card have been a significant challenge in recent decade. Using of advanced optical systems could remarkably reduce copy and counterfeiting of such national and international documents. Novel ecofriendly multi-color photoluminescent inks were developed for information encryption on cellulosic papers and optical authentication of confidential/original documents by synthesis of water-based latex nanoparticles modified with photoluminescent coumarin (blue emission) and two photochromic spiropyran derivatives (red and orange emissions). Some of the latexes with higher fluorescence emission were formulated to water-based inks, and then loaded to stamps with different marks for printing of quick response code, barcode, finger print, and other marks on cellulosic documents. All of the printed marks display ultra-bright blue, red, and orange fluorescence emissions upon UV irradiation, which have potential applications in encryption, security marking and optical authentication of confidential cellulose substrates.

Light-, temperature-, and pH-responsive micellar assemblies of spiropyran-initiated amphiphilic block copolymers: Kinetics of photochromism, responsiveness, and smart drug delivery.

Multi-responsive polymer assemblies are a significant class of smart polymers with potential applications in drug-delivery and gen-delivery systems. Poly(dimethylaminoethyl methacrylate) (PDMAEMA) is among the most applicable multi-responsive polymers that changes its physical and chemical properties in response to temperature, pH, and CO2. Herein, different types of light-, temperature-, pH-, and CO2-responsive polymer assemblies were developed based on multi-responsive PDMAEMA and hydrophobic poly(methyl methacrylate) blocks. In addition, spiropyran was incorporated at the chain ends by using spiropyran-initiated atom transfer radical polymerization method. Novel smart drug-delivery systems were developed by self-assembly of these amphiphilic block copolymers to micellar morphologies in aqueous media. Dynamic light scattering results showed that size of the polymer assemblies changed in response to pH variations (from 5 to 9), temperature changes (above the lower critical solution temperature (LCST) of PDMAEMA), and also UV light irradiation (wavelength of 365 nm). The LCST of PPDMAEMA showed a shift from 53 to 60 °C after isomerization of the SP to MC form, as a result of increase of polarity and water-solubility. The PDMAEMA block results in responsivity of the prepared copolymer assemblies to CO2, which display pH variation from 8-8.6 to 5-6 after 2 min of CO2 gas bubbling. All the multi-responsive micellar polymer assemblies showed various loading capacities and release profiles, and the DOX release can be controlled by pH, temperature, and light. The release efficiency is reached to 60-85% at pH 5.3, 80-90% at temperatures higher than the LCST of PDMAEMA (60 °C), and also 90-100% under UV light irradiation after 48 h. In summary, the multi-responsive polymer assemblies based on amphiphilic block copolymers containing spiropyran chain end groups in the current study have potential applications in smart drug-delivery systems, and offer controlling over the drug-release by different triggers, such as light irradiation, pH variation, and temperature change. A very low concentration of spiropyran molecules (one per polymer chain) showed light-controlling of drug-release from the assemblies with high efficiencies.

Synthesis and biological evaluation of novel isoxazolo[4,3-e]indoles as antibacterial agents.

The synthesis of a new series of 8-bromo-6-alkyl-1-aryl-6H-isoxazolo[4,3-e]indole derivatives is described. All the newly synthesized compounds were screened for their antibacterial activity against Escherichia coli HB101, Staphylococcuse aureus pathogens (methicillin resistant S. aureus and methicillin susceptible S. aureus), Pseudomonas aeruginosa, and Bacillus subtilis; also MIC values of these compounds were determined.