One-pot Synthesis of High-performance Green-emitting Carbon Dots for Cd2+ Sensing and Anti-counterfeiting Applications.

This study presents a facile one-pot solvothermal synthesis of high-performance green fluorescent carbon dots (G-CDs) using o-phenylenediamine and ethylenediamine as precursors. The G-CDs show excellent optical, temporal, and chemical stability. Notably, they exhibit the highest quantum yield of 24.2% in ethanol and a strong green emission peaking at 546 nm under 440-490 nm excitation. In addition, G-CDs have outstanding salt resistance and multi-solvent compatibility. Due to its bright photoluminescence, G-CDs can be used as a secure ink for anti-counterfeiting. More remarkably, Cd2+ ions can efficiently quench the fluorescence of G-CDs with a detection limit of 0.152 µmol/L, enabling accurate quantification of Cd2+ in water systems. The simple synthesis of high-performance G-CDs expands their applicability in sensing and bioimaging.

Carbon dots as specific fluorescent sensors for Hg2+ and glutathione imaging.

Nitrogen-doped carbon dots (NCDs) have been constructed in which coal washing wastewater is used as carbon precursor, tryptophan is added for nitrogen doping and surface functional together with polyethylene glycol. The nitrogen doping and surface functional with electron rich groups resulted in excellent fluorescent properties regarding stability, reversibility, printability with high quantum yield which not only enable the NCDs as fluorescent ink for advanced message encryption, but also realize specific on-off-on fluorescent sensing of Hg2+ and GSH as solution, hydrogel and filter paper sensors. The NCDs had a linear range of 0.01-100 µM and a detection limit of 6.27 nM (RSD 0.33%) for Hg2+ and the NCDs@Hg2+ had a linear range of 0.01-60 µM and a detection limit of 3.53 nM (RSD 1.53%) for GSH in sensing studies with aqueous solutions. In addition, with the low cytotoxicity and good biocompatibility NCDs have been successfully used for imaging Hg2+ and GSH in living MG-63 cells. The presented NCDs recycle waste coal washing water into worthwhile material which can be implemented as promising anti-counterfeiting and message encryption candidates as well as effective Hg2+ and GSH sensing, tracking and removing tools in complicated environmental and biological systems.

Synthesis of Temperature Sensing Nitrogen-Doped Carbon Dots and Their Application in Fluorescent Ink.

With the discovery of research, many properties of carbon dots are getting better and better. People have taken advantage of this and utilized them interspersed in various fields. In the present study, water-soluble nitrogen-doped carbon dots (N-CDs) with excellent optical and fluorescence thermal properties were prepared by the hydrothermal method using 4-dimethylaminopyridine and N,N'-methylenebisacrylamide as precursors. Co2+ has a selective bursting effect on the fluorescence of N-CDs. The fluorescence of N-CDs is selectively burst by Co2+, and the high sensitivity is good in the range of 0-12 µM with a detection limit of 74 nM. In addition, the good temperature response (reversible and recoverable fluorescence in the temperature range of 20~90 °C) and excellent optical properties of the N-CDs also make them new potentials in the field of fluorescent inks and temperature sensing.

Fluorescence 'off-on' probe for lead (II) detection based on Atractylodes III CQDs and bioimaging.

In this work, a type of carbon quantum dots (CQDs) with bright blue emission was readily fabricated through one-step hydrothermal treatment from Atractylodes III. We explored the surface morphology and optical properties of the CQDs using transmission electron microscopy, X-ray diffraction patterns, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and ultraviolet-visible light spectrophotometry. The obtained CQDs possessed good photoluminescence properties, water solubility, and biocompatibility. The fluorescence quantum yield of these was 3.72%. It was found that the fluorescence intensity of CQDs was quenched by picric acid. After adding lead (II), the fluorescence could be effectively recovered. Therefore, an 'off-on' fluorescence probe was designed to detect lead (II) in the range 0-580 µM and the limit of detection was 0.068 µM. In addition, the experiments showed that the CQDs could be successfully used in bioimaging and as a hidden fluorescent ink.

Physically unclonable security patterns created by electrospinning, and authenticated by two-step validation method.

Counterfeiting is a growing economic and social problem. For anticounterfeiting, random and inimitable droplet/fiber patterns were created by the electrospinning method as security tags that are detectable under UV light but invisible in daylight. To check the authenticity of the original security patterns created; images were collected with a simple smartphone microscope and a database of the recorded original patterns was created. The originality of the random patterns was checked by comparing them with the patterns recorded in the database. In addition, the spectral signature of the patterns in the droplet/fiber network was obtained with a simple and hand-held spectrometer. Thus, by reading the spectral signature from the pattern, the spectral information of the photoluminescent nanoparticles was verified and thus a second-step verification was established. In this way, anticounterfeiting technology that combines ink formula, unclonable security pattern creation and two-level verification is developed.

Photophysical Investigation of a Benzimidazole Derivative and Its Applications in Selective Detection of Fe3+, Thermosensing and Logic Gates.

The fluorescence based applications such as chemosensing of Fe3+ ion, temperature sensing, NOR-gate molecular logic operations, and fluorescent ink were achieved using an expired medicine namely Pantoprazole (sensor1) which is a derivative of benzimidazole class. The phenomenon of quenching was a basic principle used in sensing Fe3+. We found that there was a combined effect of dynamic and static processes in quenching of fluorescence of sensor1. To confirm the selectiveness of sensor1, we performed interference experiments with other metal ions. There was no interference between these metal ions and Fe3+. The low LOD value of 1.032 µM suggested that the molecule is highly sensitive towards Fe3+. A high quantum yield of 8.087% increased the possibility of using sensor1 for light applications. There was a 2:1 stoichiometric ratio between sensor1 and Fe3+. The FTIR data analysis confirmed the presence of functional groups S = O, C-O-C, etc. The average particle size found with the DLS method was 130.5 nm. The zeta potential of -12.7 mV indicated that sensor1 is quite stable in solution form. For logic gate application EDTA (Ethylenediaminetetraaceticacid) and Fe3+ were considered as inputs and fluorescence intensity was taken as an output. In thermal sensing application, the high value of activation energy i.e. 908 meV and relative sensitivity of 1.2% 0C-1 affirmed that sensor1 can be used for thermal applications. The sensor1 was also apt for fluorescent ink application. Hence this investigation deduced that sensor1 can be a potential candidate for such applications over other conventional synthesized fluorescent probes.

Green Synthesis of Self-Passivated Fluorescent Carbon Dots Derived from Rice Bran for Degradation of Methylene Blue and Fluorescent Ink Applications.

Recently, natural products are the powerful carbon source to synthesize carbon dots (CDs) with interesting physical and chemical properties. In this present work, we report a facile hydrothermal synthesis method for preparing fluorescent carbon dots using a biogenic precursor of rice bran without any surface passivation agent. The synthetic methodology was easy, simple, environmental friendly and convenient. Structural and optical properties of the RB-CDs have been studied by UV-visible, Fourier transform infrared spectroscopy (FTIR), Field emission scanning electron microscopy (FESEM), Fluorescence spectra and X-ray photoelectron spectroscopy (XPS) techniques. The prepared RB-CDs exhibited green emission upon irradiation with UV light and the calculated fluorescence quantum yield (QY) was found to be 7.4%. The morphological features of the synthesized RB-CDs were characterized by High-Resolution Transmission Electron Microscopy (HR-TEM), the average size of the RB-CDs was found to be 2.96 nm. The synthesized RB-CDs were beneficially applied as a catalyst for the catalytic degradation of methylene blue (MB) dye using NaBH4 as the reducing agent in the ambient conditions. The degradation of MB dye under light illumination was 89.20% in 30 min. Further, the obtained highly fluorescent RB-CDs were efficiently utilized as a fluorescent ink for luminescent pattern printing (patterning agent) in the anti-counterfeiting applications.

Re-usage of the Waste Drug as Molecular Chemosensor for Fe3+ Ion: Application towards Fluorescent Ink.

Herein, a novel notion is used to reuse an expired drug namely Telmisartan (Sensor 2) to optically sense the Fe3+ metal ion. Direct re-usage of the drug avoided wearisome procedures of synthesis, hence proved the method as simple and economic. Sensor 2 found highly stable in the temperature range 25-75 °C. Relative fluorescence was almost the same even after 35 days of observation. There were no significant changes in wavelength even after adding different concentrations of FeCl3, which shows the high stability of the compound. The value of Limit of Detection (LOD) observed was 34.2 nM. FTIR studies confirmed the presence of carboxylic group. The method of fluorescence quenching was used to detect the Fe3+ ion. The association between Sensor 2 and Fe3+ was analyzed using Benesi-Hildebrand relation. Positive deviation from the linearity of S-V plots suggested that the quenching was not purely dynamic. Further, this deviation was analyzed by the sphere of action quenching model. To investigate whether the quenching is diffusion limited, we applied the finite sink approximation model and deduced that quenching is due to both static and dynamic processes. Due to the high fluorescence property of the molecule, it was successfully tested to be used as fluorescent ink.

Nitrogen-doped carbon dot threads as a "turn-off" fluorescent probe for permanganate ions and its hydrogel hybrid as a naked eye sensor for gold(III) ions.

Highly fluorescent nitrogen-doped carbon dot (NCD) threads were synthesized via simple pyrolysis of citric acid, p-hydroxybenzoic acid, and ammonia. The NCDs show excitation-independent behavior with maximum excitation and emission wavelengths of 350 nm and 435 nm, respectively. The developed probe was used as a turn-off fluorescent sensor for the selective and sensitive determination of permanganate ions in aqueous media. The probe's hydrogel hybrid displayed a beautiful purple color demonstrating its potential as a naked eye sensor for gold detection. The ratiometric sensor exhibited excellent selectivity towards permanganate ions over 27 other ions with a linear range of 510 nM to 2 µM, a detection limit of 170 nM, and a linear regression value (R2) of 0.9944. Similarly, the linear range and limit of detection for gold ions was 3.89-20 µM and 1.285 µM, respectively. The synthesized NCDs were also used as a fluorescent ink as well as a naked eye marker in association with a gold solution demonstrating its potential forensic and anti-counterfeiting applications. Graphical abstract.

Ratiometric fluorescent test pen filled with a mixing ink of carbon dots and CdTe quantum dots for portable assay of silver ion on paper.

A ratiometric fluorescent test pen filled with a mixing ink of blue carbon dots (CDs) and red CdTe quantum dots (CdTe QDs) is introduced for portable assay of silver ion (Ag(I)) on paper. The mixing ink was tuned with ratiometric fluorescent intensity of 1:5, and then filled into a vacant commercial fluorescent pen core. Writing/painting a random word/figure on a blank paper can make the most portable nanoprobe determining Ag(I) by visualization. Ag(I) can adsorb onto the surface of CdTe QDs, which leads to the formation of surficial Ag2Te layer by an ion-exchanging reaction. This enables the red fluorescence of CdTe QDs (with excitation/emission maxima at 360/628 nm) to be quenched. Due to the unchanged blue fluorescence of CDs (with excitation/emission maxima at 360/440 nm) as internal standard, the solution color evolves gradually from red to blue with the increase of Ag(I) concentration with a detection limit of 3.48 nM. This is at least 2 orders of magnitude lower than the limit defined by World Health Organization (WHO) in drinkable water. The fluorescent test pen has also been used for the determination of Ag(I) in wastewater. Graphical abstract Ag(I) can adsorb on the surface of CdTe QDs to quench their fluorescence, while the fluorescent intensity of CDs keep constant, accompanying color change with the increase of Ag(I) concentration. The method offers a visual assay of Ag(I) in water.

Nitrogen-Doped Durian Shell Derived Carbon Dots for Inner Filter Effect Mediated Sensing of Tetracycline and Fluorescent Ink.

Photoluminescent carbon dots have gained increasing attention in recent years due to their unique optical properties. Herein, a facile one-pot hydrothermal process is used to develop nitrogen-doped carbon dots (NCDs) with durian shell waste as the precursor and Tris base as the doping agent. The synthesized NCDs showed a quantum yield of 12.93% with a blue fluorescence under UV-light irradiation and maximum emission at 414 nm at an excitation wavelength of 340 nm. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy showed the presence of nitrogen and oxygen functional groups on the NCD surface. The particles were quasi-spherical with an average particle diameter of 6.5 nm. The synthesized NCDs were resistant to photobleaching and stable under a wide range of pH but were negatively affected by increasing temperature. NCDs showed high selectivity to Tetracycline as the fluorescence of NCDs was quenched significantly by Tetracycline as a result of the inner filter effect. Based on sensitivity experiments, a linear relationship (R2 = 0.989) was developed over a concentration range of 0-30 µM with a detection limit of 75 nM (S/N = 3). The linear model was validated with two water samples (lake water and tap water) with relative recoveries of 98.6-108.5% and an RSD of <3.5%.

UV light-tunable fluorescent inks and polymer hydrogel films based on carbon nanodots and lanthanide for enhancing anti-counterfeiting.

Novel water-soluble green fluorescent carbon nanodots (CNs) using methacrylic acid and m-phenylenediamine as precursors were first synthesized using a one-pot hydrothermal method. Red fluorescent lanthanide complexes were prepared using lanthanide ion Eu3+ and pyridine-2,6-dicarboxylic acid. The optical properties of CNs were characterized using ultraviolet visible (UV) spectra and fluorescence spectra, microscopic morphology was characterized using transmission electron microscopy (TEM) and dynamic light scattering (DLS), and the elemental composition was characterized using Fourier transform-infrared spectroscopy (FT-IR) and X-ray photoelectron spectra (XPS). The fluorescence spectra of the lanthanide complexes were also measured. A simple strategy was developed to prepare UV light-tunable fluorescent inks and polymer hydrogels films based on CNs and lanthanide complexes. The fluorescent inks and polymer hydrogels films could be repeatedly switched between green and red fluorescence. The change of color depended on luminescence of the CNs and the lanthanide complexes under 254 and 365 nm UV light, respectively. The UV light-tunable fluorescent inks and polymer hydrogels films could enhance its anti-counterfeiting function for data and information.

One-step synthesis of N-doped carbon dots, and their applications in curcumin sensing, fluorescent inks, and super-resolution nanoscopy.

Nitrogen-doped carbon dots (N-CDs) with fluorescence excitation/emission maxima at 365/450 nm were prepared by a one-step hydrothermal approach. The dots possess remarkable photostability, fluorescence blinking and good biocompatibility, and this favors utilization in stochastic optical reconstruction microscopy (STORM). A spatial resolution down to ~60 nm was achieved when imaging HeLa cells using 647-nm laser excitation. This opens new possibilities for various super-resolution techniques based on stochastic optical switching. The remarkable optical properties of the N-CDs also enable them to be applied as invisible security ink for use in patterning, information storage and anti-counterfeiting. Further, it is found that the fluorescence of the N-CDs can be quenched by curcumin with high efficiency due to a combination of inner filter effect and static quenching. Based on this, a fluorometric assay with a detection limit of 21 ng mL-1 was developed for the determination of curcumin. Graphical abstract Schematic representation of the applications of N-doped carbon dots (N-CDs). Curcumin quenches the fluorescence of N-CDs with high efficiency. The remarkable optical properties of the N-CDs enable them to be applied in fluorescent ink, cell imaging and stochastic optical reconstruction microscopy (STORM).

Invisible Security Ink Based on Water-Soluble Graphitic Carbon Nitride Quantum Dots.

Stimuli-responsive photoluminescent (PL) materials have been widely used as fluorescent ink for data security applications. However, traditional fluorescent inks are limited in maintaining the secrecy of information because the inks are usually visible by naked eyes either under ambient light or UV-light illumination. Here, we introduced metal-free water-soluble graphitic carbon nitride quantum dots (g-CNQDs) as invisible security ink for information coding, encryption, and decryption. The information written by the g-CNQDs is invisible in ambient light and UV light, but it can be readable by a fluorescence microplate reader. Moreover, the information can be encrypted and decrypted by using oxalic acid and sodium bicarbonate as encryption reagent and decryption reagent, respectively. Our findings provide new opportunities for high-level information coding and protection by using water-soluble g-CNQDs as invisible security ink.

Luminogenic and Bactericidal Studies of an Acrylonitrile-Based AIEgen.

We have synthesized an aggregation-induced emissive molecule that exhibits promising photophysical characteristics. The aggregating aptitude is demonstrated by binary solvent mixture and it is emissive in both solution and solid state. The luminogenic characteristics are employed in creating fluorescent inks as well as for the detection of nitro antibiotics in biofluids and in solid support. Moreover, the acrylonitrile-based compound is bactericidal tested on E. coli and B. subtilis.

New phenanthridine-based multi-functional chemosensor for selective detection of Th4+ and Hg2+ ions in both aqueous and solid state.

A new phenanthridine-based multifunctional chemosensor (L), was synthesised via a green synthetic route and characterised using FT-IR, NMR and HRMS analysis. The sensing application of L towards metal ions in both solution and solid-state was studied using UV-vis and fluorescence spectroscopy, which exhibits dual-sensing behaviour for Th4+ and Hg2+ ions with good recyclability. In aqueous acetonitrile, L showed rapid response for the detection of environmental toxic metal ions and has a very low analytical detection limit of 125.5 pM and 1.94 nM for Th4+ and Hg2+ions respectively, which is remarkably lower than the World Health Organization standard. The cation binding property of the L with Th4+ and Hg2+ions was investigated by Job plot, 1H NMR titration, HR-MS and DFT calculation. The in-situ formed ensemble L-Hg2+ was further applied in the naked-eye detection of Cys (Cystine) and His (Histidine) over other common amino acids. The utility of L for real-time detection of Hg2+ and Th4+ ions was explored in various sources of environmental water samples, test paper strips, fingerprint imaging, fluorescent ink and smartphone-assisted sensing techniques, demonstrating the promising on-site visualization of the probe in controlling the toxicity levels in wastewater sources without resorting to expensive instruments.

Preparation of waterborne anti-counterfeiting ink based on dual luminescent nanohybrids of bacterial cellulose nanocrystals and lanthanide­nitrogen co-modified GQDs.

To address the growing challenge of counterfeit prevention, this study developed a novel anti-counterfeiting ink system based on bacterial cellulose nanocrystals (BCNC) and lanthanide (Er, Yb)­nitrogen (N) co-dropped graphene quantum dots (GQDs), which exhibited both photoluminescence (PL) and upconversion photoluminescence (UCPL) fluorescent properties as well as excellent rheological characteristics. The Er/Yb/N-GQDs with positive charges were synthesized by a one-step hydrothermal method and subsequently assembled with negatively charged BCNC through electrostatic self-assembly to fabricate a novel nanohybrid, Er/Yb/N-GQDs-BCNC. Raman spectroscopy results indicated an enhancement in the graphitization of GQDs due to lanthanide modification. The TEM results demonstrated a homogeneous distribution of Er/Yb/N-GQDs on BCNC, while XRD, FTIR, and XPS analyses confirmed their physical binding, thus validating the successful synthesis of novel nanohybrids. Then, Er/Yb/N-GQDs-BCNC was introduced into PVA waterborne ink and exhibited dual anti-counterfeiting properties by emitting blue fluorescence at Em 440 nm under Ex 370 nm and green fluorescence at Em 550 nm under Ex 980 nm. Furthermore, the incorporation of BCNC significantly enhanced the thixotropic behavior and yield stress of the PVA waterborne ink. This enhancement made the dual anti-counterfeiting fluorescent ink more suitable for diversified applications on different devices and various substrates, thus providing a novel approach for convenient and rapid information encryption and high security anti-counterfeiting.

Multifunctional N,S-doped and methionine functionalized carbon dots for on-off-on Fe3+ and ascorbic acid sensing, cell imaging, and fluorescent ink applying.

Fluorescent carbon dots (CDs) have been identified as potential nanosensors and attracted tremendous research interests in wide areas including anti-counterfeiting, environmental and biological sensing and imaging in considering of the attractive optical properties. In this work, we present a CDs based fluorescent sensor from polyvinylpyrrolidone, citric acid, and methionine as precursors by hydrothermal approach. The selective quantifying of Fe3+ and ascorbic acid (AA) are based on the fluorescent on-off-on process, in which the fluorescent quenching is induced by the coordination of the Fe3+ on the surface of the CDs, while the fluorescence recovery is mainly attributed to redox reaction between Fe3+ and AA, breaking the coordination and bringing the fluorescence back. Inspired by the good water solubility and biocompatibility, significant photostability, superior photobleaching resistance as well as high selectivity, sensitivity, and interference immunity, which are constructed mainly from the N,S-doping and methionine surface functionalization, the CDs have not only been employed as fluorescence ink in multiple anti-counterfeiting printing and confidential document writing or transmitting, but also been developed as promising fluorescence sensors in solution and solid by CDs doped test strips and hydrogels for effectively monitoring and removing of Fe3+ and AA in environmental aqueous solution. The CDs have been also implemented as effective diagnostic candidates for imaging and tracking of Fe3+ and AA in living cells, accelerating the understanding of their function and importance in related biological processes for the prevention and treatment specific diseases. Electronic Supplementary Material: Supplementary material (fluorescence spectra: UV and Xe irradiation, TG, thermo stability, ionic strength, relationship between fluorescence responses at different concentrations of Fe3+ and AA, reaction time-dependent fluorescent responses; XPS spectra of CDs + Fe3+ and Fe3+@CDs + AA; structural characterization; equations about fluorescence lifetime, quantum yield and LOD; comparison of the CDs for the detection of Fe3+ and AA with reported methods; detection of Fe3+ and AA in real samples; absorption of Fe3+ in environmental samples and MTT assay results) is available in the online version of this article at 10.1007/s12274-022-5107-7.

Water Soluble PMPC-Derived Bright Fluorescent Nitrogen/Phosphorous-Doped Carbon Dots for Fluorescent Ink (Anti-Counterfeiting) and Cellular Multicolor Imaging.

Here, a simple one-step hydrothermal-assisted carbonization process was adopted for the preparation of nitrogen/phosphorous-doped carbon dots from a water-soluble polymer, poly 2-(methacryloyloxy)ethyl phosphorylcholine (PMPC). By the free-radical polymerization method, PMPC was synthesized using 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) and 4,4'-azobis (4-cyanovaleric acid). The water-soluble polymers, PMPC, that have nitrogen/phosphorus moieties are used to prepare carbon dots (P-CDs). The resulting P-CDs were thoroughly characterized by various analytical techniques such as field emission-scanning electron microscopy (FESEM) with energy-dispersive X-ray spectroscopy (EDS), high-resolution transmittance electron microscopy (HRTEM), X-ray diffraction (XRD), Raman spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Ultraviolet-visible (UV-vis) spectroscopy and fluorescence spectroscopy to determine their structural and optical properties. The synthesized P-CDs displayed bright/durable fluorescence, were stable for long periods, and confirmed the enrichment of functionalities including oxygen, phosphorus, and nitrogen heteroatoms in the carbon matrix. Since the synthesized P-CDs showed bright fluorescence with excellent photostability, excitation-dependent fluorescence emission, and excellent quantum yield (23%), it has been explored as a fluorescent (security) ink for drawing and writing (anti-counterfeiting). Further, cytotoxicity study results advised for biocompatibility and thus were used for cellular multicolor imaging in nematodes. This work not only demonstrated the preparation of CDs from polymers that can be used as advanced fluorescence ink, a bioimaging agent for anti-counterfeiting, and cellular multicolor imaging candidate, but additionally prominently opened a new perspective on the bulk preparation of CDs simply and efficiently for various applications.

Fluorescent graphitic carbon nitride with photocatalytic oxidase-like activity for anti-counterfeiting application.

Herein bulk phenyl- and carbon-modified graphitic carbon nitride (PCCN) powders with tunable fluorescent emission from green-color to yellow-color were prepared by copolymerization of 2,4-diamino-6-phenyl-1,3,5-triazine and 2,2,6-triaminopyrimidine. The corresponding nanosheets with blue-color to green-color fluorescence were obtained by the oxidation of their bulk powders in sulfuric or nitric acid and then ultrasonic exfoliation. The typical PCCN0.6 nanosheets not only displayed strong green-color fluorescence but also exhibited photocatalytic oxidase-like activity, which can catalyze the oxidation of substrates 3,3',5,5'-tetramethylbenzidine and Amplex UltraRed by O2 to produce blue-color colorimetric product and pink-color fluorescent product, respectively. By taking advantage of green-color fluorescence and photocatalytic activity of PCCN0.6 nanosheets, a prototype for high-level anti-counterfeiting application was demonstrated by using the mixture of PCCN0.6 nanosheets and Amplex UltraRed as the fluorescent ink.