Electropolymerized surface ion imprinting films on a gold nanoparticles/single-wall carbon nanotube nanohybrids modified glassy carbon electrode for electrochemical detection of trace mercury(II) in water

Electrochemical detection of Hg(II) using a electropolymerized ion imprinting poly(2-mercaptobenzothiazole) films at the surface of gold nanoparticles/single-walled carbon nanotube nanohybrids modified glassy carbon electrode (PMBT/AuNPs/SWCNTs/GCE) is described for the first time. The Hg(II)-imprinted PMBT/AuNPs/SWCNTs/GCE sensor exhibits larger binding to functionalized capacity, larger affinity, faster binding kinetics and higher selectivity to template Hg(II). The differential pulse anodic stripping voltammetry (DPASV) response of the Hg(II)-imprinted PMBT/AuNPs/SWCNTs/GCE sensor to Hg(II) is ca. 3.7- and 10.5-fold higher than that at the non-imprinted PMBT/AuNPs/SWCNTs/GCE and the imprinted PMBT/AuNPs/GCE, respectively, and the detection limit for Hg(II) is 0.08 nM (S/N = 3, which is well below the guideline value given by the World Health Organization) and a sensitivity of 0.749 μA nM⁻¹ was obtained. Excellent wide linear range (0.4–96.0 nM) and good repeatability (relative standard deviation of 2.6%) were obtained for Hg(II). The interference experiments show that Ag(I), Pb(II), Cd(II), Zn(II) and Cu(II) had little or no influence on the Hg(II) signal. These values, particularly the high sensitivity and excellent selectivity in contrast to the values reported previously in the area of electrochemical Hg(II) detection, demonstrate the analytical performance of the Hg(II)-imprinted PMBT/AuNPs/SWCNTs/GCE toward Hg(II) is superior to the existing electrodes and could be used for efficient determination of Hg(II) in natural water samples.     

Enhanced Electrochemical Determination of Catechol and Hydroquinone Based on Pd Nanoparticles/Poly(Taurine) Modified Glassy Carbon Electrode

Here, Pd nanoparticles and poly(taurine) film was prepared on the glassy carbon electrode surface (Pd/Poly(TAU)/GCE) by the rapid electrochemical technique. The proposed composite surface was characterized by scanning electron microscopy(SEM), X‐ray photoelectron spectroscopy(XPS) and electrochemical impedance spectroscopy(EIS). Enhanced electron transfer ability and higher electroactive surface area were achieved at Pd/Poly(TAU)/GCE as compared to the bare GCE and polymer film electrode. The new and highly stable Pd/Poly(TAU)/GCE was employed for the individual and simultaneous determination of hydroquinone and catechol which were environmentally toxic. Under the optimized conditions, HQ and CC were individually determined by using the differantial pulse voltammetry in the linear ranges of 0.008–100 μM and 0.001–100 μM with the detection limits of (LOD) 2.1 nM and 0.68 nM, respectively. In case of simultaneous determination, LODs were found as 10 nM and 0.88 nM for HQ and CC, respectively. The content of both analytes in the real sample analysis was evaluated in the river water and tap water successfully.     

Fullerene-based anodic stripping voltammetry for simultaneous determination of Hg(II), Cu(II), Pb(II) and Cd(II) in foodstuff

Various carbon nanomaterials for use in anodic stripping voltammetric analysis of Hg(II), Cu(II), Pb(II) and Cd(II) are screened. Graphene, carbon nanotubes, carbon nanofibers and fullerene (C₆₀), dispersed in chitosan (Chit) aqueous solution, are used to modify a glassy carbon electrode (GCE). The fullerene-chitosan modified GCE (C₆₀-Chit/GCE) displays superior performance in terms of simultaneous determination of the above ions. The electrodes and materials are characterized by electrochemical impedance spectroscopy, cyclic voltammetry, scanning electron microscopy, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The excellent performance of C₆₀-Chit/GCE is attributed to the good electrical conductivity, large surface area, strong adsorption affinity and unique crystalline structure of C₆₀. Using differential pulse anodic stripping voltammetry, the assay has the following features for Hg(II), Cu(II), Pb(II) and Cd(II), respectively: (a) Peak voltages of +0.14, ?0.11, ?0.58 and???0.82 V (vs SCE); (b) linear ranges extending from 0.01–6.0 μM, 0.05–6.0 μM, 0.005–6.0 μM and 0.5–9.0 μM; and (c), detection limits (3σ method) of 3 nM (0.6 ppb), 14 nM (0.9 ppb), 1 nM (0.2 ppb) and 21 nM (2.4 ppb). Moreover, the modified GCE is well reproducible and suitable for long-term usage. The method was successfully applied to the simultaneous determination of these ions in spiked foodstuff.

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Graphical abstract Compared with graphene, carbon nanotubes and carbon nanofibers, an electrode modified with fullerene in chitosan electrode displays superior performance for the simultaneous anodic stripping voltammetric detection of Hg(II), Cu(II), Pb(II) and Cd(II).

     

A sensitive mercury (II) sensor based on CuO nanoshuttles/poly(thionine) modified glassy carbon electrode

Shuttle-like copper oxide (CuO) was prepared by a hydrothermal decomposition process. The resulting material was characterized by scanning electron microscopy and X-ray diffraction. It was then immobilized on the surface of a glassy carbon electrode modified with a film of poly(thionine). A pair of well-defined and reversible redox peaks for Hg(II) was observed with the resulting electrode in pH 7.0 solutions. The anodic and cathodic peak potentials occurred at 0.260 V and 0.220 V (vs. Ag/AgCl), respectively. The modified electrode displayed excellent amperometric response to Hg(II), with a linear range from 40 nM to 5.0 mM and a detection limit of 8.5 nM at a signal-to-noise ratio of 3. The sensor exhibited high selectivity and reproducibility and was successfully applied to the determination of Hg(II) in water samples.     

Organic‐inorganic‐hybrid‐enhancement Electrochemical Sensor for Determination of Cu (II) in River Water

A dual strategy that the L‐cysteine self‐assembling on three‐dimensional network of organic‐hybrid‐materials realized by successive interaction of Au−S bond is employed to construct as the amplified electrochemical sensor for determination Cu (II). Specifically, the sensor combined a rigid three‐dimension inorganic net which provides a higher interfacial area as well as faster adsorption of ions. Accordingly, surface and interfacial‐dominated electro‐catalysis reactivity is used as an ideal test‐bed to verify the reliability of electrochemical sensor that reveal enhancement sensitiveness and selectivity, low detection limit, and stability over a long period of time. Time‐dependent density functional theory (TD‐DFT) were used to calculating the all complexes energies at the B3LYP/LANL2DZ level associated with the polarized continuum model (PCM). The result of calculation indicates that the binding strength of Cu (II), Cd (II), As (III), Hg (II) with L‐cysteine are decrease successively, and this is in well agreement with experimental results. This work not only achieves an unprecedented understanding to L‐cysteine/Au/TiO₂/GCE sensor but also provides a new perspective for application in detection of Cu (II) in real river waters.     

Selective solid-phase extraction of lead(II) from biological and natural water samples using surface-grafted lead(II)-imprinted polymers

A new Pb(II)-imprinted amino-functionalized silica gel sorbent was synthesized by an easy one-step reaction by combining a surface imprinting technique for selective solid-phase extraction of trace Pb(II) prior to its determination by inductively coupled plasma optical emission spectrometry. The Pb(II)-imprinted amino-functionalized silica gel sorbent was characterized by Fourier transform infrared spectroscopy. Compared to non-imprinted polymer particles, the ion-imprinted polymers had higher selectivity and adsorption capacity for Pb(II). The maximum static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Pb(II) was 19.66 and 6.20 mg g^?1, respectively. The largest selectivity coefficient of the Pb(II)-imprinted sorbent for Pb(II) in the presence of Cd(II) was over 450. The relative selectivity (α _r) values of Pb(II)/Cd(II) were 49.3 and 46.3, which were greater than 1. The distribution ratio (D) values of Pb(II)-imprinted polymers for Pb(II) were much larger than that for Cd(II). The detection limit (3σ) was 0.20 μg L^?1. The relative standard deviation was 2.0% for 11 replicate determinations. The method was validated for the analysis three certified reference materials (GBW 08301, GBW 08504, GBW 08511), and the results are in good agreement with standard values. The method was also successfully applied to the determination of trace lead in plants and water samples with satisfactory results.     

Impedimetric Aptasensors Based on Carbon Nanotubes – Poly(methylene blue) Composite

The effect of aptamer structure and immobilization platform on the efficiency of thrombin binding and its detection using electrochemical impedance spectroscopy (EIS) characteristics was investigated with aptasensors based on glassy carbon electrodes covered with multiwalled carbon nanotubes (MWNTs). Aptamers with one or two binding sequences GGTTGGTGTGGTTGG specific for thrombin and poly(dA) and poly(dT) tags able to form dimeric products (aptabodies) were used to establish significance of steric and electrostatic factors in aptasensor performance. We have shown that electropolymerization of methylene blue onto MWNTs significantly improved electrochemical characteristics and sensitivity of thrombin detection against bare MWNTs. Charge transfer resistance and capacitance of the surface layer were measured in the presence of redox probe [Fe(CN)₆]^3?/4?. Aptasensors make it possible to detect thrombin in the concentration range 1 nM–1 µM with the limit of detection of 0.7 nM (monitoring resistance changes) and 0.5 nM (capacitance changes), respectively.     

Highly sensitive and selective voltammetric detection of mercury(II) using an ITO electrode modified with 5-methyl-2-thiouracil, graphene oxide and gold nanoparticles

We have developed an electrochemical sensor for highly selective and sensitive determination of Hg(II). It is based on the specific binding of 5-methyl-2-thiouracil (MTU) and Hg(II) to the surface of an indium tin oxide (ITO) electrode modified with a composite made from graphene oxide (GO) and gold nanoparticles (AuNPs). This leads to a largely enhanced differential pulse voltammetric response for Hg(II). Following optimization of the method, a good linear relationship (R?=?0.9920) is found between peak current and the concentration of Hg(II) in the 5.0–110.0 nM range. The limit of detection (LOD) is 0.78 nM at a signal-to-noise ratio of 3. A study on the interference by several metal ions revealed no interferences. The feasibility of this method was demonstrated by the analyses of real water samples. The LODs are 6.9, 1.0 and 1.9 nM for tap water, bottled water and lake water samples, respectively, and recoveries for the water samples spiked with 8.0, 50.0 and 100.0 nM were 83.9–96.8 %, with relative standard deviations ranging from 3.3 % to 5.2 %.

Reaction of Cd(II)-Morin with dsDNA for biosensing of ssDNA oligomers with complementary, GCE-immobilized ssDNA

In this work, the complex cadmium(II)-morin was synthesized and its interaction with double-stranded salmon sperm DNA was studied by electrochemical methods on glassy carbon electrode (GCE). It was shown that Cd(II)-Morin with high electrochemical activity can intercalate into the double-helix DNA, and the binding stoichiometry and equilibrium dissociation constant according to the Hill model for cooperative binding were calculated to be 1.761 and 2.5 x 10(-5) M, respectively. Using Cd(II)-Morin as a novel hybridization indicator, the hybridization between the probe and its complementary and mismatched sequence was investigated by differential pulse voltammetry (DPV), which was to access the selectivity of the developed electrochemical DNA biosensor. The complementary target ssDNA could be quantified over the range from 2.69 x 10(-8) M to 9.16 x 10(-7) M with a linear correlation of 0.9971 and a detection limit of 9.30 x 10(-9) M. These results demonstrated that the Cd(II)-Morin indicator provides great promise for the rapid and selective measurement of the target DNA.     

Carbon Quantum Dots Co‐catalyzed with ZnO Nanoflowers and Poly (CTAB) Nanosensor for Simultaneous Sensitive Detection of Paracetamol and Ciprofloxacin in Biological Samples

A novel platform based incorporation of carbon quantum dots (CQDs) and zinc oxide nanoflowers (ZnO‐NFs) decorated with poly cetyltrimethylammonium bromide (CTAB) was developed as electrochemical sensor for the sensitive and selective simultaneous detection of Paracetamol (PAR) and Ciprofloxacin (CIP) in biological samples. For this, CQDs and ZnO‐NFs were first deposited on a glassy carbon electrode (GCE) and subsequently a Poly (CTAB) layer was grown onto their surfaces through electro‐polymerization. The synthesized nanostructures and the corresponding fabricated sensor were characterized by the techniques of TEM, XRD, FE‐SEM, and EDX analysis. Moreover electrochemical characterization by CV and DPV were performed to elucidate the construction process and electron transfer abilities of the CQDs/ZnO‐NFs/Poly(CTAB)/GCE. Increased sensitivity and efficiency of this sensing system was obtained due to the synergistic effects of CQDs, ZnO‐NFs and Poly (CTAB) with multi‐signal amplification. Under the optimum conditions, the DPV response of proposed sensor to PAR and CIP was linear at 0.05–30.0 μM and 0.01–30.0 μM, with the detection limit of 2.47 nM and 1.97 nM respectively. The sensor possessed high stability, reproducibility, sensitivity, and selectivity toward PAR and CIP detection, over potential interferents and presented high recovery percentage in the real sample matrices.     

Hg(II)-imprinted thiol-functionalized mesoporous sorbent micro-column preconcentration of trace mercury and determination by inductively coupled plasma optical emission spectrometry

Hg(II)-imprinting thiol-functionalized mesoporous sorbent was prepared by a sol–gel method and characterized by X-ray diffraction (XRD), FT-IR spectroscopy and nitrogen gas adsorption–desorption. The static adsorption capacity of the Hg(II)-imprinted and non-imprinted sorbent was 78.5 and 26.6 mg g⁻¹, respectively. The breakthrough capacity was 4.46 mg g⁻¹, and the relative selectivity coefficient for Hg(II) in the presence of Cd and Pb was 3.3 and 3.9, respectively. A new method using a micro-column packed with Hg(II)-imprinting thiol-functionalized mesoporous sorbent has been developed for preconcentration of trace mercury prior to its determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The effects of pH, sample flow rate and volume, elution solution and interfering ions on the recovery of the analyte have been investigated. The limit of detection was 0.39 ng ml⁻¹ with a concentration factor of 150 times. The developed method has been applied to the determination of trace mercury in some biological and environmental samples with satisfactory results. The accuracy was assessed through recovery experiments and analysis of certified reference material.     

Sensitive determination of hydrazine using poly(phenolphthalein), Au nanoparticles and multiwalled carbon nanotubes modified glassy carbon electrode

This study reports a detailed analysis of an electrode material containing poly(phenolphthalein), carbon nanotubes and gold nanoparticles which shows superior catalytic effect towards to hydrazine oxidation in Britton–Robinson buffer (pH 10.0). Glassy carbon electrode was modified by electropolymerization of phenolphthalein (PP) monomer (poly(PP)/GCE) and the multiwalled carbon nanotubes (MWCNTs) was dropped on the surface. This modified surface was electrodeposited with gold nanoparticles (AuNPs/CNT/poly(PP)/GCE). The fabricated electrode was analysed the determination of hydrazine using cyclic voltammetry, linear sweep voltammetry and amperometry. The peak potential of hydrazine oxidation on bare GCE, poly(PP)/GCE, CNT/GCE, CNT/poly(PP)/GCE, and AuNPs/CNT/poly(PP)/GCE were observed at 596 mV, 342 mV, 320 mV, 313 mV, and 27 mV, respectively. A shift in the overpotential to more negative direction and an enhancement in the peak current indicated that the AuNPs/CNT/poly(PP)/GC electrode presented an efficient electrocatalytic activity toward oxidation of hydrazine. Modified electrodes were characterized with High-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Amperometric current responses in the low hydrazine concentration range of 0.25–13 µM at the AuNPs/CNT/poly(PP)/GCE. The limit of detection (LOD) value was obtained to be 0.083 µM. A modified electrode was applied to naturel samples for hydrazine determination.     

Construction of a carbon nanocomposite electrode based on amino acids functionalized gold nanoparticles for trace electrochemical detection of mercury

A simple, highly sensitive and selective carbon nanocomposite electrode has been developed for the electrochemical trace determination of mercury. This mercury nanocomposite sensor was designed by incorporation of thiolated amino acids capped AuNps into the carbon ionic liquid electrode (CILE) which provides remarkably improved sensitivity and selectivity for the electrochemical stripping assay of Hg(II). Mercury ions are expected to interact with amino acids through cooperative metal–ligand interaction to form a stable complex which provides a sensitive approach for electrochemical detection of Hg(II) in the presence of other metal ions. The detection limit was found to be 2.3 nM (S/N = 3) that is lower than the permitted value of Hg(II) reported by the Environmental Protection Agency (EPA) limit of Hg(II) for drinkable water. The proposed nanocomposite electrode exhibits good applicability for monitoring Hg(II) in tap and waste water.     

电聚合烟酰胺制备电化学传感器：同时测定多巴胺、尿酸和抗坏血酸

用循环伏安法（CV）选择不同电位区间来电聚合烟酰胺（NA）得到了两种聚合物膜修饰电极：poly-niacinamide/GCE (poly-NA/GCE)和poly- nicotinic acid /GCE (poly-NC/GCE)。这两电极都具有显著电化学催化作用,能明显地降低多巴胺（DA）、尿酸（UA）和抗坏血酸(AA)的氧化过电位,并在混合溶液中使这些物质的氧化峰电位距离足够大,可进行三物质的同时测定。poly-NC/GCE的电催化性能更好一些,用差分脉冲伏安法（DPV）测定抗坏血酸,线性范围为75–3000 µmol L-1,电流灵敏度为5.6 mA•L•mol-1;测定多巴胺,线性范围为0.37 – 16 µmol L-1,电流灵敏度为1140 mA•L•mol-1; 测定尿酸,线性范围为0.74 – 230 µmol L-1,电流灵敏度为102 mA•L•mol-1。该电极具有很高的灵敏度、选择性和抗污染能力。     

A glassy carbon electrode modified with antimony and poly(p-aminobenzene sulfonic acid) for sensing lead(II) by square wave anodic stripping voltammetry

We have developed a sensor for the square wave anodic stripping voltammetric determination of Pb(II). A glassy carbon electrode was modified with a thin film of an antimony/poly(p-aminobenzene sulfonic acid) composite in air-saturated aqueous solution of pH 2.0. Compared to a conventional antimony film electrode, the new one yields a larger stripping signal for Pb(II). The conditions of polymerization, the concentration of Sb(III), the pH value of the sample solution, the deposition potential and time, frequency, potential amplitude, and step increment potential were optimized. Under the optimum conditions, a linear response was observed for Pb(II) in the range of 0.5 to 150.0 μg?L^?1. The detection limit for Pb(II) is 0.1 μg?L^?1.

Tridentate lysine-based fluorescent sensor for Hg(II) in aqueous solution

A novel homoplastic podand fluorescent sensor based on flexible hydrophilic lysine was prepared. Lysine with two dansyl groups-appended at both ends supplied a possibility for a tridentate binding toward Hg(II) and finally resulted in a unique selectivity to Hg(II) over other transition-metal ions with a hypersensitivity (detection limit 2.0 nM) in neutral buffered aqueous solutions. Notably, the coordination of chloride ion to the complex of sensor-Hg(II) brought forth that the trend in the NMR chemical shift for hydrogen and carbon atoms of the sensor was contrary to the findings in the former reports, which shows upfield shifts for the hydrogens and the alkane carbons but downfield shifts for the dansyl carbons, respectively.     

Selective solid-phase extraction of nickel(II) using a surface-imprinted silica gel sorbent

A new Ni(II)-imprinted amino-functionalized silica gel sorbent with excellent selectivity for nickel(II) was prepared by an easy one-step reaction by combining a surface imprinting technique for selective solid-phase extraction (SPE) of trace Ni(II) in water samples prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Compared with non-imprinted polymer particles, the ion-imprinted polymers (IIPs) had higher selectivity and adsorption capacity for Ni(II). The maximum static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Ni(II) was 12.61 and 4.25 mg g⁻¹, respectively. The relatively selective factor (α_r) values of Ni(II)/Cu(II), Ni(II)/Co(II), Ni(II)/Zn(II) and Ni(II)/Pd(II) were 45.99, 32.83, 43.79 and 28.36, which were greater than 1. The distribution ratio (D) values of Ni(II)-imprinted polymers for Ni(II) were greatly larger than that for Cu(II), Co(II), Zn(II) and Pd(II). The detection limit (3σ) was 0.16 ng mL⁻¹. The relative standard deviation of the method was 1.48% for eight replicate determinations. The method was validated by analyzing two certified reference materials (GBW 08618 and GBW 08402), the results obtained is in good agreement with standard values. The developed method was also successfully applied to the determination of trace nickel in plants and water samples with satisfactory results.     

A gold electrode modified with amino-modified reduced graphene oxide,ion specific DNA and DNAzyme for dual electrochemical determination of Pb(II) and Hg(II)

Multilayered reduced graphene oxide (rGO) was functionalized with amino groups by treatment with nitrogen plasma. Raman spectroscopy showed plasma treatment not to substantially alter the chemical structure of rGO and that a wide range of functional nitrogen groups is evenly incorporated into the carbon lattice. The amino-modified rGO was used to design an electrochemical biosensor in which a DNAzyme, substrate DNA and Pb(II) and Hg(II) binding DNA were immobilized on the amino-rGO placed on a gold electrode. The high concentration of amino groups and the rough surface of the rGO favor DNA immobilization. Heavy metal ions are bound to the surface via specific interaction between DNA and the two ions which are detected by electrochemical impedance spectroscopy at a potential of 0.2 V (vs. Ag/AgCl). The detection limits for Pb(II) and Hg(II) are as low as 7.8 and 5.4 pM, respectively, and the analytical ranges extend from 0.01 to 100 nM. The sensor is highly specific and stable and therefore represents a highly promising tool for use in environmental monitoring.

A nanofilm of reduced graphene oxide was first modified with amino groups by treatment with nitrogen plasma. A special DNA was then anchored to the surface to obtain a biosensor for simultaneous detection of Pb(II) and Hg(II). The sensor has detection limits as low as 7.8 and 5.4 pM and is highly selective.

     

A sensitive sensor for determination of l-tryptophan based on gold nanoparticles/poly(alizarin red S)-modified glassy carbon electrode

This work described a novel sensor for detection of l -tryptophan (Trp) by electrodeposition of gold nanoparticles (AuNPs) onto the poly(alizarin red S) film pre-cast on a glassy carbon electrode (GCE). Alizarin red S (ARS) was deposited on the surface of the GCE by electropolymerization, and gold nanoparticles (AuNPs) were attached onto the poly(ARS) film by electrodeposition, forming an AuNPs–PARS nanocomposite film-modified GCE (AuNPs–PARS/GCE). Then electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) were used to characterize modified electrodes. The Nyquist diagrams of EIS indicated that the PARS film and AuNPs were successfully immobilized on the surface of GCE, and the electron transfer resistance value of electrode changed efficiently. The SEM image showed that the immobilized AuNPs were spherical in shape. The AuNPs–PARS/GEC displayed excellent amperometric response for Trp. The amperometric responses have two linear ranges from 0.02 to 0.5 μM and 0.5 to 20.0 μM, with sensitivities of 1.63(±0.08) and 0.21(±0.01)?μAμM^?1, respectively. Its detection limit was 6.7 nM at a signal-to-noise ratio of 3. The proposed method was applied to determine Trp.

The Determination of Timolol Maleate Using Silver/Tannic Acid/Titanium Oxide Nanocomposite as an Electrochemical Sensor in Real Samples

Herein, a portable and cost-effective electrochemical sbased on Silver/tannic acid/titanium dioxide/glassy carbon electrode (Ag/TA@ TiO₂/GCE) was fabricated to determine timolol(TM) assay. The Ag/TA@TiO₂/GCE offered an irreversible oxidation peak at +0.99 V, and exhibited an extraordinary electrochemical performance with a wide linear working ranges from 0.01–0.84 and 0.84–49.0 μM and a low detection limit of 5.2 nM. The detection of TM in the presence of interfering agents and real samples was also analyzed. The sensor‘s selectivity was studied by comparing the binding of TM, propranolol, nebivolol, and metoprolol. The developed electrochemical sensing platform could have promising potential for the determination of TM in clinical samples.