RESUMO
In this work, hollow CoS2 particles were prepared by a one-step sulfurization strategy using polyoxometalate-based metal-organic frameworks as the precursor. The morphology and structure of CoS2 have been monitored by scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray powder diffraction. The mechanism for the formation of CoS2 is discussed. The reaction time and sulfur content are found to be important factors that affect the morphology and pure phase formation of CoS2, and a hollow semioctahedral morphology of CoS2 with open voids was obtained when the sulfur source was twice as large as the precursor and the reaction time was 24 h. The CoS2 (24 h) particles show an excellent peroxidase-like activity for the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized (oxTMB) by hydrogen peroxide. The polyoxometalate used as a precursor helps to stabilize oxTMB during catalytic oxidation, forming a stable curve platform for at least 8 min. Additionally, the colorimetric detection of hydroquinone is developed with a low detection limit of 0.42 µM. This research provides a new strategy to design hollow materials with high peroxidase-mimicking activity.
RESUMO
A stable and innovative composite film-modified electrode based on Dawson polyoxometalates H8P2Mo16V2O62 (P2Mo16V2) and ionic liquid (BMIMBr)-decorated carbon nanotubes, annotated as PEI/(P2Mo16V2/BMIMBr-CNTs)8, has been constructed by using the layer-by-layer self-assembly (LBL) method for the determination of L-tyrosine. The combination of three active components not only offers higher conductivity to facilitate rapid electron transfer, but also avoids the accumulation of P2Mo16V2 to expand the contact area and increase the reactive active sites. The modified electrode exhibits outstanding sensing performance for determination of Tyr with wide linear determination range of 5.8×10-7 M ~ 1.2×10-4 M, low determination limit of 1.7×10-7M (S/N=3), high selectivity for common interferences, and excellent stability at the potential of +0.78 V (vs. Ag/AgCl (3 M KCl)). The relative standard deviation (RSD) of 4.3% for five groups of parallel experiments shows the satisfactory repeatability of PEI/(P2Mo16V2/BMIMBr-CNTs)8. In addition, for determination of Tyr, the PEI/(P2Mo16V2/BMIMBr-CNTs)8 shows good recoveries of 98.8-99.8% in meat floss, which can be feasible in practical application.
Assuntos
Líquidos Iônicos , Nanotubos de Carbono , Tirosina , EletrodosRESUMO
The development of high-performance fluorescence probes has been an active area of research. In the present work, two new pH sensors Zn-3,5-Cl-saldmpn and Zn-3,5-Br-saldmpn based on a halogenated Schiff ligand (3,5-Cl-saldmpn = N, N'-(3,3'-dipropyhnethylamine) bis (3,5-chlorosalicylidene)) with linearity and a high signal-to-noise ratio were developed. Analyses revealed an exponential intensification in their fluorescence emission and a discernible chromatic shift upon pH increase from 5.0 to 7.0. The sensors could retain over 95% of their initial signal amplitude after 20 operational cycles, demonstrating excellent stability and reversibility. To elucidate their unique fluorescence response, a non-halogenated analog was introduced for comparison. The structural and optical characterization suggested that the introduction of halogen atoms can create additional interaction pathways between adjacent molecules and enhance the strength of the interaction, which not only improves the signal-to-noise ratio but also forms a long-range interaction process in the formation of the aggregation state, thus enhancing the response range. Meanwhile, the above proposed mechanism was also verified by theoretical calculations.
Assuntos
Corantes Fluorescentes , Bases de Schiff , Ligantes , Fluorescência , Bases de Schiff/química , Corantes Fluorescentes/química , Concentração de Íons de HidrogênioRESUMO
In this work, a noble-metal-free composite electrode was prepared based on PMo12O403- (PMo12), C9H5FeO7 (MIL-100(Fe), a Fe-based metal organic framework) and polyvinylpyrrolidone (PVP), and served as a high performance electrochemical sensor for synchronous detection of dopamine (DA) and uric acid (UA). The PMo12@MIL-100(Fe)@PVP composite electrode was fabricated by a in-situ hydrothermal method. Thanks to the synergistic effect of three active components (PMo12, MIL-100 and PVP), the electrode possesses large specific surface area and high electrical conductivity and therefore it shows high electrocatalytic oxidation performance of DA and UA with a spacing of 0.146 V between the two peak positions. These benefits of the electrode enable its electrochemical sensor to synchronously detect of DA and UA. Namely, the linear ranges can achieve 1-247 µM for DA and 5-406 µM for UA. Meanwhile, the detection limits are 0.586 µM for DA and 0.372 µM for UA. Moreover, the sensor can be applied to simultaneous determination of UA and DA in human serums with satisfactory recovery values.
Assuntos
Grafite , Nanocompostos , Humanos , Ácido Ascórbico , Dopamina , Técnicas Eletroquímicas/métodos , Eletrodos , Limite de Detecção , Povidona , Ácido ÚricoRESUMO
Phenols are widely used for commercial production, while they pose a hazard to the environment and human health. Thus, investigation of convenient and efficient methods for the detection, discrimination, and degradation of phenols becomes particularly important. Herein, two new polyoxometalate (POM)-based compounds, [Co2(btap)4(H2O)4][SiW12O40] (Co-POM) and [Ni2(btap)4(H2O)4][SiW12O40] (Ni-POM) (btap = 3,5-bis(triazol-1-yl)pyridine), are prepared via a hydrothermal synthesis method. The compounds show a fascinating structural feature of a POM-encapsulated twofold interpenetrating dia metal-organic framework. More importantly, besides the novel structures, the compound Co-POM realizes three functions, namely, the simultaneous detection, discrimination, and degradation of phenols. Specifically, Co-POM shows an excellent colorimetric detection performance toward phenol with a detection limit (LOD) ca. 1.32 µM, which is lower than most reported colorimetric detectors for phenol. Also, a new colorimetric sensor system based on Co-POM can discriminate phenol, 4-chlorophenol, and o-cresol with ease. Further, Co-POM exhibits a photocatalytic degradation property for 4-chlorophenol under irradiation of visible light with the highest degradation rate at 62% after irradiation for 5 h. Therefore, this work provides the first example of a POMs-based multifunctional material for achieving the detection, discrimination, and degradation of phenolic pollutants.
Assuntos
Poluentes Ambientais , Estruturas Metalorgânicas , Compostos de Tungstênio , Ânions , Dióxido de Carbono , Clorofenóis , Humanos , Fenol , Fenóis , Polieletrólitos , Piridinas , Compostos de Tungstênio/químicaRESUMO
In situ molecular transformation under hydrothermal conditions is a feasible method to introduce distinct organic ligands and suppress competitive reactions between different synthons. However, this strategy has not yet been explored for the preparation of polyoxometalate (POM)-encapsulated metal-organic frameworks (MOFs). In this work, we designed and prepared a new compound, [Co2(3,3'-bpy)(3,5'-bpp)(4,3'-bpy)](H2O)3[SiW12O40] (1) (4,3'-bpy = 4,3'-dipyridine, 3,5'-bpp = 3,5'-bis(pyrid-4-yl)pyridine, and 3,3'-bpy = 3,3'-bis(pyrid-4-yl) dipyridine), via an in situ ligand synthesis route. The compound shows a novel POM-encapsulated MOF structure with two pairs of left- and right-handed double helixes. These left- and right-handed helical chains further lead to triangular and rhombus-like channels, respectively. Moreover, the as-synthesized title compound shows superior electrocatalytic activity toward the hydrogen evolution reaction (HER) in 1 M KOH aqueous solution with a low overpotential and Tafel slope of 92 mV and 92.1 mV dec-1, respectively, under a current density of 10 cm-2. Also, the compound exhibits a high activity for the photocatalytic degradation of the dye rhodamine B. The excellent performance of the compound may be attributed to the synergistic effect between W and Co elements and the presence of encapsulated POMs. The title compound proves that it is possible to prepare multifunctional MOFs with POMs and transition metals showing HER activity and dye degradation activity.
RESUMO
Optical signals of pH probes mainly driven from the formation or rupture of covalent bonds, whereas the changes in covalent bonds usually require higher chemical driving forces, resulting in limited sensitivity and reversibility of the probes. The exploration of high-performance pH probes has been a subject of intense investigation. Herein, a new pH probe has been developed, with optical property investigation suggesting the probe has excellent signal-to-noise ratio, and fluorescence intensity shows exponential growth, combined with a visible color change, as pH increased from 5.1 to 6.0; Moreover, the probe has outstanding stability and reversibility, with more than 90% of the initial signal intensity remaining after 30 cycles. In order to better understand the special fluorescence behavior of the reported probe, the non-halogenated isomer is introduced for comparison, combined with the results of structural analysis, quantitative calculation and optical experiments, and the possible mechanism of the special supramolecular aggregation-caused quenching effect induced by the halogen atom is discussed.
Assuntos
Halogênios , Bases de Schiff , Halogênios/química , Concentração de Íons de Hidrogênio , Isomerismo , Bases de Schiff/química , Espectrometria de FluorescênciaRESUMO
High-energy density supercapacitors have attracted extensive attention due to their electrode structure design. A synergistic effect related to core-shell structure can improve the energy storage capacity and power density of electrode materials. The Ni-foam (NF) substrate coupled with polypyrrole (PPy) conductive coating can serve as an internal/external bicontinuous conductive network. In this work, the distinctive PPy@FeNi2S4@NF and PPy@NiCo2S4@NF materials were prepared by a simple two-step hydrothermal synthesis with a subsequent in situ polymerization method. PPy@FeNi2S4@NF and PPy@NiCo2S4@NF could deliver ultrahigh specific capacitances of 3870.3 and 5771.4 F·g-1 at 1 A·g-1 and marvelous cycling capability performances of 81.39% and 93.02% after 5000 cycles. The asymmetric supercapacitors composed of the prepared materials provided a high-energy density of over 47.2 Wh·kg-1 at 699.9 W·kg-1 power density and 67.11 Wh·kg-1 at 800 W·kg-1 power density. Therefore, the self-assembled core-shell structure can effectively improve the electrochemical performance and will have an effective service in advanced energy-storage devices.
Assuntos
Polímeros , Pirróis , Condutividade Elétrica , Capacitância Elétrica , EletrodosRESUMO
Oxygen defects and hollow structures positively impact pseudocapacitive properties of diffusion/surface-controlled processes, a component of critical importance when building high-performance supercapacitors. Hence, we fabricated hollow nickel/cobalt molybdate rods with O-defects (D-H-NiMoO4 @CoMoO4 ) through a soft-template and partial reduction method, enhancing D-H-NiMoO4 @CoMoO4 's electrochemical performance, yielding a specific capacitance of 1329â F g-1 , and demonstrating excellent durability with 95.8 % capacity retention after 3000â cycles. D-H-NiMoO4 @CoMoO4 was used as the positive electrode to construct an asymmetric supercapacitor, displaying an energy density of up to 34.13â Wh kg-1 and demonstrating good predisposition towards practical applications. This work presents an effective approach to fabricate and use hollow nickel/cobalt molybdate rods with O-defects as pseudocapacitor material for high-performance capacitive energy storage devices.
RESUMO
The development of a negative electrode for supercapacitors is a critical challenge for the next-generation of energy-storage devices. Herein, two new electrodes formed by the coordination polymers [Ni(itmb)4 (HPMo12 O40 )]·2H2 O (1) and [Zn(itmb)3 (H2 O)(HPMo12 O40 )]·4H2 O (2) (itmb = 1-(imidazo-1-ly)-4-(1,2,4-triazol-1-ylmethyl)benzene), synthesized by a simple hydrothermal method, are described. Compounds 1 and 2 show high capacitances of 477.9 and 890.2 F g-1 , respectively. An asymmetric supercapacitor device assembled using 2 which has novel water-assisted proton channels as negative electrode and active carbon as positive electrode shows ultrahigh energy density and power density of 23.4 W h kg-1 and 3864.4 W kg-1 , respectively. Moreover, the ability to feed a red light emitting diode (LED) also demonstrates the feasibility for practical use. The results allow a better elucidation of the storage mechanism in polyoxometalate-based coordination polymers and provide a promising direction for exploring novel negative materials for new-generation high-performance supercapacitors.
RESUMO
A composite modified electrode was prepared based on α-K7P2VW17O62·18H2O (P2W17V), CNTs and AuCo nanoparticles (AuCo NPs), and used as a structurally stable and highly sensitive electrochemical sensor for simultaneous determination of dopamine (DA) and uric acid (UA). The combination of three active components endows the electrode with large specific surface area, high electrical conductivity, and excellent electrochemical activity. The as-prepared modified electrode exhibited impressive electrocatalytic oxidation performance of DA and UA at an optimum working potential (0.172 V vs. Ag/AgCl for DA and 0.288 V vs. Ag/AgCl for UA) with linear detection range from 1.25 × 10-6 to 2.81 × 10-4 M and 0.75 × 10-6 to 1.66 × 10-4 M and the detection limit of 0.15 and 0.25 µM (S/N = 3) for DA and UA, respectively. Additionally, the peak-to-peak separation signals in DPV are 116 mV. The influence of several possible co-existing substances was investigated. The applicability of the method for real samples analysis was tested by determination of DA and UA in human serums. This new sensor holds great promise for sensitive determination of DA and UA in real application. Graphical abstract.
Assuntos
Dopamina/sangue , Técnicas Eletroquímicas/métodos , Nanopartículas Metálicas/química , Nanotubos de Carbono/química , Compostos de Tungstênio/química , Ácido Úrico/sangue , Quitosana/química , Cobalto/química , Dopamina/química , Técnicas Eletroquímicas/instrumentação , Eletrodos , Ouro/química , Humanos , Limite de Detecção , Oxirredução , Óxidos/química , Ácido Úrico/químicaRESUMO
To investigate the relationship between the structures of polyoxometalate host-guest materials and their energy-storage performance, three novel polyoxometalate-based metal-organic compounds, [Ag10(C2H2N3)8][HVW12O40], [Ag10(C2H2N3)6][SiW12O40], and [Ag(C2H2N3)][Ag12(C2H2N3)9][H2BW12O40] are synthesized by a one-step hydrothermal method and further confirmed by single-crystal X-ray diffraction analyses and other numerous characterization techniques. In compound [Ag10(C2H2N3)8][HVW12O40], the Keggin clusters are intersected into channels formed by a 3D open metal-organic framework. In contrast, in compounds [Ag10(C2H2N3)6][SiW12O40] and [Ag(C2H2N3)][Ag12(C2H2N3)9][H2BW12O40], the Keggin clusters are encapsulated into silver-triazole metal-organic nanocages to construct core-shell structures, which are further fused together by covalent bonds to form 3D polyoxometalate-based metal-organic frameworks. The electrochemical properties of three compound-based electrodes are estimated by cyclic voltammetry, galvanostatic charge-discharge, electrochemically active surface area, and electrochemical impedance spectroscopy. The results of the electrochemical performance tests indicate that these compounds possess high specific capacitance and cycling stability, especially [Ag10(C2H2N3)8][HVW12O40], showing a specific capacitance of 93.5 F g-1, which is higher than that of many other polyoxometalate-based electrode materials. A possible mechanism of the electrochemical performance is explored, which is mainly related to the redox capacity of polyoxometalate, the electrochemically active surface area, the electrochemical impedance spectroscopy, and the microstructures of polyoxometalate-based metal-organic frameworks.
RESUMO
A Cr-based metal-organic framework MIL-101(Cr) was used to load platinum nanoparticles (PtNPs) that were placed on a glassy carbon electrode (GCE). The modified GCE was used as a non-enzymatic xanthine sensor. Compared to bare GCE, it requires a strongly decreased working potential and an increased signal current for xanthine oxidation. This is due to the crystalline ordered structure and large specific surface of the MIL-101(Cr), and to the high conductivity of the Pt NPs. Differential pulse voltammetry (DPV) shows the sensor to have a wide linear range (0.5 - 162 µM), a low detection limit (0.42 µM), and high selectivity. It was applied to the simultaneous determination of dopamine, uric acid, xanthine and hypoxanthine at working potentials of 0.13, 0.28, 0.68 and 1.05 V, respectively (vs. Ag/AgCl) and to quantify xanthine in spiked serum samples. Graphical abstract This is the first report of non-enzymatic xanthine electrochemical sensor based on metal-organic framework loaded with nanoparticles.
Assuntos
Técnicas Biossensoriais/métodos , Dopamina/sangue , Técnicas Eletroquímicas/métodos , Hipoxantina/sangue , Nanopartículas Metálicas/química , Ácido Úrico/sangue , Xantina/sangue , Humanos , Estruturas Metalorgânicas/química , Platina/químicaRESUMO
Two novel helical compounds based on polyoxovanadates, [Co(H2O)2V2O6] (1) and [Co(bimb)V2O6] (2) (bimb = 1,3-bis(1-imidazoly)benzene), have been synthesized under identical hydrothermal conditions, providing two structurally different helical motifs due to introduction of a V-shaped bimb ligand in 2. Compound 1 possesses a pair of entanglement double helixes in a 3D inorganic framework, whereas compound 2 shows a single entangled double helix in a 3D inorganic-organic network owing to the influences of steric hindrance of ligands as well as coordination geometries of metal cations. The electrocatalytic and photocatalytic properties of 1 and 2 were also investigated in details.
Assuntos
Cobalto/química , Vanadatos/química , Ligantes , Modelos Moleculares , Difração de Pó , Espectrofotometria UltravioletaRESUMO
Photocatalytic hydrogen (H2) evolution can effectively solve the global energy problem, in which the key factor is the synthesis of efficient photocatalytic materials. In this study, we successfully synthesized a novel photocatalyst, BiWCo/CuS/PGCN, by functionalizing porous graphitic carbon nitride (PGCN) with sandwich-type polyoxometalate Na3.5Co4[Bi2Co2W19.75O70(H2O)6]·39.5H2O (BiWCo) and introducing copper sulfide (CuS) nanoparticles as a cocatalyst. This approach was aimed at enhancing the built inner electric field between interfaces, resulting in a significant improvement in photocatalytic H2 evolution performance. This research adopts a step-by-step method to synthesize BiWCo/CuS/PGCN composites with p-n heterojunctions, which has high visible light absorption and a synergistic effect of multiple elements. PGCN with a high specific surface area contributes to the uniform distribution of active sites. In addition, the nano-CuS cocatalyst provides abundant active sites and more electron transfer pathways for photocatalysis. Therefore, the H2 production efficiency of BiWCo/CuS/PGCN is 6.3 times that of PGCN, 4.5 times that of BiWCo and 2.5 times that of BiWCo/PGCN under visible light. The H2 production rate of BiWCo/CuS/PGCN reaches 3477.58 µmol g-1 h-1. At the same time, the ternary photocatalyst shows high stability after 30 hours and 5 cycles. This work demonstrates that BiWCo/CuS/PGCN has good application prospects in H2 evolution, and provides a new strategy for the design of efficient ternary photocatalytic materials.
RESUMO
Platinum-based catalysts exhibit outstanding electrocatalytic performance in the hydrogen evolution reaction (HER). However, platinum-based catalysts face significant challenges due to their rarity and high cost. This paper endeavors to shed light on a promising alternative: polyoxometalate (POM)-based catalysts, which possess significant potential for the synthesis of non-noble metal-based catalysts for the HER. Utilizing POMs as raw materials to assemble POM-derived materials, including POM-derived crystalline materials, metal sulfides, phosphides, carbides, nitrides, and so on, has emerged as an effective approach for the synthesis of hydrogen evolution electrocatalysts. This approach offers advantages in both stability and electrocatalytic performance. This comprehensive review navigates through latest progress in the assembly strategy and HER performance of POM-based crystal materials, alongside discussion on transition metal compounds derived from POMs, such as carbides, phosphides, and sulfides. Besides, future developments in POM-derived electrocatalyst regulation of the electrochemical HER are prospected.
RESUMO
MoS2-based materials have emerged as photoelectric semiconductors characterized by a narrow band gap, high capacity for absorbing visible light, and reduced H2 adsorption energy comparable to Pt. These attributes render them appealing for application in photocatalytic hydrogen production. Despite these advantages, the widespread adoption of MoS2-based materials remains hindered by challenges associated with limited exposure to active sites and suboptimal catalytic hydrogen production efficiency. To address these issues, we have designed and synthesized a new class of highly dispersed bimetallic/trimetallic sulfide materials. This was achieved by developing polyoxometalate synthons containing Ni-Mo elements, which were subsequently reacted with thiourea and CdS. The resulting Ni3S2-MoS2 and Ni3S2-MoS2-CdS materials achieve photocatalytic hydrogen production rates of 2770 and 2873 µmol g-1h-1, respectively. Notably, the rate of 2873 µmol g-1h-1 for Ni3S2-MoS2-CdS surpassed triple (3.23 times) the performance of CdS and nearly sextuple (5.77 times) that of single MoS2. These materials outperformed the majority of MoS2-based photocatalysts. Overall, this study introduces a straightforward methodology for synthesizing bimetallic/trimetallic sulfides with enhanced photocatalytic H2 evolution performance. Our findings underscore the potential of transition metal sulfide semiconductors in the realm of photocatalysis and pave the way for the development of more sustainable energy production systems.
RESUMO
Heteroatom doping and phase engineering are effective ways to promote the catalytic activity of nanoenzymes. Nitrogen-doped 1 T/2H mixed phase MoS2/CuS heterostructure nanosheets N-1 T/2H-MoS2/CuS are prepared by a simple hydrothermal approach using polyoxometalate (POM)-based metal-organic frameworks (MOFs) (NENU-5) as a precursor and urea as nitrogen doping reagent. The XPS spectroscopy (XPS) and Raman spectrum of N-1 T/2H-MoS2/CuS prove the successful N-doping. NENU-5 was used as the template to prepare 1 T/2H-MoS2/CuS with high content of 1 T phase by optimizing the reaction time. The use of urea as nitrogen dopant added to 1 T/2H-MoS2/CuS, resulted in N-1 T/2H-MoS2/CuS with an increase in the content of the 1 T phase from 80 % to 84 % and higher number of defects. N-1 T/2H-MoS2/CuS shows higher peroxidase activity than 1 T/2H-MoS2/CuS and a catalytic efficiency (Kcat/Km) for H2O2 twice as high as that of 1 T/2H-MoS2/CuS. The enhanced catalytic activity has probably been attributed to several reasons: (i) the insertion of urea during the hydrothermal process in the S-Mo-S layer of MoS2, causing an increase in the interlayer spacing and in 1 T phase content, (ii) the replacement of S atoms in MoS2 by N atoms from the urea decomposition, resulting in more defects and more active sites. As far as we know, N-1 T/2H-MoS2/CuS nanosheets have the lowest detection limit (0.16 µm) for the colorimetric detection of hydroquinone among molybdenum disulfide-based catalysts. This study affords a new approach for the fabrication of high-performance nanoenzyme catalysts.
RESUMO
The hydrogen evolution reaction (HER) is important for "green" hydrogen production from water electrolysis. Nowadays, there is an urgent need to construct highly efficient electrocatalysts to boost the HER and achieve hydrogen production. Herein, we present the preparation of a new composite Co-Mo bimetallic sulfide supported on carbon cloth (MoS2/CoS2/CC) via a one-pot hydrothermal sulfurization strategy using (C3H5N2)6[CoMo12O40]·10H2O (CoMo12) as a metal source and thiourea as a sulfur source. The obtained MoS2/CoS2/CC catalyst exhibited outstanding HER ability, with an overpotential of 69 mV when the current density is 10 mA cm-2 in KOH solution, showing comparable performance with those of the advanced Pt/C electrodes tested under the same conditions. Additionally, the results of XRD after the catalytic reaction showed that the electrode had excellent stability in the electrolyte of 1.0 M KOH.
RESUMO
The development of photocatalysts toward highly efficient H2 evolution reactions is a feasible strategy to achieve the effective conversion of solar energy and meet the increasing demand for new energy. To this end, we prepared two different CdS-MoS2 photocatalysts with unique morphologies ranging from hexagonal prisms to tetragonal nanotubes by carefully tuning polyoxometalate synthons. These two photocatalysts, namely, CdS-MoS2-1 and CdS-MoS2-2, both exhibited remarkable photocatalytic efficiency in H2 generation, among which CdS-MoS2-2 showed superior performance. In fact, the best catalytic hydrogen desorption rate of CdS-MoS2-2 is as high as 1815.5 µmol g-1 h-1. Such performance is superior to twice that of single CdS and almost four times that of pure MoS2. This obvious enhancement can be accredited to the highly open nanotube morphology and highly dispersed heterometallic composition of CdS-MoS2-2, which represents an excellent example of the highest noble-metal-free H2 evolution photocatalysts reported so far. Taken together, these findings suggest that the development of highly dispersed heterometallic catalysts is an auspicious route to realize highly efficient conversion of solar energy and that CdS-MoS2-2 represents a major advance in this field.