CN115636942A - Preparation method of high-spin Fe3+ trimetal MIL-101 (FeNiTi) material - Google Patents
Preparation method of high-spin Fe3+ trimetal MIL-101 (FeNiTi) material Download PDFInfo
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Abstract
The invention provides Fe with high sensitivity and high spin for Surface Enhanced Raman Scattering (SERS) detection 3+ The preparation method of the trimetal MIL-101 (FeNiTi) material. The method gradually introduces an aliovalent transition metal Ni by modifying MIL-101 (Fe) 2+ And Ti 4+ Fe in MOF can be realized 3+ Successfully converting from low spin to high spin, and regulating and controlling the proportion of the high spin to finally obtain the non-noble metal-based SERS active substrate with high detection sensitivity. The invention takes a metal organic framework MIL-101 (Fe) as a raw material, and an aliovalent transition metal element Ni is added 2+ And Ti 4+ Obtaining Fe with high spin 3+ Trimetal MIL-101 (FeNiTi) material in a proportion of 100%. High spin Fe prepared 3+ The trimetal MIL-101 (FeNiTi) material shows excellent SERS detection activity and stability in SERS detection.
Description
Technical Field
The inventionRelates to a method for detecting Surface Enhanced Raman Scattering (SERS) with high proportion of Fe 3+ A high-spin trimetal MIL-101 (FeNiTi) material belongs to the field of nano materials and the technical field of SERS. .
Background
Surface Enhanced Raman Spectroscopy (SERS) is widely used in many research fields as a non-destructive analysis technique. The traditional noble metal substrate (such as Au and Ag) has strong Surface Plasmon Resonance (SPR) effect to greatly enhance the electromagnetic field intensity, so the traditional noble metal substrate is widely applied to the SERS field. However, noble metal SERS substrates suffer from several unavoidable limitations, including high cost, poor chemical stability, and low biocompatibility, which have prompted extensive researchers to shift the focus of research to some non-noble metal materials, such as semiconductors, metal Organic Frameworks (MOFs), graphene, and others. It is generally believed that the primary SERS enhancement mechanism of these non-noble metal materials is due to the Charge Transfer (CT) process between the substrate and the detected molecules. For example, metal oxides (e.g., moO) having an abundance of oxygen vacancies 3-x 、TiO 2-x And WO 3-x ) It has been shown that the CT process between the adsorbed molecule and the SERS substrate can be effectively facilitated because such materials can create additional energy levels or increase their ability to resonantly absorb. However, the surface defects of these materials are not stable enough under the irradiation of raman laser and are easily oxidized even under laboratory conditions, which severely limits the application of these materials in practical SERS. Therefore, it is highly desirable and necessary to develop flexible enhancement strategies to produce robust SERS-based substrate materials.
In contrast to defect engineering, the impact of other intrinsic electronic states of non-noble metal SERS substrates, including orbital filling (spin state) of transition metals and electronic localized/delocalized states of materials, on substrate SERS performance has not been studied extensively to date. It is well known in the fields of electrocatalysis and photocatalysis that the strength of the bond between the crystalline material and the adsorbate and the electron transfer can be modulated by modulating the spin state of the transition metal ion.
Based on the background of the above research, a high SER was prepared by a simple coprecipitation methodS active high spin Fe 3+ Of trimetallic MIL-101 (FeNiTi) material having up to 6.1 x 10 for Methylene Blue (MB) molecules 6 Enhancement Factor (EF) of (2), detection limit is also as low as 10 -9 And M. In addition, the SERS material also exhibits excellent detection stability. The results show that three transition metal atoms have different 3d orbital electron filling degrees and high-spin Fe 3+ With a hetero-valent transition metal Ni 2+ And Ti 4+ The three-metal MIL-101 (FeNiTi) material is subjected to electron delocalization due to the orbital coupling. Having high spin of Fe 3+ The MIL-101 (FeNiTi) material is beneficial to detecting the adsorption of molecules, and the electron delocalization promotes the charge transfer process from the molecules to the MIL-101 (FeNiTi), so that the MIL-101 (FeNiTi) material has excellent SERS performance.
Disclosure of Invention
The invention provides Fe with high sensitivity and high spin for Surface Enhanced Raman Scattering (SERS) detection 3+ The method for preparing the trimetal MIL-101 (FeNiTi) material comprises the steps of modifying MIL-101 (Fe) and gradually introducing an aliovalent transition metal Ni 2+ And Ti 4+ Fe in MOF can be realized 3+ The method is characterized in that the high spin is converted from low spin success, and the proportion of the high spin is regulated, so that the non-noble metal-based SERS active substrate with high detection sensitivity is finally obtained. The invention takes a metal organic framework MIL-101 (Fe) as a raw material, and an aliovalent transition metal element Ni is added 2+ And Ti 4+ Obtaining Fe with high spin 3+ Trimetal MIL-101 (FeNiTi) material in a proportion of 100%. After the introduction of the aliovalent transition metal elements, the octahedral structure of the Fe-O species is deformed to a certain degree, so that the crystal field splitting energy of the transition metal is further reduced, and the Fe is realized 3+ The transition of the spin state. Having high spin of Fe 3+ The trimetal MIL-101 (FeNiTi) material and the detected molecules have stronger bonding capability, and can promote the charge transfer process of the materials and the detected molecules, thereby greatly improving the SERS signal. High spin Fe prepared 3+ The trimetal MIL-101 (FeNiTi) material shows excellent SERS detection activity and stability in SERS detection.
The method specifically comprises the following scheme:
high-sensitivity high-spin Fe for Surface Enhanced Raman Spectroscopy (SERS) detection 3+ The preparation method of the trimetal MIL-101 (FeNiTi) material is characterized by comprising the following steps:
the first step is as follows: feCl 3 ·6H 2 O、NiCl 2 ·6H 2 Dissolving O and TTIP in N, N-Dimethylformamide (DMF) to obtain a solution A; terephthalic acid (H) 2 BDC) is dissolved in DMF to obtain solution B;
the second step is that: slowly adding the solution A into the solution B, stirring and reacting completely, transferring the mixed solution into a closed high-pressure kettle, and placing the closed high-pressure kettle in an oven for heating and reacting completely;
the third step: after the reaction is finished, centrifugally washing to obtain a light yellow solid product; and finally, drying the solid product to obtain Ti-doped MIL-101 (FeNiTi), wherein the mass of Fe and Ni is 1.
Further, in the first step, feCl is added 3 ·6H 2 O、NiCl 2 ·6H 2 Dissolving O and TTIP in N, N-Dimethylformamide (DMF) to obtain solution A, wherein FeCl 3 ·6H 2 O、NiCl 2 ·6H 2 The ratio between O and TTIP was 2.5mmol:2.5mmol:100 mu L of the solution; terephthalic acid (H) 2 BDC) was dissolved well in DMF to give solution B.
Further, in a second step, according to FeCl 3 ·6H 2 O、H 2 The ratio between BDC is 0.676g:0.776g of solution A and B were mixed, stirred vigorously at room temperature for thorough reaction and transferred to a polytetrafluoroethylene liner.
Further, in the third step, each of the solutions was washed three times by centrifugation with DMF, ethanol and water, respectively.
Further, the solid was dried in a constant temperature oven at 75 ℃ for 12 hours.
Further, the method specifically comprises the following steps:
the first step is as follows: 0.676g FeCl 3 ·6H 2 O(2.5mmol)、0.595g NiCl 2 ·6H 2 O (2.5 mmol) and 100. Mu.L TTIP were dissolved well in 40mL of N, N-Dimethylformamide (DMF) to give a solution A; 0.776g of terephthalic acid (H) 2 BDC) is fully dissolved in 40mLDMF to obtain solution B;
the second step is that: slowly adding the solution A into the solution B, stirring vigorously at room temperature for 20min, transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 100mL, packaging into a stainless steel autoclave, and placing the stainless steel autoclave in a drying oven at 120 ℃ for reaction for 20 hours;
the third step: after the reaction is finished, respectively centrifuging and washing the mixture for three times by using DMF (dimethyl formamide), ethanol and water to obtain a light yellow solid product; and finally, drying the solid in a constant-temperature oven at 75 ℃ for 12h to obtain MIL-101 (FeNiTi) with the Ti doping amount of 4% by mass.
The invention has the beneficial technical effects
1. The invention modifies MIL-101 (Fe) and introduces an aliovalent transition metal element Ni 2+ And Ti 4+ Induce total Fe 3+ Successful transition from low spin to high spin, resulting in fully high spin Fe 3+ The trimetal MIL-101 (FeNiTi) material. By controlling the addition of the elements of the aliovalent transition metal Ni and Ti, the electronic structure and the valence state of each element are successfully regulated and controlled, so that the octahedral configuration of Fe-O species is deformed to a certain degree, the crystal field splitting energy of the Fe-O species is reduced, and Fe is triggered 3+ Successful transition from low spin to high spin with high spin of Fe 3+ The ratio is 100%. Having high spin of Fe 3 + The trimetal MIL-101 (FeNiTi) material and the detected molecules have stronger bonding capability, and can promote the charge transfer process of the material and the detected molecules, thereby greatly improving the SERS signal. The nano material prepared by the method has high SERS detection capability, and shows excellent SERS detection activity and stability in a non-noble metal SERS substrate.
2. The preparation process of the trimetal MIL-101 (FeNiTi) material is greatly simplified by adopting a one-step coprecipitation method, the raw materials are simple and easy to obtain, and the cost is reduced. Successfully regulates and controls Fe by introducing simple valence transition metal ions without any complicated preparation process 3+ Spin shape ofAnd the state is simple and feasible.
Drawings
FIG. 1 (a) is an X-ray diffraction pattern of the monometallic MIL-101 (Fe), bimetallic MIL-101 (FeNi) and trimetallic MIL-101 (FeNiTi) materials of comparative examples 1-2 and example 1. (a) The X-ray diffraction patterns for the monometallic MIL-101 (Fe), bimetallic MIL-101 (FeNi), and trimetallic MIL-101 (FeNiTi) materials of comparative examples 1-2 and example 1; (b) Is a scanning electron microscope image of the trimetal MIL-101 (FeNiTi) material in example 1.
FIG. 2 Mossbauer spectra of monometallic MIL-101 (Fe), bimetallic MIL-101 (FeNi), and trimetallic MIL-101 (FeNiTi) materials. (a-c) Fe of the three materials of comparative examples 1-2 and example 1 3+ The spin state of (3).
Fig. 3 SERS activity plots for three materials. (a) For the monometallic MIL-101 (Fe), bimetallic MIL-101 (FeNi) and trimetallic MIL-101 (FeNiTi) materials versus MB molecules (10) in comparative examples 1-2 and example 1 -5 M) SERS detection activity diagram; (b) Is a SERS detection activity graph of the trimetal MIL-101 (FeNiTi) material of example 1 to MB molecules with different concentrations; (c) For the trimetallic MIL-101 (FeNiTi) material of example 1, different times later, the MB molecule (10) -5 M) SERS detection activity diagram.
Detailed description of the preferred embodiments
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples within the scope not exceeding the gist thereof.
High-sensitivity high-spin Fe for SERS detection 3+ The method of the trimetal MIL-101 (FeNiTi) material is as follows: 0.676g FeCl 3 ·6H 2 O(2.5mmol)、0.595g NiCl 2 ·6H 2 O (2.5 mmol) and 100. Mu.L Tetraisopropyl Titanate (TTIP) were dissolved in 40mL of N, N-Dimethylformamide (DMF) to give solution A; 0.776g of terephthalic acid (H) 2 BDC) was dissolved in 40mL DMF to give solution B. And then slowly adding the solution A into the solution B, stirring vigorously at room temperature for 20min, transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 100mL, packaging into a stainless steel high-pressure kettle, and placing the stainless steel high-pressure kettle in an oven with the temperature of 120 ℃ for reaction for 20 hours. Reaction ofAfter completion, the product was washed three times each with DMF, ethanol and water by centrifugation to give a yellow solid. And finally, drying the solid in a constant-temperature oven at 75 ℃ for 12 hours to obtain an MIL-101 (FeNiTi) sample with the Ti doping amount of 4%.
The inventors have surprisingly found that when the aliovalent transition metal element Ni is introduced simultaneously 2+ And Ti 4+ When the Fe-O crystal is in use, the octahedral configuration of Fe-O species is deformed to a certain extent, so that the crystal field splitting energy is reduced, and all Fe is triggered 3+ Successful transition from low spin to high spin with high spin Fe 3+ The ratio is 100%.
Comparative example 1
Synthesis of MIL-101 (Fe)
First, 1.351g of FeCl was added 3 ·6H 2 O (5 mmol) was dissolved in 40MLDMF to obtain solution A; 0.776g of H 2 BDC was dissolved in 40mL DMF and was designated solution B. And then slowly adding the solution A into the solution B, vigorously stirring at room temperature for 20min, transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 100mL, packaging into a stainless steel autoclave, and placing the stainless steel autoclave in an oven at 120 ℃ for reaction for 20 hours. After the reaction was completed, it was centrifuged and washed three times with DMF, ethanol and water, respectively, to obtain an orange solid product. And finally, drying the solid in a constant-temperature oven at 75 ℃ for 12 hours to obtain MIL-101 (Fe).
Comparative example 2
Synthesis of bimetallic MIL-101 (FeNi)
First, 0.676g FeCl was added 3 ·6H 2 O (2.5 mmol) and 0.595g of NiCl 2 ·6H 2 O (2.5 mmol) was dissolved in 40mL DMF to give solution A; 0.776g of H 2 BDC was dissolved in 40ml of dmdm and named solution B. And then slowly adding the solution A into the solution B, vigorously stirring at room temperature for 20min, transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 100mL, packaging into a stainless steel autoclave, and placing the stainless steel autoclave in an oven at 120 ℃ for reaction for 20 hours. After the reaction is finished, the product is respectively centrifuged and washed three times by DMF, ethanol and water to obtain a yellow solid product. And finally, drying the solid in a constant-temperature oven at 75 ℃ for 12h to obtain the MIL-10 with the molar ratio of Fe to Ni being 11(FeNi)。
Comparative example 3
Synthesis of bimetallic MIL-101 (FeTi)
1.351g of FeCl 3 ·6H 2 Dissolving O (2.5 mmol) and 100. Mu.L TTIP in 40ml DMF to obtain solution A; 0.776g of H 2 BDC was dissolved in 40mL DMF to give solution B. And then slowly adding the solution A into the solution B, vigorously stirring at room temperature for 20min, transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 100mL, packaging into a stainless steel autoclave, and placing the stainless steel autoclave in an oven at 120 ℃ for reaction for 20 hours. After the reaction is finished, the mixture is respectively centrifuged and washed by DMF, ethanol and water for three times to obtain a yellow solid product. And finally, drying the solid in a constant-temperature oven at 75 ℃ for 12h to obtain an MIL-101 (FeTi) sample with the Ti doping amount of 4% by mass.
Example 1
Synthesis of trimetal MIL-101 (FeNiTi)
0.676g of FeCl 3 ·6H 2 O(2.5mmol)、0.595g NiCl 2 ·6H 2 O (2.5 mmol) and 100. Mu.L TTIP were dissolved in 40mL DMF to give solution A; 0.776g of H 2 BDC was dissolved in 40mL DMF to give solution B. And then slowly adding the solution A into the solution B, stirring vigorously at room temperature for 20min, transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 100mL, packaging into a stainless steel autoclave, and placing the stainless steel autoclave in an oven at 120 ℃ for reaction for 20 h. After the reaction is finished, the product is respectively centrifuged and washed three times by DMF, ethanol and water to obtain a yellow solid product. And finally, drying the solid in a constant-temperature oven at 75 ℃ for 12 hours to obtain an MIL-101 (FeNiTi) sample with the Ti doping amount of 4%.
Experiment and data
The detection activity investigation method of the SERS substrate provided by the invention comprises the following steps:
first, 1mL of methylene blue solution (10) -5 M, dissolved in deionized water) and 5mg of the MIL-101 nanoparticle solution are uniformly mixed, after standing for 12 hours, 600 mu L of the mixed solution is taken out and placed on a clean glass sheet, and after the mixed solution is naturally dried, the glass sheet is washed twice by the deionized water and then used for Raman detection experiments. At 532nm (the maximum power is 45mW,1% work)Power) was recorded under a laser with a lens magnification of 50 x and an integration time of 10s.
FIG. 1 (a) is an X-ray diffraction pattern of the monometallic MIL-101 (Fe), bimetallic MIL-101 (FeNi) and trimetallic MIL-101 (FeNiTi) materials of comparative examples 1-2 and example 1. As can be seen from fig. 1a, the diffraction peaks of the three materials are substantially consistent, which indicates that the crystal form of the material is not changed after the introduction of the aliovalent transition metal element, and the crystal form of the material of comparative example 3 is not changed (X-ray diffraction pattern is not shown). However, the diffraction peak intensity of the trimetal MIL-101 (FeNiTi) material is slightly decreased compared with other materials, which indicates that the crystallinity of the trimetal material is decreased, probably because the introduction of the aliovalent transition metal ions changes the crystallinity. The above results confirmed that the samples in comparative examples 1-2 and example 1 are both of the MIL-101 (Fe) series. FIG. 1 (b) is a scanning electron microscope image of a trimetal MIL-101 (FeNiTi) material, in which it can be observed that the material is in a shuttle shape with uniform size and regular appearance.
Fig. 2 (a-c) are mossbauer spectra of the three materials of comparative examples 1-2 and example 1, the spectrum of comparative example 3 not being shown. Fe in monometallic MIL-101 (Fe) material 3+ Mainly presents a low spin state, a small part is a high spin state, and the bimetallic MIL-101 (FeNi) material is compared with the MIL-101 (Fe), fe 3+ The high spin ratio of (2) is increased, and the low spin ratio is decreased; the bimetallic MIL-101 (FeTi) and MIL-101 (FeNi) materials are substantially the same (not shown); surprisingly, the Fe in the trimetallic MIL-101 (FeNiTi) material of the present invention 3+ All exhibited high spin states and no low spin states were detected. The above results show that Fe in the MIL-101 (Fe) material is effectively regulated and controlled by introducing the aliovalent transition metal ions 3+ From low spin to high spin.
FIG. 3 (a) is a SERS activity graph of detecting Methylene Blue (MB) molecules of three materials of comparative examples 1-2 and example 1; the activity diagram of comparative example 3 is not shown; it can be seen that the SERS detection activity of the trimetal MIL-101 (FeNiTi) material is the best, the activity of the bimetal MIL-101 (FeNi) material is the second most, the activity of the bimetal MIL-101 (FeTi) material is the second most, and the activity of the single metal MIL-101 (F)e) The activity of the material is the worst, wherein the SERS detection activity of the trimetal MIL-101 (FeNiTi) material is greatly superior to that of the comparative example. (b) And (c) a SERS activity graph for detecting MB molecules with different concentrations of the trimetal MIL-101 (FeNiTi) material of example 1 and a SERS activity graph for detecting MB molecules of the trimetal MIL-101 (FeNiTi) material stored for different time periods. By introducing the aliovalent transition metal ions, the Fe in the MIL-101 (Fe) material can be effectively regulated and controlled 3+ Spin state of (1), fe in trimetallic MIL-101 (FeNiTi) material 3+ The product is completely in a high-spin state, has excellent SERS detection activity, and has a detection limit of MB molecules as low as 10 -9 M, after long-term storage, the material still has excellent SERS detection performance, which indicates that the material has good chemical stability.
The above experimental results prove that the Fe with high spin synthesized by us 3+ The trimetal MIL-101 (FeNiTi) material has excellent SERS detection activity and stability.
While the present invention has been described in detail with reference to the preferred embodiments thereof, it should be understood that the above description should not be taken as limiting the invention.
Claims (6)
1. Fe with high sensitivity and high spin for Surface Enhanced Raman Scattering (SERS) detection 3+ The preparation method of the trimetal MIL-101 (FeNiTi) material is characterized by comprising the following steps:
the first step is as follows: proportionally mixing FeCl 3 ·6H 2 O、NiCl 2 ·6H 2 Dissolving O and TTIP in N, N-Dimethylformamide (DMF) to obtain a solution A; terephthalic acid (H) 2 BDC) is dissolved in DMF to obtain solution B;
the second step: slowly adding the solution A into the solution B, stirring and reacting completely, transferring the mixed solution into a closed high-pressure kettle, and placing the closed high-pressure kettle in an oven for heating and reacting completely;
the third step: after the reaction is finished, centrifugally washing to obtain a light yellow solid product; and finally, drying the solid product to obtain the Ti-doped MIL-101 (FeNiTi) material, wherein the mass ratio of Fe to Ni is 1.
2. High-spin Fe with high sensitivity according to claim 1 3+ The preparation method of the trimetal MIL-101 (FeNiTi) material is characterized by comprising the following steps: in a first step, feCl is introduced 3 ·6H 2 O、NiCl 2 ·6H 2 Dissolving O and TTIP in N, N-Dimethylformamide (DMF) to obtain solution A, wherein FeCl 3 ·6H 2 O、NiCl 2 ·6H 2 The ratio between O and TTIP was 2.5mmol:2.5mmol:100 mu L of the solution; mixing terephthalic acid (H) 2 BDC) was dissolved well in DMF to give solution B.
3. High-spin Fe with high sensitivity according to claim 2 3+ The preparation method of the trimetal MIL-101 (FeNiTi) material is characterized by comprising the following steps: in a second step, according to FeCl 3 ·6H 2 O、H 2 The ratio between BDCs is 0.676g:0.776g of solution A and B were mixed, stirred vigorously at room temperature and reacted further into a polytetrafluoroethylene liner.
4. High-spin Fe with high sensitivity according to claim 1 3+ The preparation method of the trimetal MIL-101 (FeNiTi) material is characterized by comprising the following steps: in the third step, each of the samples was washed three times with DMF, ethanol and water, respectively, by centrifugation.
5. High-spin Fe with high sensitivity according to claim 1 3+ The preparation method of the trimetal MIL-101 (FeNiTi) material comprises the step of drying the solid in a constant-temperature oven at 75 ℃ for 12 hours.
6. High-spin Fe with high sensitivity according to claim 1 3+ The preparation method of the trimetal MIL-101 (FeNiTi) material specifically comprises the following steps:
the first step is as follows: 0.676g FeCl 3 ·6H 2 O(2.5mmol)、0.595g NiCl 2 ·6H 2 O (2.5 mmol) and 100. Mu.L TTIP were dissolved well in 40mL of N, N-dimethylFormamide (DMF) to obtain a solution A; 0.776g of terephthalic acid (H) 2 BDC) was fully dissolved in 40mL DMF to obtain solution B;
the second step is that: slowly adding the solution A into the solution B, stirring vigorously at room temperature for 20min, transferring the mixed solution into a polytetrafluoroethylene lining with the volume of 100mL, packaging into a stainless steel autoclave, and placing the stainless steel autoclave in a drying oven at 120 ℃ for reaction for 20 hours;
the third step: after the reaction is finished, respectively centrifuging and washing the mixture for three times by using DMF (dimethyl formamide), ethanol and water to obtain a light yellow solid product; and finally, drying the solid in a constant-temperature oven at 75 ℃ for 12h to obtain MIL-101 (FeNiTi) with the Ti doping amount of 4% by mass.
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| CN106670495A (en) * | 2015-11-06 | 2017-05-17 | 南京大学 | Preparation method of network-state Ag-Au-Pd trimetal porous material |
| CN112961650A (en) * | 2021-02-06 | 2021-06-15 | 安徽理工大学 | Tri-metal organic framework derived iron-nickel alloy/porous carbon ultrathin wave absorber and preparation method thereof |
| WO2022142109A1 (en) * | 2020-12-29 | 2022-07-07 | 中国检验检疫科学研究院 | Preparation method for sers substrate, sers substrate, and application |
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| CN106670495A (en) * | 2015-11-06 | 2017-05-17 | 南京大学 | Preparation method of network-state Ag-Au-Pd trimetal porous material |
| WO2022142109A1 (en) * | 2020-12-29 | 2022-07-07 | 中国检验检疫科学研究院 | Preparation method for sers substrate, sers substrate, and application |
| CN112961650A (en) * | 2021-02-06 | 2021-06-15 | 安徽理工大学 | Tri-metal organic framework derived iron-nickel alloy/porous carbon ultrathin wave absorber and preparation method thereof |
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| JIE LIN ET AL.: "Ultrasensitive SERS Detection by Defect Engineering on Single Cu2O Superstructure Particle", ADVANCED MATERIALS, vol. 29, pages 1 - 7 * |
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