Solid-state NMR detection, characterization, and quantification of the multiple aluminum environments in US-Y catalysts by (27)Al MAS and MQMAS experiments at very high field.

The detection of all of the aluminum present in steamed zeolite H-Y catalysts by (27)Al MAS NMR at 14.4 T (600 MHz for (1)H) and 18.8T (800 MHz for (1)H) is reported. Further, it is shown that it is possible by (27)Al MAS and MQMAS NMR measurements to clearly identify four separate aluminum environments which are characteristic of these materials and to unambiguously assign their coordinations. Average chemical shift and quadrupolar coupling parameters are used to accurately simulate the (27)Al MAS NMR spectra at 9.4 T (400 MHz for (1)H), 14.4 T (600 MHz for (1)H) and 18.8 T (800 MHz for (1)H) in terms of these four aluminum environments. In addition, these average chemical shift and quadrupolar coupling parameters are used to calculate peak positions in the (27)Al MQMAS isotropic dimension that are in good agreement with the experimental data acquired at 9.4 and 18.8 T.     

17O MAS and 3QMAS NMR investigation of crystalline V(2)O(5) and layered V(2)O(5).nH(2)O gels

The environments for oxygen sites in crystalline V(2)O(5) and in layered vanadia gels produced via sol-gel synthesis have been investigated using (17)O MAS and 3QMAS NMR. For crystalline V(2)O(5), three structural oxygen sites were observed: V=O (vanadyl), V(2)O (doubly coordinated), and V(3)O (triply coordinated). Line-shape parameters for these sites were determined from numerical simulations of the MAS spectra. For the vanadia gels at various stages of dehydration, assignments have been proposed for numerous vanadyl, doubly coordinated, and triply coordinated oxygen sites. In addition, by correlating the (17)O MAS and 3QMAS NMR, (51)V MAS NMR, and thermogravimetric analysis data, the coordination of water sites has been established. On the basis of these results, the gel structure and its evolution at various stages of hydration have been detailed. Upon rehydration of the layered gel, we observed a preferred site for initial water readsorption. The oxygen atoms of these readsorbed water molecules readily exchanged into all types of oxygen sites even at room temperature.     

Multinuclear NMR investigations of the oxygen, water, and hydroxyl environments in sodium hexaniobate

Solid-state (1)H, (17)O MAS NMR, (1)H-(93)Nb TRAPDOR NMR, and (1)H double quantum 2D MAS NMR experiments were used to characterize the oxygen, water, and hydroxyl environments in the monoprotonated hexaniobate material, Na(7)[HNb(6)O(19)].15H(2)O. These solid-state NMR experiments demonstrate that the proton is located on the bridging oxygen of the [Nb(6)O(19)](8-) cluster. The solid-state NMR results also show that the NbOH protons are spatially isolated from similar protons, but undergo proton exchange with the water species located in the crystal lattice. On the basis of double quantum (1)H MAS NMR measurements, it was determined that the water species in the crystal lattice have restricted motional dynamics. Two-dimensional (1)H-(17)O MAS NMR correlation experiments show that these restricted waters are preferentially associated with the bridging oxygen. Solution (17)O NMR experiments show that the hydroxyl proton is also attached to the bridging oxygen for the compound in solution. In addition, solution (17)O NMR kinetic studies for the hexaniobate allowed the measurement of relative oxygen exchange rates between the bridging, terminal, and hydroxyl oxygen and the oxygen of the solvent as a function of pH and temperature. These NMR experiments are some of the first investigations into the proton location, oxygen and proton exchange processes, and water dynamics for a base stable polyoxoniobate material, and they provide insight into the chemistry and reactivity of these materials.     

Local environments and lithium adsorption on the iron oxyhydroxides lepidocrocite (gamma-FeOOH) and goethite (alpha-FeOOH): a 2H and 7Li solid-state MAS NMR study

2H and 7Li MAS NMR spectroscopy techniques were applied to study the local surface and bulk environments of iron oxyhydroxide lepidocrocite (gamma-FeOOH). 2H variable-temperature (VT) MAS NMR experiments were performed, showing the presence of short-range, strong antiferromagnetic correlations, even at temperatures above the Néel temperature, T(N), 77 K. The formation of a Li+ inner-sphere complex on the surface of lepidocrocite was confirmed by the observation of a signal with a large 7Li hyperfine shift in the 7Li MAS NMR spectrum. The effect of pH and relative humidity (RH) on the concentrations of Li+ inner- and outer-sphere complexes was then explored, the concentration of the inner sphere complex increasing rapidly above the point of zero charge and with decreasing RH. Possible local environments of the adsorbed Li+ were identified by comparison with other layer-structured iron oxides such as gamma-LiFeO2 and o-LiFeO2. Li+ positions of Li+-sorbed and exchanged goethite were reanalyzed on the basis of the correlations between Li hyperfine shifts and Li local structures, and two different binding sites were proposed, the second binding site only becoming available at higher pH.     

Characterization of C18 chemically modified silica-gel and porous glass phases by high resolution solid state NMR spectroscopy and other physico-chemical methods

Summary Two types of packing materials, porous glass (PG) and silica gel (SG) have been modified by mono- and difunctional octadecylchlorosilane. The packing surfaces before and after chemical modification have been characterized by CP/MAS NMR, SIMS, porosimetrical, elemental and chromatographic methods. On the basis of the physico-chemical and chromatographic data the PG and SG (of similar porosity) used as supports of chemically bonded phases for RP HPLC, have been compared. Presented at 13th Symposium on Column Liquid Chromatography, Stockholm, June 25–30, 1989.     

Double quantum 1H MAS NMR studies of hydrogen-bonded protons and water dynamics in materials

Two-dimensional double quantum (DQ) 1H MAS NMR was used to investigate different proton environments in a series of alkali (Na, K, Rb, Cs) [Nb6O19]8- Lindqvist salts, with the water and hydrogen-bound intercluster protons being clearly resolved. Through the analysis of the DQ 1H NMR spinning sideband pattern, it is possible to extract both the mean and distribution of the motionally averaged intramolecular homonuclear 1H-1H dipolar coupling for the different water environments and the intercluster protons. Motional order parameters for the water environments were then calculated from the averaged dipolar couplings. The influence of additional intermolecular dipolar couplings due to multispin interactions were simulated and discussed.     

Characterization of a new hexasodium diphosphopentamolybdate hydrate, Na6[P2Mo5O23]x7H2O, by 23Na MQMAS NMR spectroscopy and X-ray powder diffraction

A novel hexasodium disphosphopentamolybdate hydrate, Na6[P2Mo5O23]x7H2O, has been identified using X-ray powder diffraction, 1H, 23Na, and 31P magic-angle spinning (MAS) NMR, and 23Na multiple-quantum (MQ) MAS NMR. Powder XRD reveals that the hydrate belongs to the triclinic spacegroup P1 with cell dimensions a = 10.090(3) A, b = 15.448(5) A, c = 8.460(4) A, alpha = 101.45(6) degrees, beta = 104.09(2) degrees, gamma = 90.71(5) degrees, and Z = 2. The number of water molecules of crystallization has been determined on the basis of a quantitative evaluation of the 1H MAS NMR spectrum, the crystallographic unit cell volume, and a hydrogen content analysis. The 23Na MQMAS NMR spectra of Na6[P2Mo5O23]x7H2O, obtained at three different magnetic fields, clearly resolve resonances from six different sodium sites and allow a determination of the second-order quadrupolar effect parameters and isotropic chemical shifts for the individual resonances. These data are used to determine the quadrupole coupling parameters (CQ and eta Q) from simulations of the complex line shapes of the central transitions, observed in 23Na MAS NMR spectra at the three magnetic fields. This analysis illustrates the advantages of combining MQMAS and MAS NMR at moderate and high magnetic fields for a precise determination of quadrupole coupling parameters and isotropic chemical shifts for multiple sodium sites in inorganic systems. 31P MAS NMR demonstrates the presence of two distinct P sites in the asymmetric unit of Na6[P2Mo5O23].7H2O while the 31P chemical shielding anisotropy parameters, determined for this hydrate and for Na6[P2Mo5O23]x13H2O, show that these two hydrates can easily be distinguished using 31P MAS NMR.     

Synthesis,crystal structure,and solid state NMR spectroscopy of NH(4)[(V(2)O(3))(2)(4,4'-bpy)(2)(H(2)PO(4))(PO(4))(2)].0.5H(2)O,a mixed-valence vanadium(IV,V) phosphate with a pillared layer structure

A mixed-valence vanadium phosphate, NH(4)[(V(2)O(3))(2)(4,4'-bpy)(2)(H(2)PO(4))(PO(4))(2)].0.5H(2)O, has been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group C2/c (No. 15) with a = 12.6354(8) A, b = 9.9786(6) A, c = 23.369(1) A, beta = 92.713(1) degrees, and Z = 4 with R(1) = 0.0389. The structure consists of dimers of edge-sharing vanadium(IV,V) octahedra that are connected by corner-sharing phosphate tetrahedra to form layers in the ab-plane, which are further linked through 4,4'-bipyridine pillars to generate a 3-D framework. Magnetic susceptibility confirms the valence of the vanadium atoms. The (31)P MAS NMR spectrum shows a resonance centered at 80 ppm with a shoulder at ca. 83 ppm in an intensity ratio close to 1:2, which correspond to two distinct P sites. The observed large downfield (31)P NMR shifts can be ascribed to magnetic exchange coupling involving phosphorus atoms. The unpaired electron spin density at the phosphorus nucleus was determined from variable-temperature (31)P NMR spectra. The (1)H MAS NMR spectrum was fitted to six components in accordance with the structure as determined from X-ray diffraction.     

Enhanced sensitivity and resolution in (1)H solid-state NMR spectroscopy of paramagnetic complexes under very fast magic angle spinning

High-resolution NMR spectroscopy for paramagnetic complexes in solids has been rarely performed because of its limited sensitivity and resolution due to large paramagnetic shifts and associated technical difficulties. The present study demonstrates that magic angle spinning (MAS) at speeds exceeding 20 kHz provides unusually high sensitivity and excellent resolution in 1H solid-state NMR (SSNMR) for paramagnetic systems. Spinning-speed dependence of 1H MAS spectra showed that very fast MAS (VFMAS) at 24-28 kHz enhanced sensitivity by a factor of 12-18, compared with the sensitivity of 1H SSNMR spectra under moderate MAS at 10 kHz, for Cu(dl-alanine)2.H2O and Mn(acac)3, for which the spectral ranges due to 1H paramagnetic shifts reach 200 and 1000 ppm, respectively. It was theoretically and experimentally confirmed that the absolute sensitivity of 1H VFMAS for small paramagnetic complexes such as Cu(dl-alanine)2 can be an order of magnitude higher than that of equimolar diamagnetic ligands because of short 1H T1 ( approximately 1 ms) of the paramagnetic systems and improved sensitivity under VFMAS. On the basis of this demonstrated high sensitivity, 1H SSNMR micro analysis of paramagnetic systems in a nanomole scale is proposed. Applications were performed on two polymorphs of Cu(II)(8-quinolinol)2, which is a suppressor of human cancer cells. It was demonstrated that 1H VFMAS SSNMR spectra accumulated for 20 nmol of the polycrystalline samples in 10 min enabled one to distinguish alpha- and beta-forms of Cu(II)(8-quinolinol)2 on the basis of shift positions and line widths.     

Low-load rotor-synchronised Hahn-echo pulse train (RS-HEPT) 1H decoupling in solid-state NMR: factors affecting MAS spin-echo dephasing times

Transverse dephasing times T(2)' in spin-echo MAS NMR using rotor-synchronised Hahn-echo pulse-train (RS-HEPT) low-load (1)H decoupling are evaluated. Experiments were performed at 300 and 600 MHz for (13)CH-labelled L-alanine and (15)NH(delta)-labelled L-histidine.HCl.H(2)O, together with SPINEVOLUTION simulations for a ten-spin system representing the crystal structure environment of the (13)CH carbon in L-alanine. For 30 kHz MAS and nu(1)((1)H) = 100 kHz at 300 MHz, a RS-HEPT T(2)' value of 17 +/- 1 ms was obtained for (13)CH-labelled L-alanine which is approximately 50% of the XiX T(2)' value of 33 +/- 2 ms. Optimum RS-HEPT decoupling performance is observed for a relative phase of alternate RS-HEPT pi-pulses, Deltaphi = phi'- phi, between 40 and 60 degrees . For experiments at 600 MHz and 30 kHz MAS with (13)CH-labelled L-alanine, the best RS-HEPT (nu(1)((1)H) = 100 kHz) T(2)' value was 3 times longer than that observed for low-power continuously applied sequences with nu(1)((1)H) < or =40 kHz, i.e. corresponding to the same average power dissipated in the probe. A marked improvement in RS-HEPT (1)H decoupling is observed for increasing MAS frequency: at 55.6 kHz MAS, a best RS-HEPT T(2)' value of 34 +/- 5 ms was recorded for (13)CH-labelled L-alanine. Much improved RS-HEPT broadband performance was also observed at 55.6 kHz MAS as compared to 30 kHz MAS.     

Two-dimensional (13)C-(13)C correlation spectroscopy with magic angle spinning and dynamic nuclear polarization

The sensitivity of solid-state NMR experiments can be enhanced with dynamic nuclear polarization (DNP), a technique that transfers the high Boltzmann polarization of unpaired electrons to nuclei. Signal enhancements of up to 23 have been obtained for magic angle spinning (MAS) experiments at 5 T and 85-90 K using a custom-designed high-power gyrotron. The extended stability of MAS/DNP experiments at low temperature is demonstrated with (1)H-driven (13)C spin-diffusion experiments on the amino acid proline. These (13)C-(13)C chemical shift correlation spectra are the first two-dimensional MAS/DNP experiments performed at high field (>1.4 T).     

High-pressure delta-Al(OH)3 and delta-AlOOH phases and isostructural hydroxides/oxyhydroxides: new structural insights from high-resolution 1H and 27Al NMR

In order to shed light on the proton distributions and order/disorder in high-pressure delta-Al(OH)3 and delta-AlOOH phases, two-dimensional, high-resolution 1H CRAMPS (FSLG)-MAS NMR and 27Al 3QMAS NMR spectra have been obtained. For delta-Al(OH)3, the 1H CRAMPS-MAS NMR revealed two peaks with an intensity ratio close to 2:1. The 27Al MAS and 3QMAS NMR suggest a single Al site with a well-defined local structure. For delta-AlOOH, the 1H and 27Al NMR indicate the presence of a single H and Al site each. These results are consistent with crystal structures refined from X-ray diffraction. For comparison, 1H MAS and CRAMPS-MAS NMR spectra were also obtained for several other hydroxides/oxyhydroxides, including In(OH)3 and InOOH that have similar structures to delta-Al(OH)3 and delta-AlOOH, respectively. These data not only provide additional insights into the proton distributions in these important crystal structure classes but also together provide a better defined quantitative correlation between 1H chemical shift and hydrogen-bonding O...O distance.     

Characterization of a chiral stationary phase by HR/MAS NMR spectroscopy and investigation of enantioselective interaction with chiral ligates by transferred NOE

The surface chemistry of a chiral stationary phase (CSP) with a (tert-butyl carbamoyl) quinine selector immobilized on thiol-modified silica has been characterized by (1)H HR/MAS NMR and (29)Si CP/MAS NMR spectroscopy. The mostly well-resolved (1)H signals could be assigned to stem from the surface-bound selector and the latter suggested a bi- and trifunctional silane linkage. Suspended-state NMR spectroscopy thus proved a well-characterized surface chemistry as proposed. To study chiral recognition phenomena in the presence of the CSP, (1)H HR/MAS 2D transfer NOESY investigations in methanol-d(4) have been undertaken with various solutes including N-3,5-dinitrobenzoyl derivatives of leucine (DNB-Leu) and N-acetyl phenylalanine (Ac-Phe). Both (R)- and (S)-enantiomers of DNB-Leu and Ac-Phe interacted with the tBuCQN-CSP as indicated by negative cross-peaks in the trNOESY spectra, while the 2D NOESY of the dissolved solutes in absence of the chiral stationary phase showed positive cross-peaks. The intensities of the trNOE cross-peaks were much stronger for the (S)-enantiomers. This stereoselectivity paralleled the experimental chromatographic behavior, where the (S)-enantiomers revealed stronger binding and retention on the tBuCQN-CSP as well. Hence, we were able to correlate the retention behavior to the trNOE NMR spectroscopic data in a qualitative manner.     

固体核磁法研究苯酚与聚4-乙烯基吡啶的相互作用

采用高速魔角旋转(MAS)偶极滤波结合氘代稀释固体核磁技术, 研究了极性吸附分离材料聚乙烯吡啶与氘代苯酚之间的相互作用. 固体核磁结果表明, 聚乙烯吡啶与苯酚之间存在强的氢键作用, 与液体氢谱结果一致. 由MAS中水峰强度在吸附前后的变化揭示了苯酚部分置换了聚乙烯吡啶中的水, 且苯酚和聚乙烯吡啶氢键作用位点在靠近N的一端. 此种方法对于原位研究吸附剂的吸附机理以及新型吸附分离材料的设计具有重要的指导意义.     

High-resolution solid-state NMR studies of poly(vinyl phosphonic acid) proton-conducting polymer: molecular structure and proton dynamics

The structure and the local proton mobility of poly(vinyl phosphonic acid) were studied by solid-state NMR under fast magic-angle spinning. At elevated temperatures, the signature of the hydrogen-bonded P-OH protons is observed in 1H magic-angle spinning (MAS) NMR as a single resonance at 10.5 ppm. Both 1H double-quantum NMR and variable-temperature experiments demonstrate that P-OH protons are mobile and thus able to contribute to proton conductivity. Below room temperature, two different types of hydrogen-bonded P-OH resonances are observed at 10.5 and 15 ppm, and 1H double-quantum NMR demonstrates that these protons are immobile on the NMR time scale. By means of first-principles calculations of a model polymer, we have assigned the additional hydrogen-bonded species at lower temperatures to phosphonic acid anhydride and charged anhydride. Also, in the 31P MAS NMR spectrum, two distinct resonances appear, arising from "normal" phosphonic acid and phosphonic acid anhydride. 31P double-quantum NMR experiments reveal that there is no phase segregation between normal and phosphonic acid anhydride and the condensation reaction occurs randomly throughout the system. The formation of acid anhydride leads to a decrease in proton conductivity through two mechanisms, (1) decrease in the number of charge carriers and (2) blockage of charge transport pathways through immobilization of charge carriers together with a hindered reorientation of the anhydride group. Our results provide strong evidence for these mechanisms by demonstrating that the conductivity is greatly influenced by the presence of phosphonic acid anhydride.     

Thermal history effects and methyl tunneling dynamics in a supramolecular complex of calixarene and para-xylene

The low-temperature structure and dynamics of guest molecules of p-xylene incorporated in the isopropyl-calix[4] arene(2:1) p-xylene complex have been investigated by solid state nuclear magnetic resonance (NMR). Using one-dimensional 1H-decoupled 13C cross-polarization magic-angle-spinning (MAS) NMR and two-dimensional 1H-13C correlation spectroscopy, a full assignment of the 13C and 1H chemical shifts has been made. Using 1H NMR relaxometry, the effects of thermal history on the structure of the system have been investigated. Rapidly cooled samples have 1H spin-lattice relaxation times T1, which at low temperature (T<60 K) are typically two orders of magnitude faster than those observed in annealed samples which have been cooled slowly over many hours. In both forms, the low-temperature relaxation is driven by the dynamics of the weakly hindered methyl rotors of the p-xylene guest. The substantial difference in T1 is attributed in the rapidly cooled sample to disorder in the structure of the complex leading to a wide distribution of correlation times and methyl barrier heights. A comparison of the linewidths and splittings in the high resolution 13C MAS spectra of the two forms provides structural insight into the nature of the disorder. Using 1H field-cycling NMR relaxometry, the methyl dynamics of the p-xylene guest in the annealed sample have been fully characterized. The B-field dependence of the 1H T1 maps out the spectral density from which the correlation times are directly measured. The methyl barrier heights are determined from an analysis of the temperature dependence.     

Solid‐State NMR investigations of anhydrous proton‐conducting acid–base poly(acrylic acid)– poly(4‐vinyl pyridine) polymer blend system: A study of hydrogen bonding and proton conduction

NMR studies of the structure and dynamics of a system composed of the acidic polymer poly(acrylic acid) (PAA) and the basic polymer poly(4‐vinyl pyridine) (P4VP) are presented. This system aims at the application of anhydrous proton‐conducting membranes that can be used at elevated temperatures at which the proton conduction of hydrated membranes breaks down. The ¹H NMR measurements have been preformed under fast magic angle spinning (MAS) conditions to achieve sufficient resolution and the applied ¹H NMR methods vary from simple ¹H MAS to double‐quantum filtered methods and two‐dimensional ¹H double‐quantum spectroscopy. The dynamic behavior of the systems has been investigated via variable temperature ¹H MAS NMR. ¹³C cross‐polarization MAS NMR provides additional aspects of dynamic and structural features to complete the picture. Different types of acidic protons have been identified in the studied PAA‐P4VP systems that are nonhydrogen‐bonded free acidic protons, hydrogen‐bonded dicarboxylic dimers, and protons forming hydrogen bonds between carboxylic protons and ring nitrogens. The conversion of dimer structures in dried PAA to free carboxylic acid groups is accomplished at temperatures above 380 K. However, the stability of hydrogen‐bonding strongly depends on the hydration level of the polymer systems. The effect of hydration becomes less apparent in the complexes. An inverse proportionality between hydrogen‐bonding strength and proton conduction in the PAA‐P4VP acid–base polymer blend systems was established. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 138–155, 2009     

1H detection in MAS solid-state NMR spectroscopy of biomacromolecules employing pulsed field gradients for residual solvent suppression

In this communication, we demonstrate the feasibility of 1H detection in MAS solid-state NMR for a microcrystalline, uniformly 2H,15N-labeled sample of a SH3 domain of chicken alpha-spectrin, using pulsed field gradients for suppression of water magnetization. Today, B0 gradients are employed routinely in solution-state NMR for coherence order selection and solvent suppression. We suggest to use gradients to purge water magnetization which cannot be suppressed using conventional water suppression schemes. The achievable gain in sensitivity for 1H detection is in the order of 5 compared to the 15N detected version of the experiment (at a MAS rotation frequency of 13.5 kHz). We expect that this labeling concept which achieves high sensitivity due to 1H detection, in combination with the possibility to measure long range 1H-1H distances as we have shown previously, to be a useful tool for the determination of protein structures in the solid state.     

Incorporation of aluminum in the calcium silicate hydrate (C-S-H) of hydrated portland cements: a high-field 27Al and 29Si MAS NMR investigation

The calcium silicate hydrate (C-S-H) phase resulting from hydration of a white Portland cement (wPc) in water and in a 0.3 M NaAlO(2) solution has been investigated at 14 and 11 hydration times, respectively, ranging from 6 h to 1 year by (27)Al and (29)Si MAS NMR spectroscopy. (27)Al MAS NMR spectra recorded at 7.05, 9.39, 14.09, and 21.15 T have allowed a determination of the (27)Al isotropic chemical shift (delta(iso)) and quadrupolar product parameter (P(Q) = C(Q)) for tetrahedrally coordinated Al incorporated in the C-S-H phase and for a pentacoordinated Al site. The latter site may originate from Al(3+) substituting for Ca(2+) ions situated in the interlayers of the C-S-H structure. The spectral region for octahedrally coordinated Al displays resonances from ettringite, monosulfate, and a third aluminate hydrate phase (delta(iso) = 5.0 ppm and P(Q) = 1.20 MHz). The latter phase is tentatively ascribed to a less-crystalline aluminate gel or calcium aluminate hydrate. The tetrahedral Al incorporated in the C-S-H phase has been quantitatively determined from (27)Al MAS spectra at 14.09 T and indirectly observed quantitatively in (29)Si MAS NMR spectra by the Q(2)(1Al) resonance at -81.0 ppm. A linear correlation is observed between the (29)Si MAS NMR intensity for the Q(2)(1Al) resonance and the quantity of Al incorporated in the C-S-H phase from (27)Al MAS NMR for the different samples of hydrated wPc. This correlation supports the assignment of the resonance at delta(iso)((29)Si) = -81.0 ppm to a Q(2)(1Al) site in the C-S-H phase and the assignment of the (27)Al resonance at delta(iso)((27)Al) = 74.6 ppm, characterized by P(Q)((27)Al) = 4.5 MHz, to tetrahedrally coordinated Al in the C-S-H. Finally, it is shown that hydration of wPc in a NaAlO(2) solution results in a C-S-H phase with a longer mean chain length of SiO(4) tetrahedra and an increased quantity of Al incorporated in the chain structure as compared to the C-S-H phase resulting from hydration of wPc in water.