BUNSEKI KAGAKU Vol. 60, No. 9, pp The Japan Society for Analytical Chemistry 749 X X 1,2 1 X X X X X X Parallel Beam Method X X X X

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1 BUNSEKI KAGAKU Vol. 6, No. 9, pp The Japan Society for Analytical Chemistry 749 X X 1,2 1 X X X X X X Parallel Beam Method X X X X 1 1 X X 1 : Rigaku Europe SE : Grosse-Berliner Damm 151, 12487, Berlin Germany X X Table mg 5 mg 2 1 X X X Parallel beam method X

2 75 B U N S E K I K A G A K U Vol Table 1 Parameters of analgesic antipyretic drugs Manufacturer Purchased Country Production Country Factory Lot. No. Tablet type Size (mm) a) Weight (mg) Color A JAPAN JAPAN Standard 12.2f, 5.t 597 White A GERMANY GERMANY G Standard 12.2f, 5.t 594 White A POLAND GERMANY H J Standard 12.2f, 5.t 597 White A SLOVENIA GERMANY H K Standard 12.2f, 5.t 596 White A ROMANIA GERMANY H L Effervescent 25.8f, 4.t 3184 White A RUSSIA GERMANY H M Effervescent 25.8f, 4.t 3165 White A UKRAINE GERMANY H N Effervescent 25.8f, 4.t 3175 White A FRANCE GERMANY H O Chewable 18.3f, 5.2t 1521 Pink A SLOVENIA GERMANY H P Chewable 18.3f, 5.2t 1495 Pink B FRANCE FRANCE I Q Effervescent 23.f, 4.4t 2677 White B RUSSIA FRANCE I R Effervescent 23.f, 4.4t 2691 White B UKRAINE FRANCE I S Effervescent 23.f, 5.6t 3469 White C UK (GB) UK (GB) Standard 12.8f, 4.t 597 White D ROMANIA ROMANIA Standard 13.2f, 5.t 843 White E JAPAN JAPAN Standard 1.2f, 5.4t 488 White a) f ; diameter, t ; maximum thickness Table 2 Measurement conditions of XRD analysis Bragg-Brentano (BB) Parallel beam (PB) Scanning axis θ-2θ (θs-θd) a) θ-2θ (θs-θd) Scanning mode Continuous Continuous Scanning range (2θ) Sampling width.2.2 Scanning speed 5. /min 5. or 1. /min X-ray Power 1.6 kw, 4 kv-4 ma 1.6 kw, 4 kv-4 ma Multilayer mirror Not used Used Incident Soller slit 5. deg 5. deg Divergence slit 2/3 deg 1 mm Vertical limitation 1 mm 1 mm slit Parallel slit analyzer Not used.114 deg Scattering slit 2/3 deg Open Receiving Soller slit 5. deg 5. deg Receiving slit.45 mm Open Slit for monochromator.8 mm Not used Monochromator Bent Flat a) θs ; θ sourse, θd ; θ detector X X 2 X 3 X θ-θ X X X X Ultima IV Ultima IV X θs θd θ-θ X X 3 kw 6 kv 6 ma Cross Beam Optics 4 X ; 1 1 mm 2 DS SS RS 3 SC Table 2 2 θ 5. /min 1. /min

$: X X 751 Table 3 Parameters of (2) diffraction peak in different measurement methods and sample preparations Peak position (2θ) Peak top intensity FWHM (Δ2θ) Photo 1 A tablet analgesic antipyretic$

3 : X X 751 Table 3 Parameters of (2) diffraction peak in different measurement methods and sample preparations Peak position (2θ) Peak top intensity FWHM (Δ2θ) Photo 1 A tablet analgesic antipyretic drug on an Al sample holder 1 Powder sample with BB a) cps.26 Powder sample with PB b) cps.21 Tablet sample with PB cps.222 Tablet sample with BB cps.33 a) BB ; Bragg-Brentano method, b) PB ; Parallel beam method 1 1 (2) Fig. 1 XRD patterns of powder and tablet analgesic antipyretic drug with Bragg-Brentano (BB) and Parallel Beam (PB) methods ; a) powder sample with BB, b) powder sample with PB, c) tablet sample with PB, d) tablet sample with BB (shifted) a b c d (1) (112) Fig. 2 XRD patterns of powder of analgesic antipyretic drug with ; e) smooth sample surface with BB method and f) rough sample surface with PB method (shifted) e f 1 A.5 mm 2 A Photo 1 Fig. 1 X (2) Table 3 X X 3 2 θ X (2) ICDD θ Fig. 2 A ICDD (2) (112) 1 : 74

4 752 B U N S E K I K A G A K U Vol : 28 (2) 1 : 56 ICDD A 5 5 Fig. 3 (2) (2) (112) (112)/(2) Table 4 (2) (112)/(2) ICDD st run 2nd run 3rd run 4th run 5th run Fig. 3 XRD patterns of reproducibility measurement of analgesic antipyretic drug with rough sample surface with PB method (shifted) X.5 mm 15 mg.1 mg X 1 mg 2 2 X X WD-XRF Primus II Primus II X 4 kw 6 kv 15 ma 48 4 X.5 mm 35 mm 6 3 rpm 3 1 SC PC X Table 4 Reproducibility of (2) diffraction peak top intensity (Units ; cps) and ratios of (112)/(2) Diffraction peaks 1st 2nd 3rd 4th 5th Average RSD a) BB with Smooth surface Intensity Ratio PB with Rough surface Intensity Ratio a) Relative Standard Deviation

5 : X X 753 Table 5 Measurement conditions of XRF analysis (EZ Scan Standard Measurement) Element X-ray Power 2-Theta (deg) Slit Crystal Detector (kv-ma) (W) Low High Step (deg) Scan speed (deg/min) Heavy Fine LiF SC Ca Normal LiF PC K Normal LiF PC Cl Fine Ge PC S Normal Ge PC P Normal Ge PC Si Normal PET PC Al Normal PET PC Mg Normal RX-25 a) PC Na Normal RX-25 PC F Normal RX-25 PC O Normal RX-35 b) PC N Coarse RX-4 c) PC C Coarse RX-61 d) PC B Coarse RX-75 e) PC a) e) Synthetic multilayer mirror Primus II EZ Scan He Standard Table 5 SQX 5 6 ; 1 ; 2 ; 25 Kα 1 Kβ 1 A E 1 mm A E A mm 1 t/cm 2 2 mm 3 Fig X X A Fig. 5 5 mg 596 mg 96 mg

6 754 B U N S E K I K A G A K U Vol a b c d e f g h i j k l m n o Fig. 4 XRD patterns of analgesic antipyretic drug ; a) Standard 1 A Japan, b) Standard A Germany, c) Standard A Poland, d) Standard A Slovenia, e) Effervescent 2 A Romania, f) Effervescent A Russia, g) Effervescent A Ukraine, h) Chewable 3 A France, i) Chewable A Slovenia, j) Effervescent B France, k) Effervescent B Russia, l) Effervescent B Ukraine, m) Standard C UK, n) Standard D Romania, o) Standard E Japan (shifted) 1 : standard tablet, 2 : effervescent tablet, 3 : chewable tablet, A E : company name a b c d Fig. 5 XRD patterns of standard type tablet analgesic antipyretic drug from company A ; a) Japan, b) Germany, c) Poland, d) Slovenia (shifted) *A e *B A C C L- Fig mg 4 mg 5 mg 15 mg : 6.6 : 1 (1) (2) (112) : 12. : θ 1 L- (2) 25 f g Fig. 6 XRD patterns of effervescent type tablet analgesic antipyretic drug from company A ; e) Romania, f) Russia, g) Ukraine (shifted) *A : (2) diffraction peak of Vitamin C (L-ascorbic acid), *B : (2) diffraction peak of Vitamin C (L-ascorbic acid) Fig. 6 *A θ 28 L- (2) Fig. 6 *B A Fig. 7

7 : X X h a m n i 2 o Fig. 7 XRD patterns of chewable type tablet analgesic antipyretic drug from company A ; h) France, i) Slovenia (shifted) Fig. 9 XRD patterns of standard type tablet analgesic antipyretic drug ; m) company C UK, n) company D Romania, o) company E Japan and a) company A Japan as a reference (shifted) j k l *A *B *B Fig. 8 XRD patterns of effervescent type tablet analgesic antipyretic drug from company B ; j) France, k) Russia, l) Ukraine (shifted) *A : Diffraction peaks of Vitamin C (L-ascorbic acid), *B : Not assigned diffraction peak 7 X X B Fig. 8 L- Fig. 8 *A 2 θ 12 Fig. 8 *B *A 2 θ 12 5 mg 5 mg 33 mg Table 1 15 mg : : 2 : 2 : : 2.5 : 1 A B C D E Fig. 9 A C D E C 3 mg D 5 mg E 33 mg 15 mg A : C : D : E 1 :.6 :.7 :.8 1 :.2 :.5 :.5

8 756 B U N S E K I K A G A K U Vol Table 6 Elemental analysis result of analgesic antipyretic drugs (Units : mass ) Manufacturer Purchased country Tablet type Measured element F Na Mg Al Si P S Cl K Ca Ti Fe Sr A JAPAN S a) A GERMANY S A POLAND S A SLOVENIA S A ROMANIA E b) A RUSSIA E A UKRAINE E A FRANCE C c) A SLOVENIA C B FRANCE E B RUSSIA E B UKRAINE E C UK S D ROMANIA S E JAPAN S a) Standard type, b) Effervescent type, c) Chewable X C, H, O X Table 6 X X 1 X A 2 A C X 2 3 A X X 4 B X C X 6 D X X X 7 E A Fig. 1 X 4 X

9 : X X Cr-Kα1 (5.415 kev) Cu-Kα1 (8.48 kev) Zn-Kα1 (8.639 kev) As-Kα1 (1.544 kev).8.4 Cd-Kα1 ( kev) Rh Kβ1 Compton Sn-Kα1 ( kev) Hg-Lα1 (9.989 kev) 8 7 Pb-Lα1 (1.542 kev) Fig. 1 Possible hazardous elements XRF spectra of standard type tablet analgesic antipyretic drug from company A (Germany) 2 X X X X X X X Alexander Klug 8 9

10 758 B U N S E K I K A G A K U Vol Integral intencity of main 3 diffraction peaks(cps deg) Ij = Kj Vj µ 1 Ij j Kj Vj j μ 1 Wj Ij = Kj µ / ρ Measured weight of Acetylsalicylic acid (mg) Fig. 11 Measured weight vs. Integral intensity of Acetylsalicylic acid 2 Wj j μ/ρ 15 mg X 15 mg Fig X WD-XRF C CH 3 15 mg Fig. 12 σ d accuracy σ d = Integral intencity mass absorption coefficient (arbitary units) Measured weight of Acetylsalicylic acid (mg) Ci Wi ˆ ( ) i ( mass% ) n m 2 C Fig. 12 Measured weight vs. Integral intensity x mass absorption coefficient of Acetylsalicylic acid A : company E Japan, B : company D Romania, C : Chewable type company A France 3 Ci Ŵi X n m m mass 3.52 mass X X Fig. 12 E A D B A C 3 B A

11 : X X 759 X X X 5 X X X X X X X X X X X X X Rigaku Europe SE 1) : , ( ). 2) K. Shimizu, K. Omote : The Rigaku J. Vol. 24 No. 1, 1 (28). 3) : X 5 p. 42 (26), ( ). 4) : (P ), ( ). 5) J. Sherman : Spectrochim. Acta, 7, 283 (1955). 6) T. Shiraiwa, N. Fujino : Jpn. J. Appl. Phys., 5, 886 (1966). 7) : 155, 285 ( ). 8) L. Alexander, H. P. Klug : Anal. Chem., 2, 886 (1948). 9) H. P. Klug, L. Alexander : X-ray diffraction procedures (2nd edition) (1973), (John Wiley & Sons, Inc., New York). 1) : X 5 p. 62 (26), ( ).

12 76 B U N S E K I K A G A K U Vol Comparative Analysis of Acetylsalicylic Acid Based Analgesic Antipyretic Drugs Using XRD Parallel Beam Method and Wavelength Dispersive-XRF Akihiko IWATA 1,2 and Jun KAWAI 1 1 Department of the Materials Science and Engineering Kyoto University, Sakyo-Ku, Kyoto Rigaku Europe SE, Grosse-Berliner Damm 151, 12487, Berlin, Germany (Received 18 April 211, Accepted 1 June 211) Many organic compounds, including medicines, have preferred orientation, affected by the sample-preparation methods, which might cause problems in X-ray diffraction (XRD) analysis. To arrive at accurate and correct XRD analysis results of such compounds, we need a specially designed diffractometer, or special techniques to avoid the preferred-orientation effect. X-ray fluorescence (XRF) analysis is liable to cause misunderstandings that it is weak for anlyzing organic compounds, since they are composed in mainly of light elements. The recent progress of synthesized multilayer mirror technology has brought new possibilities in XRD and XRF analyses. The parallel beam method has been widely used in XRD analysis due to its high resolution and sufficiently good brilliance. In XRF analysis, specially designed synthesized multilayer mirrors enable us to carry out low-concentration light elemental analysis such as for boron, carbon, oxygen and so on. In the present work we evaluated the availability of recent progress related to the synthesized multilayer mirror technology in XRD and XRF techniques for organic compounds, including medicines, by performing comparative analyses of acetylsalicylic acid based analgesic antipyretic drugs. Keywords : comparative analysis ; synthesized multilayer mirror ; XRD parallel beam method ; WD-XRF ; acetylsalicylic acid.

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