Identification of Phytochemicals of Phoenix dactylifera L. Cv Ajwa with UHPLC-ESI-QTOF-MS/MS

Figures & data

Table 1. Classification of characterized phytochemical compounds in Ajwa date fruit

Classification			Phytochemical compounds	References
Polyphenols	Phenolic acid	Hydroxycinnaminic acids	Caffeic acid	Ahmed et al., 2016a; Hamad et al., 2015; Yasin et al., 2015; Ragab et al., 2013; Saleh et al., 2011.
			Caffeic acid hexoside	Yasin et al., 2015
			Caffeic acid hexoside conjugate	-
			Caffeoyl acid	-
			O-caffeoyl shikimic acid	Farag et al., 2014; Yasin et al., 2015
			O-dicaffeoyl shikimic acid	Farag et al., 2014; Yasin et al., 2015
			O-dicaffeoyl shikimic acid acetate	-
			Sinapic acid hexoside	Farag et al., 2014
			Ferulic acid	Ahmed et al., 2016a; Hamad et al., 2015; Yasin et al., 2015; Martins et al., 2011
			Chlorogenic acid	Ahmed et al., 2016a; Hamad et al., 2015; Reis et al., 2012
			p-Coumaroyl hexose	Amessis-Ouchemoukh et al., 2014
		Hydroxybenzoic acids	p-Hydroxybenzoylhexose	-
			Protocatechuic acid hexoside	Yasir et al., 2016
			Gallic acid	Ahmed et al., 2016a; Hamad et al., 2015; Yasin et al., 2015;
		Flavonoids	Flavones	Apigenin pentosyl hexoside	Yasin et al., 2015
			Apigenin 7-O-neohesperidoside	Yasin et al., 2015
			Chrysoeriol	Farag et al., 2014
			Chrysoeriol hexosyl sulfate	Farag et al., 2014
			Luteolin	Ahmed et al., 2016a; Hamad et al., 2015; Yasin et al., 2015; Farag et al., 2014
			Luteolin hexoside	Farag et al., 2014
			Luteolin rhamnosyl hexoside	Farag et al., 2014
			Luteolin rhamnosyl dihexoside	Farag et al., 2014
		Flavonoles	Quercetin	Ahmed et al., 2016a; Hamad et al., 2015; Yasin et al., 2015; Farag et al., 2014
			Quercetin rhamnosyl dihexoside	Yasin et al., 2015; Farag et al., 2014
			Quercetin 3-hexose	Yasin et al., 2015
			Quercetin 7-O-hexoside-3-O-rhamnoside	Yasin et al., 2015
			Isoquercetin	Ahmed et al., 2016a; Hamad et al., 2015; Yasin et al., 2015; Farag et al., 2014
			Isoquercetrin acetate	Farag et al., 2014; Yasin et al., 2015
			Isoquercetin sulfate	Farag et al., 2014; Yasin et al., 2015
			Dihydrokaempferol hexoside	-
			Rutin	Ahmed et al., 2016a; Hamad et al., 2015; Farag et al., 2014; Martins et al., 2011
			Isorhamnetin rhamnosyl hexoside	Farag et al., 2014
			Isorhamnoetin-3-O-glucoside	Farag et al., 2014
			Chrysoeriol rhamnosyl hexoside	Farag et al., 2014
			Kaempferol-3-O-glucoside-7-O-rhamnoside	-
			Afzelin-O-gallate	-
		Flavanones	Eriodictyol xyloyl deoxy hexose	-
Terpenoids			Pinenol-O-glucoside	-
Fatty acids			Trihydroxy-9,14-octadecadienoic acid	Farag et al., 2014
			Trihydroxy-octadecenoic acid	Farag et al., 2014
			Hydroxy octadecadienoic acid	Farag et al., 2014
Organic acids			Malic acid	Hamad et al., 2015; Abu-Reidah et al., 2015
			Gluconic acid	Ramachandran et al., 2006
			Ascorbic acid	Ahmed et al., 2016a; Yasir et al., 2016

Figure 1. Examples LC-MS/MS data of Ajwa date fruit extract. Ai and Aii: Peak with retention time 4.671 min was analyzed with a pseudomolecular peak [M-H]- at m/z = 497.1 indicating the presence of O-dicaffeoyl shikimic acid and confirmed by MS/MS fragments at m/z = (135.0274, 161.0038, 179.0126, 335.0464). Bi and Bii: Peak with retention time 4.178 min was analyzed with a pseudomolecular peak [M-H]- at m/z 179.0 indicating the presence of caffeic acid and confirmed by MS/MS fragments at m/z = (59.0165, 71.0150, 89.0254, 134.0367, 135.0450, 136.0486)

Table 2. Phytochemical compounds detected after 2, 5 and 24 h of extracted Ajwa date fruit with water using LC/ESI-QTOF-MS/MS

Extraction time	Peak no.	Retention time (min)	Molecular weight	[M-H] m/z	Identified compounds	Molecular formula	Major fragments (MS/MS)	References
2 h	1	2.143	564	563.2	Apigenin pentosyl hexoside	C26H27O14	176.953, 176.937, 285.044, 220.924, 337.061, 393.026, 427.089	Farag et al., 2014
	2	2.467	342	341.1	Caffeic acid hexoside	C15H18O9	59, 71, 73, 89, 101, 113, 119, 131, 143, 161, 179, 207, 221, 251	-
	3	2.496	623	622.1	Unknown	-	292, 310, 343, 416, 460, 532	-
	4	2.573	426	425.2	Unknown	-	73.02, 129.06, 129.02, 128.02, 176.03, 219.04, 218.04, 317.08, 334.08, 335.08, 335.1, 425.04, 425.15, 425.13	-
	5	2.817	196	195.0	Gluconic acid	C6H12O7	59, 71, 74.9, 85, 98.9, 129, 159, 177	-
	6	2.869	237	236	Unknown	-	71.9, 103, 144.1, 146, 147, 164.1, 181, 206.1	-
	7	4.158	300	299.1	p-Hydroxybenzoylhexose	C13H16O8	93, 135.9, 137, 179, 239	-
	8	4.709	326	325.1	p-Coumaroyl hexose	C15H17O8	96.6, 119, 163.1	Amessis-Ouchemoukh et al. (2014)
	9	4.745	498	497.1	O-dicaffeoyl shikimic acid	C22H25O13	135.1, 161, 179, 335	Farag et al., 2014
	10	5.617	450	449.2	Dihydrokaempferol hexoside	C21H22O11	59, 119, 207, 209.1, 251.1, 269, 287, 448.1, 449	Abu-Reidah et al., 2015
	11	5.667	756	755.4	Luteolin rhamnosyl dihexoside	C33H39O20	128, 233, 306, 385.1, 413.1, 531.1, 593.16, 593.1, 593.2, 663.1, 709.18, 709.16, 755.16, 755.2, 755.10, 755.3	Farag et al., 2014
	12	5.742	544	543.0	Isoquercetin sulfate	C21H19O15	150.6, 24.9, 300.9, 301, 463	Farag et al., 2014
	13	6.062	464	463.1	Isoquercetin	C21H19O12	178.9, 255, 270.9, 299.9, 301	Farag et al., 2014
	14	6.378	644	643.2	Unknown	-	165, 191, 284, 299, 342.9, 607.2, 607.1	-
	15	6.471	776	775.4	Unknown	-	150, 165, 195.04, 195.07, 387.11, 387.14, 417.1, 535.1, 565.2, 595.2, 613.2, 775.1, 775.2, 775.3	-
	16	7.475	328	327.2	Trihydroxy-9,14-octadecadienoic acid	C18H31O5	171.1, 183.1, 211.1, 229.1, 309.2	Farag et al., 2014
	17	7.934	330	329.2	Unknown	-	171.1, 211.1	-
	18	8.064	300	299.0	Chrysoeriol	C16H11O6	256, 284	Farag et al., 2014
	19	8.900	294	293.2	Unknown	-	131.1, 177.1, 205.1, 221.1, 220.1, 236.07, 236.1	-
	20	9.468	226	225.0	Unknown	-	59, 71, 89, 113, 119, 127.1, 179, 224.77	-
	21	11.482	340	339.2	Unknown	-	119, 169.9, 182.9, 197, 339.2	-
	22	11.714	180	179.0	Unknown	-	59, 65, 71, 89	-
	23	19.147	689	688.0	Unknown	-	255.2, 363.5, 387.2, 405.2, 387.2, 641.6, 641.5, 687.5	-
	24	20.603	911	910.0	Unknown	-	701.4, 773.5	-
	25	21.009	199	198.0	Unknown	-	160.86, 160.82, 162.6, 197.78	-
	26	22.710	914	913.0	Unknown	-	703.5, 774.5, 774.6, 775.5, 776.5, 912.5, 912.4	-
5 h	1	2.567	326	325.1	p-Coumaroyl hexose	C15H17O8	101, 127, 145, 144	(Amessis-Ouchemoukh et al., 2014)
	2	2.724	196	195.0	Gluconic acid	C6H12O7	59, 71, 74.9, 98.9, 108, 129, 159, 177	-
	3	3.902	494	493.1	Unknown	-	120.5, 194, 209, 243	-
	4	4.209	300	299.0	p-Hydroxybenzoylhexose	C13H16O8	93, 137, 179, 239.02, 239.05	-
	5	4.352	422	421.0	Unknown	-	135, 149, 161, 179, 251, 281, 341	-
	6	4.671	498	497.1	O-dicaffeoyl shikimic acid	C22H25O13	135, 161, 179, 335	Farag et al., 2014
	7	5.224	336	335.2	O-caffeoyl shikimic acid	C16H18O8	131.1, 133, 135, 137, 155, 161, 161.03, 179, 335	Farag et al., 2014
	8	5.294	790	789.2	Unknown	-	389.1, 419.1, 581.1, 743.2	-
	9	5.931	610	609.1	Rutin	C27H30O16	255, 299.9, 301	Abu-Reidah et al., 2013; Farag et al., 2014
	10	6.090	464	463.0	Isoquercetrin	C21H20O12	150.9, 178.9, 255, 270.9, 299.9, 301	Farag et al., 2014
	11	6.213	506	505.2	Isoquercetrin acetate	C23H21O13	150.9, 255, 270.9, 299.9, 301.0, 301.03, 343.2, 505.05, 505.1	Farag et al., 2014
	12	6.306	624	623.2	Isorhamnetin rhamnosyl hexoside	C28H31O16	240.9, 299, 269, 314, 315.02, 315.06, 577, 541, 543, 623.11, 623.19	Farag et al., 2014
	13	6.440	608	607	Unknown	-	284.09, 299.02	-
	14	6.640	510	509.2	Unknown	-	161, 167.1, 221	-
	15	7.035	740	739.3	Unknown	-	119.9, 128, 200, 249, 321, 377.1, 393.1, 409.7, 411.1, 577.2, 649.3, 693.3, 739.2	-
	16	7.843	330	329.2	Ttihydroxy octadecenoic acid	C18H33O5	99.1, 193, 171.1, 211.1, 229.1, 209.1, 293.2, 311.2	Farag et al., 2014
	17	8.095	300	299.0	Chrysoeriol	C16H11O6	255, 256, 284	Farag et al., 2014
24 h	1	1.636	895	894.1	Unknown	-	86.9, 131, 175, 351, 365, 527, 717.6, 805.6, 893.6, 893.8	-
	2	1.875	196	195.0	Gluconic acid	C6H12O7	59, 72.9, 74.9, 86.9, 58.9, 96.9, 129, 159, 177	-
	3	2.167	133	132.9	Malic acid	C4H6O5	71, 114.58	-
	4	2.484	344	343	Unknown	-	161, 163.02, 164, 163.03, 180, 181, 223	-
	5	2.924	584	583.2	Afzelin O-gallate	C28H24O14	135, 164, 179, 251, 281, 341, 403.1, 443.1, 583	(Moharram et al., 2006)
	6	3.453	316	315.0	Protocatechuic acid hexoside	C13H16O9	109, 135, 152.9, 153	Abu-Reidah et al., 2015
	7	3.593	500	499.1	Unknown	-	89, 179, 319.1, 341.07, 341.14, 453.2, 498.8	-
	8	3.949	396	395.0	Unknown	-	96.9, 138.9, 228.9, 240.9	-
	9	4.169	566	565.1	Eriodictyol xyloyldeoxy hexose	C25H26O15	160, 162, 177, 195, 357, 519.1	Abu-Reidah et al., 2015
	10	4.373	300	299.0	p-Hydroxybenzolhexose	-	59, 71, 93, 92, 101, 135.9, 151, 137, 179.01, 179.04, 209, 239.03, 239.05	-
	11	4.481	448	447.2	Luteolin hexoside	C21H19O11	89, 120, 145, 163.05, 163.07, 197.05, 197.04, 285, 447.05, 447.09, 447.15	Farag et al., 2014
	12	4.762	498	497.2	O-dicaffeoyl shikimic acid	C22H25O13	93, 135, 161, 179.01, 179.02, 335.04, 335.01, 497.2, 497.09, 497.12	Farag et al., 2014
	13	5.063	384	383.0	Unknown	-	74.9, 119, 145, 163, 221, 205, 325	-
24 h	14	5.240	450	449.0	Dihydrokaempferol hexoside	C21H22O11	125, 243, 148.9, 259, 269, 287	Abu-Reidah et al., 2015
	15	5.641	476	475.2	Unknown	-	59, 138, 153, 225, 313, 210, 269.1, 475.1, 429.2, 387.1, 475.03	-
	16	5.871	544	543.0	Isoquercetrin sulfate	C21H19O15	150.9, 178.9, 300, 301, 463	Farag et al., 2014
	17	6.151	742	741.2	Unknown	-	179.02, 179.03, 161, 263, 221, 305, 417.1, 433.1, 533.2, 695.3, 741.1, 323	-
	18	6.191	464	463.2	Isoquercetrin	C21H20O12	150.9, 295, 270.9, 299.9, 301, 463.05, 463.13	Farag et al., 2014
	19	6.251	506	505.2	Isoquercetrin acetate	C23H21O13	150.9, 255.03, 255.00, 270.9, 299.9, 301, 343.2, 343.01, 463.04, 503.5, 505.1	Farag et al., 2014
	20	6.458	608	607.1	Chrysoeriol rhamnosyl hexoside	C28H31O15	151, 298, 284, 299, 357.1, 443.1, 607	Farag et al., 2014
	21	6.549	450	449.1	Unknown	-	121, 137, 149, 164.9, 195, 223, 225, 208, 210, 283, 327, 401.1	-
	22	6.675	510	509.2	Unkown	-	89, 179, 167.1, 185.1, 221	-
	23	8.076	326	325.2	p-Coumaroyl hexose	C15H17O8	83, 163.1, 209.1, 307.2, 289	(Amessis-Ouchemoukh et al., 2014)
	24	8.128	542	541.1	Chrysoeriol hexosyl sulfate	C22H21O14S	96.9, 240.9, 241, 241.03, 284.04, 284, 299.02, 299.04, 541.06, 541.02, 541.10	Farag et al., 2014
	25	8.150	300	299.0	Chrysoeriol	C16H11O6	254.9, 256, 284	Farag et al., 2014
	26	8.255	474	473.4	Unknown	-	89, 119, 275.2, 293.2, 311.2, 455.2, 473.2	-
	27	8.958	294	293.1	Unknown	-	131.04, 131.02, 192.09, 205.09, 221.1, 220.1, 236.08, 236.1	-

Table 3. Phytochemical compounds detected after 2, 5 and 24 h of extracted Ajwa date fruit with methanol–water (80%) using LC/ESI-QTOF-MS/MS

Extraction Time	Peak no.	Retention time (min)	Molecular weight	[M-H] m/z	Identified compounds	Molecular formula	Major fragments (MS/MS)	References
2 h	1	1.722	342	341.1	Caffeic acid hexoside	C15H18O9	89.02, 101.02, 179.05, 207.05, 221.06, 251.07, 263.07, 323.09.	-
	2	2.828	500	499.2	Unknown	-	89.02, 161.04, 179.05, 191.1, 341.1, 415.16, 499.16	-
	3	2.953	682	681.2	Unknown	-	101.02, 143.03, 161.04, 179.05, 221.06, 263.07, 323.09, 341.1, 473.16, 501.13, 635.2, 681.2	-
	4	4.378	336	335.1	O-caffeoyl shikimic acid	C16H18O8	132.02, 133.02, 135.04, 155.03, 161.02, 179.03.	Farag et al., 2014
	5	4.422	544	543.2	Isoquercetrin sulfate	C21H19O15	135.04, 179.03, 241, 300.02, 301.03, 335.17, 335.07, 463.09, 497.13, 543.04, 543.16.	Farag et al., 2014
	6	4.462	498	497.1	O-dicaffeoyl shikimic acid	C22H25O13	135.04, 161.02, 179.03, 341.08, 335.07, 361.1.	Farag et al., 2014
	7	4.579	211	210.0	Unknown	-	59.01, 71.01, 87.01, 89.02, 101.02, 113.02, 119.03, 137.02, 165.01, 179.05, 180.04, 195.02.	-
	8	4.751	772	771.3	Quercetin rhamnosyl dihexoside	C33H39O21	299.01, 379.16, 609.15, 608.14, 691.13, 771.21	Farag et al., 2014
	9	4.873	610	609.2	Quercetin7-O-hexoside-3-O-rhamnoside	-	179.05, 284.03, 285.04, 283.02, 327.05, 447.09, 446.09, 489.1, 609.27, 609.15	-
	10	5.065	386	385.2	Sinapic acid hexoside	C17H21O10	59.01, 125.09, 149.02, 205.05, 187.09, 223.06, 265.07, 325.09, 385.04, 385.12, 385.15	Farag et al., 2014
	11	5.710	528	527.0	Unknown	-	241.0, 285.04	-
	12	5.773	286	285.2	Luteolin	C15H9O6	133.04, 151, 133.02, 223.13, 285.13, 285.04, 285.16	(Kim et al., 2009)
	13	6.214	464	463.1	Isoquercetrin	C21H19O12	151.0, 255.03, 271.02, 300.02, 301.03	Farag et al., 2014
	14	6.887	478	477.1	Isorhamnetin-3-O-glucoside	C22H21O12	243.02, 257.04, 271.02, 314.04, 315.05	Farag et al., 2014
	15	8.540	538	537.3	Unknown	-	119.03, 161.04, 179.05, 221.06, 329.23	-
	16	11.007	332	331.3	Unknown	-	185.11, 215.12, 313.24	-
	17	12.906	313	312.2	Unknown	-	183.01, 197.02, 311.17	-
	18	14.054	510	509.3	Unknown	-	152.99, 281.24	-
	19	19.126	326	325.2	Unknown	-	183.01, 184.01	-
	20	20.079	747	746.5	Unknown	-	152.99, 281.24, 255.23, 256.23, 280.23, 279.23, 416.23, 509.29, 510.29	-
	21	20.731	598	597.4	Unknown	-	389.25, 461.29, 535.3, 551.35	-
5 h	1	2.868	460	459.2	Unknown	-	87.05, 128.03, 129.06, 146.04, 200.13, 285.2, 286.14, 330.16, 371.19, 415.18, 459.12	-
	2	3.062	336	335.1	O-caffeoyl shikimic acid	C16H18O8	123.05, 131.08, 137.02, 179.03, 229.08, 239.05, 245.09, 335.07, 335.13	Farag et al., 2014
	3	3.363	775	774.3	Unknown	-	119.04, 163.03, 164.04, 234.07, 294.09, 293.08, 325.09, 326.09, 422.11, 448.15, 447.15, 612.17, 774.15, 774.26	-
	4	3.503	498	497.3	O-dicaffeoyl shikimic acid	C22H25O13	135.04, 137.02, 161.02, 179.03, 195.06, 203.07, 289.07, 335.07, 407.16, 451.22, 497.17, 497.13, 497.25	Farag et al., 2014
	5	4.149	180	179.0	Caffeoyl acid	-	59.01, 71.01, 134.03, 135.04, 136.048	-
	6	5.266	772	771.4	Quercetin rhamnosyl dihexoside	C33H39O21	217.1, 231.05, 249.05, 301.03, 321.07, 411.1, 463.09, 563.23, 563.18, 609.15, 609.19, 691.12, 771.27, 771.22, 725.19, 771.3	Farag et al., 2014
	7	5.558	194	193.0	Ferulic acid	C10H10O4	137.02, 149.06, 133.02, 134.03, 178.02	Yasir et al., 2016
	8	6.081	448	447.1	Leteolin hexoside	C21H19O11	256.03, 285.04, 284.03, 327.05	Farag et al., 2014
	9	6.283	542	541.1	Chrysoeriol hexosyl sulfate	C22H21O14S	241.0, 299.05, 284.03, 299.76	Farag et al., 2014
	10	6.673	478	477.1	Isorhamnetin-3-O-glucoside	C22H21O12	151.0, 242.02, 257.04, 243.02, 271.02, 314.04, 315.05, 357.06	Farag et al., 2014
	11	6.722	608	607.1	Chrysoeriol rhamnosyl hexoside	C28H31O15	298.04, 284.03, 297.03, 299.05	Farag et al., 2014
	12	7.250	806	805.3	Unknown	-	195.06, 225.07, 417.15, 595.22, 643.24	-
	13	8.033	286	285.2	Luteolin	C15H9O6	132.02, 133.02, 151.0, 175.03, 285.04	(Kim et al., 2009)
	14	9.676	464	463.3	Isoquercetrin	C21H19O12	221.18, 239.20, 283.19, 301.2, 343.21, 445.24, 463.09	Farag et al., 2014
	15	9.746	474	473.3	Unknown	-	293.21, 311.22	-
	16	10.601	368	367.2	Unknown	-	157.03, 187.04, 205.05, 277.07, 331.25	-
	17	12.531	313	312.2	Unknown	-	183.01, 197.02, 311.17	-
	18	17.343	326	325.2	Unknown	-	183.01, 279.23	-
	19	19.105	472	471.3	Unknown	-	393.31, 409.35	-
	20	21.391	312	311.2	Unknown	-	183.01	-
	21	23.125	748	747.6	Unknown	-	255.23, 281.25	-
24 h	1	1.731	388	387.1	Caffeic acid hexoside conjugate	-	89.02, 119.03, 179.05, 221.06, 207.04, 251.07, 341.1	-
	2	1.898	478	477.2	Isorhamnetin-3-O-glucoside	C22H21O12	71.01, 134.04, 120.99, 153.01, 195.02, 255.05, 315.07, 417.1, 477.12, 477.17	Farag et al., 2014
24 h	3	2.059	170	169.0	Gallic acid	C7H6O5	97.03, 125.02, 169.01	-
	4	2.493	448	447.2	Luteolin hexoside	C21H19O11	71.01, 120.99, 161.04, 239.12, 225.05, 285.07, 343.11, 401.14, 401.18, 447.15, 447.10, 447.19	Farag et al., 2014
	5	3.077	300	299.1	Unknown	-	136.01, 137.02, 179.03, 239.05, 240.05	-
	6	4.201	498	497.1	O-dicaffeoyl shikimic acid	C22H25O13	135.04, 179.03, 341.08, 335.07	Farag et al., 2014
	7	5.256	610	609.2	Quercetin 3 hexose	-	195.07, 241.0, 301.03, 285.04, 300.02, 327.04, 443.14, 447.09, 563.27, 609.15	-
	8	5.284	544	543.0	Isoquercetrin sulfate	C21H19O15	151.0, 241.0, 301.03, 300.02, 463.09	Farag et al., 2014
	9	5.843	300	299.1	Chrysoeriol	C16H11O6	151.0, 256.03, 284.03	Farag et al., 2014
	10	5.914	514	513.0	Unknown	-	151.0, 178.99, 273.04, 301.03, 433.07	-
	11	6.308	543	542.1	Unknown	-	242.0, 241.0, 285.03, 284.03, 299.05, 300.06	-
	12	6.642	578	577.2	Apigenin 7-O-neohesperidoside	C27H30O14	268.18, 268.03, 269.04, 397.22, 577.07, 577.02	Matsuda, 1966
	13	7.686	226	225.1	Unknown	-	59.01, 71.01, 89.02, 113.02, 179.05	-
	14	7.898	302	301.2	Quercetin	C15H10O7	121.02, 151.0, 178.99, 255.23, 280.98, 301.03	(Shabana et al., 2011)
	15	8.010	286	285.0	Luteolin	C15H10O6	105.02, 133.02, 151.0, 201.01	(Kim et al., 2009)
	16	8.463	226	225.1	Unknown	-	89.02, 71.01, 113.02, 119.03, 207.13	-
	17	9.036	330	329.2	Trihydroxy-octadecenoic acid	C18H33O5	139.11, 183.13, 171.10, 211.13, 229.14, 209.11, 311.22	Farag et al., 2014
	18	9.434	542	541.2	Chrysoeriol hexosyl sulfate	C22H21O14S	96.95, 151.0, 241.0, 284.03, 284.04, 299.05, 377.01, 503.16, 541.07, 541.13	Farag et al., 2014
	19	9.568	368	367.1	Unknown	-	115.02, 157.03, 187.04, 205.05, 277.07, 329.23	-
	20	9.637	464	463.3	Isoquercetrin	C21H19O12	59.03, 138.98, 221.19, 255.19, 301.20, 283.19, 367.1, 463.0, 463.09	Farag et al., 2014
	21	10.604	368	367.1	Unknown	-	115.02, 157.03, 187.04, 277.07, 205.05, 331.24	-
	22	12.196	299	298.1	Unknown	-	119.04, 183.01, 184.01, 197.02, 297.15	-
	23	12.997	313	312.2	Unknown	-	119.05, 183.01, 184.01, 197.02, 311.17	-
	24	13.244	326	325.2	Unknown	-	183.01	-
	25	13.878	341	340.2	Unknown	-	183.01, 184.01	-
	26	15.101	488	487.3	Unknown	-	293.24, 279.23, 321.24	-
	27	18.567	283	282.2	Unknown	-	281.24	-
	28	18.954	341	340.2	Unknown	-	184.01, 183.01, 197.02, 239.07, 339.20	-
	29	19.769	670	669.4	Unknown	-	125.09, 187.09, 255.23, 261.13, 431.23, 499.36	-
	30	23.322	341	340.2	Unknown	-	170.0, 197.02, 183.01, 184.01, 339.20	-

Table 4. Phytochemical compounds detected after 2, 5 and 24 h of extracted Ajwa date fruit with acetone–water (70%) using LC/ESI-QTOF-MS/MS

Extraction time	Peak no.	Retention time (min)	Molecular weight	[M-H] m/z	Identified compounds	Molecular formula	Major fragments (MS/MS)	References
2 h	1	2.690	176	175.1	Ascorbic acid	C6H8O6	59.01, 85.06, 113.06, 115.04, 131.07, 157.04	Yasir et al., 2016
	2	3.234	550	549.2	Unknown	-	89.02, 161.04, 179.05, 179.03, 323.09, 341.12, 383.1, 443.12, 503.17	-
	3	4.178	180	179	Caffeic acid	C9H8O4	59.01, 71.01, 89.02, 134.03, 135.04, 136.04	-
	4	5.135	498	497.2	O-dicaffeoyl shikimic acid	C22H25O13	59.01, 101.02, 131.03, 149.04, 161.04, 191.05, 289.16, 319.17, 317.11, 335.16, 417.15, 451.22, 497.17, 497.1	Farag et al., 2014
	5	5.237	772	771.2	Quercetin rhamnosyl dihexoside	C33H39O21	143.04, 171.07, 200.05, 290.09, 321.07, 411.11, 425.13, 581.22, 563.18, 609.15, 609.18, 691.13, 770.8, 771.37, 771.32, 771.27	Farag et al., 2014
	6	5.897	610	609.1	Rutin	C27H30O16	271.02, 300.02, 301.03	Abu-Reidah et al., 2015
	7	6.697	608	607.2	Chrysoeriol rhamnosyl hexoside	C28H31O15	284.03, 299.05	Farag et al., 2014
	8	7.417	328	327.2	Trihydroxy-9,14-octadecadienoic acid	C18H31O5	89.02, 171.10, 242.98, 229.14, 327.11, 327.18	Farag et al., 2014
	9	7.818	714	713.5	Unknown	-	677.50	-
	10	7.996	464	463	Isoquercetrin	C21H19O12	71.01, 152.99, 193.01, 265.18, 283.19, 300.03, 301.20, 373.12, 463.21	Farag et al., 2014
	11	8.320	774	773.4	Unknown	-	611.33	-
	12	8.973	810	809.3	Unknown	-	150.03, 151.03, 165.05, 195.06, 179.07, 387.14, 417.15, 535.20, 565.21, 613.23, 713.27, 761.29, 791.30, 809.41	-
	13	9.356	329	328.2	Unknown	-	169.12, 183.13, 225.15, 239.16, 291.19, 309.20, 327.22	-
	14	9.726	226	225	Unknown	-	71.01, 89.02, 113.02, 179.05	-
	15	12.493	313	312.2	Unknown	-	119.04, 170, 183.01, 197.02, 311.17	-
	16	13.184	1046	1045.5	Unknown	-	721.42, 835.46, 1000.54, 999.53	-
	17	13.352	296	295.2	Hydroxy octadecadienoic acid	C18H31O3	183.13, 277.21	Farag et al., 2014
	18	13.745	328	327.2	Unknown	-	119.05, 185.02, 183.01, 184.01, 326.19	-
	19	14.576	341	340.2	Unknown	-	183.01, 185.02, 184.01	-
	20	17.266	327	326.2	Unknown	-	119.05, 197.02, 183.01, 184.01, 279.23, 325.18	-
	21	17.639	226	225.1	Unknown	-	89.02, 71.01, 113.02, 119.03, 179.05	-
	22	21.585	313	312.2	Unknown	-	119.04, 197.02, 183.01, 184.01, 311.17, 311.29	-
2 h	23	23.776	795	794.5	Unknown	-	365.26, 364.26, 363.25, 747.63, 729.58, 793.52, 793.63	-
	24	25.758	963	961.7	Unknown	-	89.02, 161.04, 235.08, 255.23, 277.21, 287.07, 379.12, 397.13, 415.14, 565.3, 635.37, 657.35, 675.37, 833.56, 914.61, 913.54, 913.60, 959.61,	-
5 h	1	1.083	377	376.1	Unknown	-	119.03, 142.05, 160.06, 232.08, 250.09, 322.11	-
	2	1.950	237	236.1	Unknown	-	72, 103.05, 145.05, 147.04, 164.07	-
	3	3.777	578	577.2	O-dicaffeoyl shikimic acid acetate	C24H27O14	96.95, 135.04, 179.03, 179.05, 272.08, 329.06, 371.11, 415.15, 497.13, 577.09, 577.19, 577.16	Farag et al., 2014
	4	4.253	336	335.1	O-caffeoyl shikimic acid	C16H18O8	133.02, 135.04, 137.02, 161.02, 179.03, 155.03, 289.07	Farag et al., 2014
	5	4.333	498	497.1	O-dicaffeoyl shikimic acid	C22H25O13	135.04, 179.03, 161.02, 335.07, 361.11, 341.08	Farag et al., 2014
	6	4.603	772	771.3	Quercetin rhamnosyl dihexoside	C33H39O21	195.06, 241.0, 299.02, 379.16, 463.09, 563.18, 609.15, 691.12, 771.2	Farag et al., 2014
	7	4.814	691	690.1	Unknown	-	241.0, 242.0, 285.04, 286.04, 284.0, 448.1, 447.09	-
	8	5.973	464	463.1	Isoquercetrin	C21H19O12	151.0, 255.03, 271.02, 300.03, 301.03	Farag et al., 2014
	9	5.977	594	593.2	Luteolin rhamnosyl hexoside	C27H29O15	179.03, 285.04, 284.03, 384.98, 463.09, 593.15	Farag et al., 2014
	10	5.181	542	541.2	Chrysoeriol hexosyl sulfate	C22H21O14S	96.95, 179.03, 299.05, 298.04, 341.06, 371.07, 407.16, 461.11, 541.21, 541.06, 541.12, 541.25	Farag et al., 2014
	11	6.093	448	447.1	Luteolin hexoside	C21H19O11	285.04, 284.03, 327.05	Farag et al., 2014
	12	6.064	448	447.1	Unknown	-	284.03, 285.04	-
	13	6.246	478	477.2	Isorhamnoetin-3-O-glucoside	C22H21O12	101.02, 135.98, 271.02, 299.01, 300.02, 315.05, 314.04, 329.03, 431.18, 462.08, 477.1, 477.13, 459.2	Farag et al., 2014
	14	6.510	854	853.2	Unknown	-	195.06, 225.07, 389.16, 567.22, 615.25, 645.26, 807.32	-
	15	6.830	462	461.1	Unknown	-	255.02, 283.02, 299.05, 446.08	-
	16	7.168	610	609.2	Unknown	-	166.02, 181.04, 402.13, 417.15, 563.21	-
	17	7.912	610	609.3	Unknown	-	429.25, 447.26	-
	18	9.142	376	375.2	Unknown	-	79.95, 171.1, 211.13, 229.14, 329.23, 357.17, 295.22	-
	19	9.470	330	329.2	Trihydroxy-octadecenoic acid	C18H33O5	99.08, 129.09, 169.12, 201.11, 199.13, 211.13, 229.14, 275.20, 293.21, 311.22, 329.23	Farag et al., 2014
5 h	20	10.424	328	327.2	Trihydroxy-9,14-octadecadienoic acid	C18H31O5	129.09, 171.10, 199.13, 197.11, 242.98, 327.16, 309.2, 309.22, 326.99, 227.12	Farag et al., 2014
	21	11.485	225	224.8	Unknown	-	89.02, 71.01, 113.02, 222.07, 224.09, 59.01	-
	22	13.220	327	326.2	Unknown	-	119.04, 170.0, 183.01, 197.02, 325.18	-
	23	13.800	340	339.2	Unknown	-	170.00, 183.01, 197.02, 293.21	-
	24	18.376	257	256.2	Unknown	-	255.23	-
	25	18.607	328	327.2	Unknown	-	185.00, 282.25, 281.24	-
	26	21.591	313	312.2	Unknown	-	119.05, 197.02, 18.3.01, 184.01, 239.07, 311.17	-
	27	23.281	341	340.2	Unknown	-	184.01, 183.01, 197.02, 339.32, 339.20	-
	28	26.114	787	786.5	Unknown	-	119.03, 179.05, 560.51, 578.52, 668.58, 740.58	-
	29	5.977	594	593.2	Kaempferol-3-O-glucoside-7-O-rhamnoside	-	179.03, 585.04, 284.03, 384.98, 463.09	-
24 h	1	1.223	166	165.0	Unknown	-	75.00, 147.02	-
	2	1.777	354	353.1	Chlorogenic acid	C16H18O9	137.02, 155.03, 173.04, 172.06	Reis et al., 2012
	3	2.656	176	175.0	Ascorbic acid	C6H8O6	85.06, 115.04, 113.06, 157.04	Yasir et al., 2016
	4	3.409	422	421.0	Unknown	-	135.04, 161.02, 179.03, 251.05, 281.06, 341.08	-
	5	3.791	578	577.2	O-dicaffeoyl shikimic acid acetate	C24H27O14	87.00, 135.04, 179.03, 221.04, 241.00, 321.07, 392.02, 497.13, 577.09, 577.15, 577.18, 577.13	Farag et al., 2014
	6	3.911	690	689.3	Unknown	-	152.04, 165.05, 151.03, 241.0, 285.04, 391.12, 392.12, 447.09, 527.18, 599.20, 689.11, 689.24, 689.29	-
	7	4.147	364	363.2	Unknown	-	183.10, 201.11	-
	8	4.818	802	801.2	Unknown	-	367.05, 368.05, 510.09, 639.14, 638.13, 755.21	-
	9	4.903	484	483.2	Unknown	-	89.02, 119.03, 179.05, 221.06, 483.16	-
	10	5.303	498	497.2	O-dicaffeoyl shikimic acid	C22H25O13	89.02, 149.04, 191.04, 273.11, 335.17, 317.01, 407.20, 453.18, 497.17, 497.08	Farag et al., 2014
	11	5.358	392	391.1	Unknown	-	59.01, 201.12, 271.08, 373.18, 391.12	-
	12	5.425	544	543.0	Isoquercetrin sulfate		151.00, 241.00, 301.03, 463.09	Farag et al., 2014
	13	5.791	668	667.1	Unknown	-	241.00, 249.03, 284.03, 299.05, 320.96, 389.16, 425.05, 505.14, 623.24, 667.15, 667.19	-
24 h	14	6.439	572	571.1	Unknown	-	241.00, 329.06, 314.04	-
	15	6.797	608	607.2	Chrysoeriol rhamnosyl hexoside		283.02, 284.03, 299.05, 298.04, 443.10	Farag et al., 2014
	16	7.301	328	327.2	Trihydroxy-9,14-octadecadienoic acid	C18H31O5	127.03, 167.05, 171.09, 183.14, 225.14, 242.98, 265.18, 283.19, 283.11, 309.17, 327.05, 327.11, 327.14	Farag et al., 2014
	17	7.490	342	341.2	Unknown	-	101.02, 209.11, 221.06, 237.05, 236.99, 216.98, 267.06, 282.09, 341.10, 326.08	-
	18	7.519	542	541.3	Chrysoeriol hexosyl sulfate	C22H21O14S	96.96, 179.03, 241.0, 284.03, 299.05, 333.20, 343.04, 495.26, 541.07	Farag et al., 2014
	19	8.009	226	225	Unknown	-	59.01, 71.01, 89.0, 85.03, 101.02, 113.02, 119.03, 143.03, 161.04, 179.05, 180.05, 225.11	-
	20	8.282	614	613.3	Unknown	-	151.03, 165.01, 150.03, 165.05, 195.06, 225.07, 341.1, 357.13, 387.14, 417.15, 520.17, 535.20, 565.21, 613.23	-
	21	8.546	294	293.1	unknown	-	96.56, 79.95, 213.49, 293.10	-
	22	8.887	330	329.2	Trihydroxy-octadecenoic acid	C18H33O5	145.08, 171.10, 211.13, 229.14, 311.22, 329.19	Farag et al., 2014
	23	9.010	300	299.1	Chrysoeriol	C16H11O6	134.03, 255.03, 256.03, 284.03, 283.02, 284.05	Farag et al., 2014
	24	9.690	448	447.3	Luteolin hexoside	C21H19O11	78.95, 119.03, 203.00, 262.99, 285.12, 285.20, 302.98, 322.99, 346.98, 445.79, 447.0, 447.21	Farag et al., 2014
	25	9.753	1149	1148	Unknown	-	869.47, 1147.57	-
	26	10.600	368	367.1	Unknown	-	157.03, 187.04, 185.11, 277.07, 331.24	-
	27	11.460	226	225.1	Unknown	-	59.01, 71.01, 89.02, 113.02, 119.03, 149.04, 161.04, 179.05, 194.08, 224.09, 224.80	-
	28	13.117	328	327.2	Pinenol-O-glucoside	C18H31O5	119.04, 171.0, 183.01, 184.01, 185.0, 242.98, 326.18	Farag et al., 2014
	29	13.826	341	340.2	Unknown	-	170.0, 183.01, 184.01, 294.21	-
	30	14.473	488	487.3	Unknown	-	113.02, 161.04, 275.23, 279.23, 293.24, 321.24, 351.25, 441.28	-
	31	15.507	454	453.3	Unknown	-	134.95, 255.23, 371.24, 389.25, 407.26, 453.01	-
	32	17.254	327	326.2	Unknown	-	183.01, 184.01, 279.73, 325.18	-
	33	17.525	340	339.2	Unknown	-	183.01, 184.02, 197.02	-
	34	18.522	328	327.2	Unknown	-	185.0, 282.25, 281.25	-
24 h	35	18.906	472	471.3	Unknown	-	61.99, 393.31, 409.35	-
	36	21.626	313	312.0	Unknown	-	119.04, 197.02, 183.01, 184.01, 311.29, 311.17	-
	37	22.693	751	750.5	Unknown	-	119.03, 179.05, 255.23, 283.26, 512.31, 532.48, 704.55, 714.55, 712.54	-
	38	23.289	341	340.2	Unknown	-	184.01, 183.01, 197.02, 339.32, 339.20	-

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