1. Introduction
Hulless barley (
Hordeum vulgare L.
var. nudum Hook. f.), also known as naked barley, is a distinctive cereal crop of the genus Hordeum (family Poaceae) and ranks among the highest-altitude crops cultivated worldwide. It is predominantly distributed across the Qinghai–Tibetan Plateau in China, as well as the western regions of Sichuan, Yunnan, and Gansu provinces, and is also cultivated in neighboring Himalayan countries, including Bhutan and Nepal [
1]. Owing to its naked caryopsis and ease of dehulling, hulless barley offers greater convenience in grain processing and direct consumption compared with common barley. It has served as the traditional staple food for generations of inhabitants of the Qinghai–Tibetan Plateau and is revered by the Tibetan people as the “king of highland grains” [
2]. Characterized by exceptional tolerance to cold, drought, and low soil fertility, hulless barley has become an indispensable food crop in high-altitude regions, playing an irreplaceable role in ensuring regional food security.
As a premium cereal crop, hulless barley possesses a nutritional profile consistent with a healthy dietary pattern characterized by high protein, high fiber, high vitamins, low fat, and low sugar [
3,
4]. Its protein and lysine contents exceed those of most other cereal crops, playing an important role in promoting growth and development and enhancing immune function [
5,
6,
7]. Additionally, hulless barley is rich in dietary fiber, particularly β-glucan—often referred to as a “health guardian”—which has been extensively demonstrated to exert multiple physiological functions, including lowering blood glucose and blood lipids, enhancing immunity, and improving gut health [
8,
9,
10,
11]. Furthermore, hulless barley contains abundant polyphenolic compounds (e.g., ferulic acid, proanthocyanidins), γ-aminobutyric acid (GABA), and minerals such as calcium, iron, zinc, and magnesium. These functional components exhibit significant positive effects in antioxidant, anti-inflammatory, and neuroregulatory activities, as well as in maintaining cardiovascular health and bone metabolism [
12,
13,
14,
15]. Owing to this comprehensive and balanced nutritional composition, hulless barley not only satisfies basic energy requirements but also demonstrates considerable potential in promoting health among modern populations.
Hulless barley can be processed into a wide variety of food products, ranging from traditional preparations such as tsampa and hulless barley wine to innovative developments driven by the modern food industry. However, like other whole grains, hulless barley exhibits a hard pericarp and a dense starch granule structure, which result in a prolonged cooking time and a technical bottleneck wherein it fails to gelatinize synchronously when cooked together with rice [
16]. To address this issue, grain ripening (or pre-gelatinization) technology has been developed. This process involves pretreatment methods such as steaming, microwave irradiation, or conditioning to induce partial starch gelatinization, thereby significantly reducing cooking time, improving palatability, and enhancing the digestibility of nutrients [
17,
18,
19]. Based on this technology, pre-gelatinized hulless barley rice has been developed, which achieves simultaneous cooking with rice. This product combines convenience with high nutritional value, meeting the urgent consumer demand for healthy and convenient foods in a fast-paced lifestyle, and thus holds considerable market potential [
20,
21].
Progress has been achieved in the processing technology of pre-gelatinized rice, such as the simple operation but low efficiency of the steaming method and the high efficiency yet high equipment cost and susceptibility to uneven heating associated with microwave pre-gelatinization technology [
22,
23]. Against this backdrop, optimizing the processing parameters to balance product quality, nutrient retention, and production efficiency has become a key issue for industrial development. Particularly for hulless barley, which is rich in heat-sensitive and water-soluble functional components, how to maximize the retention of bioactive substances such as polyphenols, flavonoids, and β-glucan during the pre-gelatinization process represents a core scientific question for enhancing the added value of the product.
Therefore, this study focuses on two key process steps in the production of pre-gelatinized hulless barley rice: soaking and drying. To address the challenges of water-soluble nutrient loss during conventional soaking and the unclear effects of drying conditions on product texture and functional properties, this paper aims to systematically investigate the influence of soaking conditions (e.g., the balance between water absorption and nutrient retention), as well as different drying temperatures and durations, on the sensory quality, textural properties, degree of gelatinization, and major functional component contents of pre-gelatinized hulless barley rice. Through comprehensive analysis of the above evaluation indicators, we intend to identify the optimal combination of processing parameters. This will provide a scientific basis and technical support for developing a novel pre-gelatinized hulless barley rice product that combines excellent eating quality with high nutritional value, thereby enriching the variety of hulless barley products, enhancing their market competitiveness, and promoting the sustainable development of the hulless barley industry.
2. Materials and Methods
2.1. Materials
Kangding black hulless barley (Hordeum vulgare L. var. nudum Hook. f.) was provided by the Key Laboratory of Coarse Cereal Processing, Ministry of Agriculture and Rural Affairs, Chengdu University. Potassium hydroxide, methanol, hydrochloric acid, iodine, and potassium iodide were all of analytical grade and purchased from Chengdu Kelong Chemical Co., Ltd. (Chengdu, China).
2.2. Investigation of the Infiltration Process for Hulless Barley
To develop a precise moisture control method for hulless barley seeds, this study employed an infiltration technique. Under room temperature conditions, uniformly sized and disease-free hulless barley seeds were placed in distilled water. Samples were taken at 0, 1, 2, 3, 4, 5, 6, 7, and 8 h, respectively. After removing surface moisture with absorbent paper, the seeds were weighed to calculate the water absorption rate, and a dynamic seed water absorption curve was plotted. Infiltration, as a technique that regulates the degree of contact between seeds and water, provides the appropriate amount of water required for germination and avoids hypoxia and nutrient loss caused by excess water, thereby activating enzyme activity and promoting uniform and healthy germination. Unlike complete immersion (soaking), infiltration places greater emphasis on controlling the water uptake process. The time–water absorption rate curve obtained in this study can provide a reference for the appropriate amount of water to be added at different time points in subsequent infiltration processes, ensuring that seed water absorption precisely meets germination requirements.
Mt: mass of hulless barley after water absorption (with surface moisture blotted dry), M0: initial mass of hulless barley, Wt: water absorption rate of hulless barley.
2.3. Process Flow for Pre-Gelatinized Hulless Barley Rice
Grains of hulless barley with uniform size and no disease symptoms were manually screened. The grains were subjected to precise primary–secondary infiltration according to the pre-established water absorption curve, or conventional full-immersion soaking for the target duration to achieve the desired water uptake. Upon completion of infiltration or soaking, the grains were rapidly rinsed with deionized water for 30 s to remove soluble residues on the kernel surface. Afterwards, the grains were spread in a uniform single layer on stainless steel trays for hot air drying, with the drying temperature and duration strictly set in accordance with the experimental design. After drying, samples were taken out and force-air cooled to room temperature (25 °C) in a clean and dust-free environment. Once fully cooled, the samples were immediately vacuum packaged using aluminum plastic composite bags to isolate them from oxygen and ambient moisture and avoid oxidative deterioration of bioactive components. Stable pre-gelatinized hulless barley rice samples were thereby obtained for subsequent quality analysis. All processing treatments were performed in triplicate.
2.4. Optimization of the Infiltration Process for Pre-Gelatinized Hulless Barley Rice
2.4.1. Optimization of Primary and Secondary Infiltration Times
First, the primary and secondary infiltration times were optimized. Primary infiltration refers to the first-stage moisture-regulating infiltration treatment of hulless barley grains; after completing primary infiltration, surface free water was removed with absorbent paper, and then the grains immediately underwent the second-stage infiltration treatment, which is defined as secondary infiltration. Compared with single-stage infiltration, the segmented primary–secondary infiltration mode can realize more uniform water penetration inside kernels, avoid excessive free water immersion occurring in traditional full soaking, reduce leaching loss of water-soluble bioactive components, and promote uniform starch gelatinization.
Both primary and secondary infiltration times were set at 1, 2, 3, and 4 h, resulting in the following treatment groups: 1–1, 1–2, 1–3, 1–4, 2–1, 2–2, 2–3, and 2–4. The quality of the cooked pre-gelatinized hulless barley rice was comprehensively evaluated using sensory evaluation, texture profile analysis, and degree of gelatinization measurement.
2.4.2. Comparison of Infiltration and Soaking Processes
The optimized infiltration process was compared with the traditional soaking process using raw hulless barley grains. Differences between the infiltration and soaking processes were comprehensively investigated through sensory evaluation, degree of gelatinization, textural properties, and changes in water-soluble active components.
2.4.3. Optimization of the Drying Process After Infiltration
Based on the optimal infiltration conditions, the temperature and time parameters of the drying process after infiltration were further optimized. The experimental design was as follows:
Drying temperatures: 80 °C, 100 °C, 120 °C, 140 °C, and 160 °C. Drying times: For each temperature, three time points were set based on actual conditions to ensure that the moisture content of the pre-gelatinized hulless barley fell within the specified range after processing:
80 °C: 90 min, 120 min, 150 min; designated as groups 80–90, 80–120, 80–150.
100 °C: 60 min, 90 min, 120 min; designated as groups 100–60, 100–90, 100–120.
120 °C: 50 min, 80 min, 110 min; designated as groups 120–50, 120–80, 120–110.
140 °C: 40 min, 60 min, 80 min; designated as groups 140–40, 140–60, 140–80.
160 °C: 30 min, 50 min, 70 min; designated as groups 160–30, 160–50, 160–70.
Sensory evaluation, degree of gelatinization, and texture profile analysis were used to select the optimal drying time at each temperature.
The optimal time combinations at each drying temperature were further compared using a multi-index evaluation approach, including functional component analysis (polyphenol and β-glucan contents), flavor component analysis (electronic nose and electronic tongue), and antioxidant capacity determination (DPPH and ABTS+ radical scavenging activities), to investigate the effects of drying temperature and time on the nutritional quality of the pre-gelatinized rice.
2.5. Sensory Evaluation of Pre-Gelatinized Hulless Barley Rice
The sensory scoring criteria for pre-gelatinized hulless barley rice were established with reference to the Chinese national standard GB/T 15682-2008 [
24], with slight modifications. Ten panelists with a background in food science were recruited to form the scoring team. According to
Table 1, the cooked hulless barley rice was evaluated for color, aroma after co-cooking with rice, taste, chewiness, and viscoelasticity. The total score was 100 points.
2.6. Determination of Nutritional Component Contents
The contents of moisture, fat, starch, and protein were determined according to the methods specified in the corresponding Chinese national standards.
Moisture content: Determined according to GB 5009.3-2016 [
25] National Food Safety Standard—Determination of moisture in foods (direct drying method).
Fat content: Determined according to GB 5009.6-2016 [
26] National Food Safety Standard—Determination of fat in foods (Soxhlet extraction method).
Protein content: Determined according to GB 5009.5-2016 [
27] National Food Safety Standard—Determination of protein in foods (Kjeldahl method).
Starch content: Determined according to GB 5009.9-2023 [
28] National Food Safety Standard—Determination of starch in foods.
2.7. Texture Analysis of Pre-Gelatinized Hulless Barley Rice
After co-cooking the pre-gelatinized hulless barley with rice, three grains of moderate size and uniform texture were selected and placed on the platform of a texture analyzer (TA-XT plus, Stable Micro Systems Ltd., Godalming, UK). Measurements were performed using the texture profile analysis (TPA) mode with a P36R probe. The test parameters were set as follows: trigger force 5 g; two cycles of compression; compression ratio 75%; pre-test and post-test speed 5 mm/min; compression speed 1 mm/s; and interval time between cycles 5 s.
2.8. Determination of Gelatinization Degree of Pre-Gelatinized Hulless Barley Rice
The gelatinization degree of pre-gelatinized hulless barley rice was determined based on the method of Liu et al. [
29] with slight modifications. A 0.2 g sample of dried and ground pre-gelatinized hulless barley powder was weighed and mixed with 98 mL of distilled water, followed by the addition of 2 mL of 10 mol/L KOH solution, with gentle stirring for 5 min. The resulting suspension was centrifuged. Then, 1 mL of the supernatant was collected, mixed with 0.4 mL of 0.5 mol/L HCl solution, and diluted with distilled water to a final volume of 10 mL. Subsequently, 0.1 mL of iodine reagent (prepared by dissolving 1 g of iodine and 4 g of potassium iodide in 100 mL of water) was added. After thorough mixing, the absorbance was measured at 600 nm using a spectrophotometer (UV-2600 UV-Vis spectrophotometer, Shimadzu Corporation, Kyoto, Japan) and recorded as A
1. Separately, another 0.2 g sample powder was treated with 95 mL of distilled water and 5 mL of 10 mol/L KOH solution, neutralized with 1.0 mL of 0.5 mol/L HCl solution, and thoroughly mixed. The absorbance was measured at 600 nm and recorded as A
2. The gelatinization degree for each sample was calculated from the ratio of the absorbances obtained under the two conditions.
2.9. Determination of Total Phenolic Content of Pre-Gelatinized Hulless Barley Rice
The total phenolic content of pre-gelatinized hulless barley rice was determined using a Plant Total Phenol Assay Kit (96-well plate, purchased from Beijing Solarbio Science & Technology Co., Ltd., Beijing, China). The pre-gelatinized hulless barley rice was ground into powder and passed through a 60-mesh sieve. The total phenolic content was then measured according to the manufacturer’s instructions. Each sample was analyzed in triplicate.
2.10. Determination of β-Glucan Content of Pre-Gelatinized Hulless Barley Rice
The β-glucan content was quantified with a Mixed-Linkage β-Glucan Assay Kit (96-well plate format, Megazyme International, Bray, Ireland) based on the official enzymatic assay procedure provided by the manufacturer. Briefly, pre-gelatinized hulless barley rice samples were ground into fine powder and sieved through a 60-mesh screen. Then, a 100 mg sample powder was accurately weighed and transferred into a test tube, followed by the addition of 2.0 mL of sodium phosphate buffer (20 mM, pH 6.5). The mixture was vortexed and incubated in a water bath at 100 °C for 5 min to promote starch gelatinization. After cooling the tube to 50 °C, 0.2 mL of lichenase solution was added, vortexed, and incubated at 50 °C for 60 min with intermittent shaking to completely hydrolyze the mixed-linkage β-glucan. Subsequently, 2.5 mL of sodium acetate buffer (200 mM, pH 4.0) was added to terminate the enzymatic reaction. The tube was vortexed and centrifuged at 3000× g for 10 min at room temperature. An aliquot of 0.1 mL of the resulting supernatant was transferred to a new test tube, and 0.1 mL of β-glucosidase working solution was added. After thorough mixing, the mixture was incubated at 50 °C for 10 min. For the blank control, 0.1 mL of supernatant was mixed with 0.1 mL of sodium acetate buffer (200 mM, pH 4.0) without β-glucosidase. Next, 1.5 mL of GOPOD reagent was added to both sample and blank tubes, mixed well, and incubated at 50 °C for 20 min. The absorbance of each solution was measured at 510 nm using a microplate reader. The β-glucan content was calculated according to the calculation formula supplied in the kit manual. Each sample was analyzed in triplicate.
2.11. Determination of Total Flavonoid Content of Pre-Gelatinized Hulless Barley Rice
The total flavonoid content was quantified via the aluminum salt colorimetric method using rutin as the reference standard to prepare standard working solutions. The linear regression equation of the standard curve was established as y = 0.828x + 0.041, with a coefficient of determination R2 = 0.9989. Precisely 1 mL of the cooked hulless barley rice sample extract was pipetted and diluted 10-fold, followed by absorbance measurement at 510 nm. The total flavonoid content of the sample was calculated based on the standard curve, and the results were expressed in mg/100 g. All samples were analyzed in triplicate.
2.12. Determination of Reducing Sugar Content of Pre-Gelatinized Hulless Barley Rice
A 0.1 g sample of dried pre-gelatinized hulless barley powder was weighed and mixed with 5 mL of distilled water. The mixture was shaken and placed in a 50 °C water bath for 30 min, then centrifuged at 8000 r/min for 20 min. The supernatant was collected for analysis. The reducing sugar content was determined using the 3, 5-dinitrosalicylic acid (DNS) method: 0.1 mL of the supernatant was transferred into a centrifuge tube, followed by the addition of 0.4 mL of distilled water and 1.5 mL of DNS chromogenic reagent. After thorough mixing, the tube was heated in a boiling water bath for 5 min, then cooled, and the absorbance was measured at 540 nm. The reducing sugar content was calculated based on a standard curve (y = 1.3776x + 0.0363, R2 = 0.999).
2.13. Intelligent Sensory Analysis of Pre-Gelatinized Hulless Barley Rice
2.13.1. Electronic Tongue Analysis
The taste profile of pre-gelatinized hulless barley rice was determined using an electronic tongue (ASTREE V 5.1, Alpha M.O.S., Toulouse, France) following the method described by Liu et al. [
30] with slight modifications. The sensors of the electronic tongue were used to measure various taste attributes, including sourness, sweetness, bitterness, saltiness, and umami. The measurement program was set as follows: electrode cleaning for 90 s, buffer cleaning for 120 s, buffer cleaning for 120 s, stabilization for 30 s, sample testing for 30 s, buffer cleaning for 3 s, buffer cleaning for 3 s, and aftertaste determination for 30 s. Each sample was measured in five replicate cycles. The sensor performance characteristics are presented in
Table 2.
2.13.2. Electronic Nose Analysis
The electronic nose (PEN3, Arisense, Schwerin, Germany) was used to analyze the flavor profile of pre-gelatinized hulless barley rice, following the method described by Jiang et al. [
31] with slight modifications. The measurement parameters were set as follows: cleaning time 90 s, detection time 150 s, and carrier gas flow rate 500 mL/min. Each sample was measured in five replicates. The volatile compounds were detected using different sensors, and the sensor performance characteristics are presented in
Table 3.
2.14. Determination of Antioxidant Activity
The hulless barley rice powder was passed through a 60-mesh sieve. Briefly, 0.5 g of the sieved sample powder was accurately weighed into a 50 mL centrifuge tube, and 30 mL of 70% methanol solution was added. Ultrasonic extraction was performed at room temperature with a frequency of 100 Hz for 30 min. The mixture was centrifuged at 4000 r/min for 10 min, and the supernatant extract was collected. The residual pellet was re-extracted twice under identical conditions. The supernatants from the three extractions were combined and diluted to a final volume of 100 mL with 70% methanol solution to prepare a sample working solution at 5 mg/mL.
The supernatant was serially diluted with 80% methanol solution to prepare sample working solutions at concentrations of 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.4, 0.6, 0.8 and 1.0 mg/mL. The VC solution was used as the positive control, and the half-maximal inhibitory concentration (IC
50) was calculated. The DPPH radical scavenging assay was performed with slight modifications according to the method described by Uzkuç et al. [
32]. Briefly, 2 mL of the sample working solution was accurately pipetted and mixed with 2 mL of DPPH solution, followed by thorough shaking. The mixture was incubated at room temperature in the dark for 30 min, and the absorbance was measured at 517 nm and recorded as Ai. An equal volume of 80% methanol solution was used to replace the DPPH solution, and the absorbance was determined using the same procedure and denoted as Aj. An equal volume of 80% methanol solution was used to replace the sample working solution, and the absorbance was measured identically and recorded as Ac. The VC solution was set as the positive control and subjected to the same measurement procedure for DPPH radical scavenging activity. All assays were performed in triplicate. The DPPH radical scavenging rate was calculated using the following formula:
The ABTS radical scavenging assay was carried out with minor modifications based on the method reported by Segoviano-Leon et al. [
33]. Equal volumes of 7 mmol/L ABTS solution and 2.5 mmol/L potassium persulfate solution were mixed and kept in the dark at room temperature for 24 h to prepare the ABTS stock solution. Before use, an appropriate amount of the ABTS stock solution was diluted with 95% ethanol until its absorbance reached 0.70 ± 0.02 at 734 nm to obtain the ABTS working solution. Briefly, 0.1 mL of the serially diluted sample solution was added to a 5 mL centrifuge tube, mixed thoroughly with 3.9 mL of ABTS working solution, and incubated in the dark at room temperature for 6 min. The absorbance was measured at 734 nm and recorded as Ai. An equal volume of absolute ethanol was used to replace the ABTS working solution, and the absorbance was detected following the same procedure and marked as Aj. An equal volume of 80% methanol solution was used to replace the sample solution, and the absorbance was measured identically and denoted as Ac. A VC solution was used as the positive control, and the ABTS radical scavenging activity was determined by the same procedure. All assays were performed in triplicate. The ABTS radical scavenging rate was calculated according to the following formula:
2.15. Statistical Analysis
All experimental data are expressed as mean ± standard deviation. Two-way analysis of variance (ANOVA) was conducted for group comparisons. Significant differences among treatments were determined by Tukey’s HSD post-hoc multiple-comparison test, with p < 0.05 regarded as statistically significant. Tukey’s HSD test inherently performs adjustment for multiple comparisons. All statistical calculations were completed using SPSS 26.0 software. Different lowercase superscript letters in tables and figures indicate significant differences.
4. Conclusions
In this study, the processing technology of pre-gelatinized hulless barley rice was investigated, with a focus on optimizing two critical steps: infiltration and drying. For the infiltration process, the effects of different infiltration cycles and durations were evaluated using sensory scores, textural properties, and degree of gelatinization as the primary indicators. The results demonstrated that the secondary infiltration for 4 h treatment yielded the best performance in terms of mouthfeel, texture, and gelatinization degree. Compared with the traditional soaking process, this infiltration approach significantly reduced the loss of water-soluble nutrients, achieving higher retention rates for polyphenols, flavonoids, and β-glucan, effectively enhancing the nutritional value of the final product.
After determining the optimal infiltration conditions, the corresponding optimal drying times were identified. It was found that the treatments at 80 °C for 120 min and 100 °C for 90 min exhibited the best sensory quality and textural properties. Low-temperature drying was more favorable for retaining polyphenols and flavonoids, and the β-glucan content under these conditions reached about 3.1%. Antioxidant assays further confirmed that the treatments at 80 °C for 120 min and 100 °C for 90 min exhibited the highest DPPH and ABTS+ radical scavenging activities. Based on a comprehensive evaluation of sensory, textural, gelatinization, and nutritional functional indicators, the optimal drying conditions for pre-gelatinized hulless barley rice were determined to be 80–100 °C for 90–120 min. This optimized process not only ensures processing efficiency but also maximizes the retention of nutritional and functional properties of hulless barley, which shows promising potential for future large-scale manufacture.