8. Використання хімічних речовин – консервантів і біозахист

Консервантами називають хімічні речовини, які додають до харчових продуктів для пригнічення розвитку небажаних мікроорганізмів, головним чином бактерій, цвілевих грибів, дріжджів.

Консерванти не слід плутати із засобами дезінфекції. Консерванти якщо і вбивають мікроорганізми, то роблять це у багато разів повільніше, ніж дезінфектанти. Консерванти не можуть компенсувати низьку якість сировини і порушення правил виробничої гігієни. Якщо продукт сильно бактерійно забруднений, або почав псуватися, консерванти вживати вже даремно.

Консерванти дозволяють збільшити терміни зберігання готових продуктів і сировини, а також зберегти сировину від псування у процесі технологічної переробки. Консерванти застосовують у тих випадках, коли інші способи збереження продукту неможливі.

Вживання хімічних консервантів обмежується, оскільки будучи токсичними для мікроорганізмів, вони є шкідливими і для людини. Тому їх використовують у дуже невеликих концентраціях, нешкідливих для організму.

У харчовій промисловості хімічні консерванти застосовують, головним чином, в поєднанні з іншими методами консервування.

За хімічним складом це найчастіше кислоти, а їх дія, обумовлена присутністю вільної, недисоційованої молекули, тісно пов’язана з кислотністю середовища.

До харчових хімічних консервантів відносять двоокис сірки і її похідні, бензойну, сорбінову, молочну, оцтову, винну, лимонну, дегідроацетову кислоти і деякі їх солі, ефіри р-оксибензойної кислоти і ін. Борну, саліцилову, мурашину кислоти, формальдегід, перекис водню останнім часом в більшості країн не застосовують.

До речовин, які можуть надавати консервуючу дію, але не є консервантами, в точному значенні цього слова, відносяться куховарська сіль, цукор, коптильний дим, етиловий спирт, нітрит натрію і та ін. Консерванти повинні задовольняти ряду вимог. Вони повинні володіти широким спектром антимікробної дії, щоб протистояти зростанню небажаних для даного харчового продукту мікроорганізмів і перешкоджати утворенню токсинів.

При цьому консерванти не повинні впливати на традиційні мікробіологічні процеси, характерні для виробництва деяких харчових продуктів, наприклад, дозрівання сирокопчених ковбас.

При використовуванні консервантів не допускається їх взаємодія з харчовими компонентами, надання неприємного присмаку або запаху продукту.

Консерванти повинні бути нешкідливі для людини, добре виводитися з організму і не утворювати в ньому токсичні речовини при розщеплюванні. Обов’язковою є наявність гігієнічного свідоцтва для вживання у конкретній харчовій галузі. За якістю і чистотою вони повинні відповідати певним національним і міжнародним вимогам.

Важливими вимогами є простота вживання, хороша розчинність у воді і доступна ціна консерванту.

Механізм дії хімічних консервантів. Консерванти наносять клітинам мікроорганізмів зворотні (бактеріостатична дія) або незворотні пошкодження, унаслідок чого клітини гинуть (бактерицидна дія).

Ефективність і механізм дії консервуючих добавок залежить від багатьох чинників, але перш за все від їх хімічної природи, концентрації, якісного і кількісного складу мікрофлори, а також від рН середовища.

Вплив реакції середовища на мікроорганізми виражається у тому, що водневі іони змінюють електричний заряд молекул цитоплазматичної клітинної мембрани і, залежно від концентрації, збільшують або зменшують її проникність для окремих іонів. Різка зміна рН середовища, що виходить за межі значень, характерних для даного виду мікроорганізмів, приводить до припинення їх життєдіяльності.

Бактерії, за рідкісним виключенням, можуть розвиватися у середовищах з рН 4,2 – 9,4, дріжджі розвиваються у вужчому інтервалі рН (4,0 – 6,8), а цвілеві грибки – у ширших межах кислотності (1,2 – 11,1).

Багато хімічних речовин, що використовуються як консерванти, викликають різні пошкодження мікробних клітин: гідролізують білки, розщеплюють вуглеводи, блокують дію певних ферментів, впливають на проникність калієвих і натрієвих каналів і т.д.

Консерванти, здібні до електричної дисоціації, можуть проявляти антимікробну активність або за рахунок дії іонів водню, що утворюються, або у вигляді недисоційованих молекул. Прикладом консервантів, які діють за допомогою іонів водню, можуть служити оцтова або мурашина кислоти. Консерванти цього типу застосовуються у відносно високих для харчової промисловості концентраціях – не менше 1 %.

Інші консерванти кислотного типу найбільш ефективні при низьких значеннях рН, коли велика частина їх знаходиться у недисоційованому вигляді. Завдяки цьому молекули кислоти можуть проникати в клітину мікроорганізму, тоді як проникнення іонів істотно затруднене. Представниками таких речовин є сорбінова, бензойна, дегідроацетова і інші кислоти. Так, наприклад, при рН = 3 близько 93 % молекул бензойної кислоти знаходиться у недисоційованому вигляді, а при рН = 7 – тільки 0,15%. У нейтральному середовищі ці консерванти проявляють слабку антимікробну активність.

Із зменшенням константи дисоціації консервуючої кислоти навіть при нейтральній або слабокислій реакції підвищується кількість недисоційованих молекул, які гарантують їх дію. Чим слабкіше кислота-консервант, тим ближче може бути рН до нейтральної точки, причому консервуюча дія не зменшується.

Консервуюча дія сірчистої кислоти заснована на її здатності ушкоджувати клітинні ферменти мікроорганізму, порушуючи нормальне протікання метаболізму у мікробній клітині.

Механізм інгібування сорбіновою кислотою зростання цвілі полягає у її розпаді під впливом ферментів цвілі за типом окислення жирних кислот. В середовищі відбувається накопичення ненасичених жирних кислот, що інгібує дегідрогеназну активність цвілі.

При високому обсіменінні концентрація усіх ферментативних систем підвищується, унаслідок чого активність дегідрогенази не може бути інгібована. Сорбінова кислота при високому обсіменінні продукту не є активною.

Хімічні речовини можуть гальмувати ферментативні реакції, приєднуючись до білкової частини ферменту клітини (апофермента) і тим самим інактивуючи його. Такий, зокрема, один з механізмів дії бензойної кислоти і її солей, які конкурують з коферментом за апофермент.

Оскільки більшість консервантів володіє специфічною дією відносно різних видів мікроорганізмів, а псування харчових продуктів обумовлюється великим числом видів мікроорганізмів, те створення комбінованих складів має певні переваги. Адитивна дія двох речовин можлива за рахунок того, що одна з речовин, впливаючи на оболонку клітини, полегшує проникнення у клітину іншої, або один з консервантів знижує рН і тоді ефективність дії іншого консерванта підвищується. Комбінування консервантів дозволяє не тільки розширити спектр їх дії, але і зменшити необхідне дозування.

Вживання консервантів. При вживанні консервантів необхідно дотримуватися наступних основних принципів:

обробці консервантами можна піддавати тільки продукти, що мають бездоганну якість;

– використовувати можна тільки речовини, перераховані у відповідних затверджених переліках і у кількостях, що не перевищують встановлених максимальних концентрацій;

не допускається вживання більше двох консервантів, причому вміст окремих компонентів не повинен перевищувати в сумі 100 %.

Спосіб обробки продуктів консервантами залежить від виду продукту і його стану. У подрібнені продукти консерванти можна вводити безпосередньо у сировину. Продукти з незруйнованою структурою, а також вироби, в оболонці піддають поверхневій обробці, занурюючи в розчин або обприскуючи. Ковбасні оболонки можна замочувати в розчинах захисних складів перед формуванням ковбас. Антимікробні добавки можна вводити до складу високомолекулярних з’єднань, зокрема полімерних плівок і латексних композицій.

Стадія внесення консерванта в продукт залежить від технології його виробництва. Оптимальним вважається момент відразу після пастеризації або стерилізації, коли в результаті термообробки знижується рівень обсіменіння мікроорганізмами, а додавання консерванта дозволяє зберегти продукт достатньо довго.

Вживання консервантів може бути ефективним тільки при їх рівномірному розподілі в продукті, що найлегше досягається розчиненням консерванта.

Способи обробки м’ясопродуктів консервантами:

  • пряме введення (при подрібненні, перемішуванні, шприцюванні);
  • поверхнева обробка (занурення, обприскування, замочування оболонок);
  • введення до складу оболонок, пакувальних матеріалів, захисних покриттів.

Залежно від ступеня розчинності у воді консерванти використовують у вигляді водних розчинів (найчастіше солі кислот) або сухими, у вигляді порошків (кислоти).

Для введення у продукти дозволені органічні кислоти і їх солі, зокрема: лимонна кислота, цитрати, оцтова кислота, ацетати, молочна кислота, лактати. Пригноблююча дія харчових кислот, зокрема, на кишкову паличку і протей виявляється у концентраціях вище 0,01 %. За ефективністю дії на бактерії кислоти можна розташувати в наступній послідовності: оцтова > лимонна > молочна. По відношенню до термофілів найбільш бактерицидна лимонна кислота.

Препарати органічних кислот і їх солей вносять у фарш варених ковбас при куттеруванні або шприцюють у складі розсолів у вироби шинок. Подовження термінів зберігання досягається не тільки за рахунок уповільнення зростання бактерій, зокрема патогенних, але і за рахунок зниження значень активності води і рН.

У м’ясній промисловості більш поширена поверхнева обробка виробів, особливо тривалого терміну дозрівання. Вона здійснюється шляхом занурення готового продукту в розчин консерванта або шляхом його обприскування. У першу чергу така обробка необхідна для сирокопчених ковбас, на поверхні яких активно розвиваються цвілеві і дріжджові грибки, продукти життєдіяльності яких розщеплюють жири, руйнують фарбувальні пігменти, негативно впливають на смак і аромат.

Класичним засобом обробки поверхні сирокопчених ковбас є сорбат калію, проте він може викликати, як указувалося раніше, розщеплювання жирів.

Альтернативою сорбату калію можуть служити розчини харчових кислот, зокрема молочної і оцтової, або суміші кислот.

Пряме занурення в розчин харчових кислот, шприцювання і їх підвішування у капаючому стані дозволяє досягти оптимальних результатів для сирокопчених ковбас.

Добрі результати одержані при обробці оболонки дегідроацетовою кислотою (ДГК) і її натрієвою сіллю (ДГС), які володіють широким спектром дії на всі види дріжджів, цвілі, на гнильні бактерії, актиноміцети. Ковбасні оболонки замочують у водному розчині препарату перед шприцюванням.

Як ефективний засіб, що запобігає розвитку дріжджів, цвілі на поверхні сирокопчених і сиров’ялених продуктів, застосовують антибіотик натамакс, активною речовиною якого є натаміцин. Він використовується для поверхневої обробки у вигляді 0,4 %-го розчину. Розчини консервуючих речовин можна наносити під тиском спеціальним аерозольним пістолетом. Обробка повинна проходити послідовно у камері дозрівання (сирокопчені ковбаси) або охолоджування (напівкопчені ковбаси).

Для отримання необхідного ефекту консервування слід проводити попередні випробування в умовах конкретного виробництва, які дозволяють уточнити перелік вживаних консервантів і їх концентрацію, а також перевірити їх сумісність з компонентами конкретного продукту.

При використовуванні консервантів прямого введення необхідно враховувати деякі чинники. Зокрема, кислотність середовища впливає на ефективність консервантів – чим кисліший продукт, тим менше в нього додають консерванта.

Продукти зниженої калорійності, що містять менше жиру, солі і більше води, мають нижчу мікробіологічну стійкість. Кількість консерванта, що додається в них, повинна бути на 30 – 10 % більше, ніж рекомендується для звичних продуктів.

Перспективним є введення консервантів безпосередньо до складу ковбасних оболонок, полімерних плівок і латексних покриттів. Такий підхід дозволяє надійно закріпити консервант на межі захисна плівка–продукт і понизити його міграцію у товщу. Латексні покриття, формовані безпосередньо на поверхні готових ковбасних і м’ясних делікатесних виробів, забезпечують надійний захист від ураження мікрофлорою і механічних пошкоджень у процесі зберігання, транспортування і реалізації.

Токсикологічні аспекти використовування консервантів. Консервуючі речовини можуть бути схвалені як добавки до харчових продуктів тільки після доказу їх нешкідливості. При цьому необхідно враховувати можливість токсичної дії продуктів метаболізму, а також речовин, що утворюються в результаті взаємодії хімічних консервантів з компонентами продукту.

При токсикологічних дослідженнях потрібне визначення доз, що викликають гострі, підгострі і хронічні отруєння, з одночасною перевіркою канцерогенного, алергічного і інших можливих несприятливих дій добавок на організм людини.

Прояв будь-якої з перерахованих дій веде до заборони вживання харчової добавки.

Контроль за вживанням харчових добавок, у тому числі і консервантів, здійснюється працівниками санітарного нагляду.

Вирішуючи питання про використовування консервантів необхідно мати на увазі, що у суспільстві склалося насторожене відношення до додавання у продукти харчування любих хімікатів, навіть визнаних в даний час нешкідливими. Використовування хімічних засобів мікробіального захисту допустиме тільки у тому випадку, коли фізичними методами обробки не можна досягти достатньої стійкості харчових продуктів при зберіганні.

Біоконсервування. В основі поняття біологічного консервування лежить внесення у м’ясо і м’ясні продукти певної корисної мікрофлори, яка обмежує розвиток небажаної мікрофлори і є, таким чином, додатковим бар’єром. Вживання біологічного захисту дозволяє підвищити мікробіологічну безпеку м’ясопродуктів без використовування хімічних інгредієнтів. Захисна мікрофлора виконує свої основні функції пригнічення патогенної мікрофлори м’ясопродуктів шляхом синтезу органічних кислот і бактеріоцидів (антибіотиків).

Вона повинна відповідати певним вимогам, яким найбільшою мірою відповідають молочнокислі бактерії. Для різного типу продукції використовуються певні види культур.

У неферментованих продуктах (фарш, охолоджене м’ясо, ковбаски для гриля, нарізані шинки і варені ковбаси) краще всього себе проявляють Lactobacilus sakei. Staphylococcus xylosus, Leuconostoc carnosum. Вони не тільки пригнічують власну гнильну мікрофлору м’яса, але і сприяють формуванню аромату і кольору, а також підвищують стабільність кольору посолених м’ясопродуктів.

Для ферментованих продуктів (ферментовані ковбаси, шинки) використовують Lactobacilus curvatus, Pediococcus асidilactici, Staphylococcus xylosus. Комбінування таких типів сприяє синтезу бактеріоцинів. пригніченню розвитку Лістерії, а також правильній ферментації і отриманню високих органолептичних показників.

Біозахисну мікрофлору вносять у фарш при його складанні при виробництві ферментованих ковбас.

Для готових до вживання виробів (варених ковбас, шинок і ін.) захисні мікроорганізми застосовують після повної термічної обробки продукції, у процесі виготовлення сервірувальної нарізки. Розчин з культурами у вигляді аерозолю наноситься безпосередньо в машині для різання м’ясопродуктів. Аналогічно можна обробляти поверхню натуральних напівфабрикатів.

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