Okilgan sellülozaning struktura va elektron qayta tashkilotlanishini ochish: karboksil tomonidan keltirilgan o'zgartirishlarga nisbatan zichlik funksiyasi nazariyasi nuqtai nazari
Annotatsiya
Sellülozaning boshqariladigan oksidlanishi C6 pozitsiyasida karboksil funktsional guruhlarini kiritadi, bu uning vodorod bog'lanish tarmog'ini, kristall tuzilishini va elektron xususiyatlarini sezilarli darajada o'zgartiradi. Ushbu ishda zichlik funksiyasi nazariyasi (DFT) ishlatiladi, toza sellüloza Iβ va oksidlangan modelni o'rganish uchun, bunda C6 gidroksimetil guruhi (–CH₂OH) karboksil guruhiga (–COOH) aylantiriladi, bu dichromat-induksiyalangan oksidlanishni taqlid qiladi. Strukturaviy optimizatsiya anizotropik kristall panjarasining buzilishini, jumladan a-o'qi bo'ylab qisqarishni, b-o'qi bo'ylab ozgina kengayishni va panjara burchaklarining oshishini ko'rsatadi, bu esa zanjirlararo joylashishni qayta tashkil qilishni anglatadi. Vodorod bog'lanishlarini tahlil qilish oksidlanish natijasida vodorod bog'larining umumiy soni 18 dan 24 taga oshishini va eng qisqa H•••O masofasining 1.78 Å dan 1.70 Å gacha qisqarishini ko'rsatadi, bu esa kuchliroq intermolekulyar o'zaro ta'sirlarni aks ettiradi. Bader zaryad tahlili oksidlangan C6 joylarida elektronlarning sezilarli darajada kamayishini ko'rsatadi, bu esa karboksil guruhlarining elektron tortuvchi tabiatiga mos keladi. Elektron tuzilishi hisob-kitoblari bant oraliqlarining qisqarishini va kimyoviy potensialning pastga siljishini ko'rsatadi, bu esa kuchaytirilgan elektron qabul qilish xususiyatini taklif qiladi. Optik yutish spektri oksidlangan tizimda intensivlikning oshishini va aniq anisotropiyani ko'rsatadi. Ushbu topilmalar oksidlanish bilan bog'liq o'zgarishlarga atomistik nuqtai nazar beradi va funktsionalizatsiya qilingan sellüloza materiallarini loyihalash uchun nazariy asosni ta'minlaydi.
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