The main objective of “SNIFF” project is to develop efficient optical microsensor arrays (optical multi-sensor) using Surface Plasmon Resonance (SPR) for detecting various drug compounds i.e. LDS, cocaine or methamphetamine to prevent illegal transit and consumption of drugs. Furthermore, the sensitive membrane of the optical sensor will be tailored, using a molecularly imprinting technique (MI), to “sniff” (sense and detect) only the targeted drugs.

Project general objectives are:

- The enhancement of health security of the peoples, by preventing the illicit drug consumption, with impact on life quality;

- Developing of new materials, products and devices with low volume, but with high added-value;

- The optimization of the methods for border crossing controls;

- Development of new technologies for analytical devices

Project specific objectives are:

- Obtaining of molecularly imprinted polymers by polymerisation or electro polymerization (University of Toulon- MAPIEM). The outcome of this objective will be the technology for obtaining of MIP films on the SPR surface, by polymerization.

- Obtaining of molecularly imprinted membranes by phase inversion and sol-gel process (ICECHIM). The outcome of this objective will be the technology for obtaining of MIP membranes on SPR surface by phase inversion- inversion or sol-gel

-  Experiments for using MIP in SPR sensors for drug detection, including the soft of new sensor (Institute for Automation and Control Processes IACP FEB RAS). The outcome of this objective will be the technology for MIP-SPR biosensor

-  Testing of the new sensors, mechanical and electronic design and validation of the technical characteristics (SC Caloris). The outcome of this objective will be a demonstrator to prove the possibility to develop this kind of sensors at a commercial scale.

• Foreseen results:

The achievement of the project tasks will allow a future commercial production of more reliable and less expensive on filed devices, for the detection and monitoring of illicit drug transportation. Very important the new biosensors may be subsequently developed as automatic devices with remote control. This kind of devices is very useful for border passing controls, especially on the airport, where big flux of passengers and baggage are registered.

At the same time the project running will allow the acquisition of new knowledge about molecularly imprinted polymers (especially films and membranes) for SPR transducers, for electronic and soft development, allowing, at the level of the international consortium, the application for at least 2 patents, publication of at least 5 ISI articles and presentation of at least 4 communications at scientific events.

Economic results

Providing economic sustainable development, at regional and sectorial level; Increasing

turnover and income value for the project involved SME ; Development of technological performance and

competitiveness on the market of the interested industrial partners.

Scientific results:

The innovative scientific potential of the expected results is very high, taking into consideration the many original aspects. This will enable the consortium to publish high quality articles and to ask patents in their countries and at European level. Till now few biosensors are produced at commercial scale. The need of such sensors and their lack on the market, as well as the importance of preventing illicit transport of drugs opens great opportunities for producing and selling these devices with high profit rate. The knowledge gained in the project could be used for other contraband substances detection and monitoring.

Ecological results:

The project contributes to a friendly environment trough manufacture of new biosensors for the field monitoring of drugs. The project aims in environment protection are: monitoring illicit drugs transportation, obeying regulations concerning working place quality and of the whole environment, fulfillment of the requests related to quality of environment, including bioethics and biosecurity

Social results:

- Providing human health, Setting up opportunities for education;

- Creating new jobs in theresearch unities and in interested beneficiary,

- Drawing young students and graduates in research activity

The main social impact will be of maintaining the health of the population from UE countries and Russia by preventing the illicit commerce with drugs. All over the world, billions of dollars are spent annually on chemical/biological detection related to medical diagnosis, environmental monitoring, public security and food safety because laboratory analysis using expensive equipment is usually cumbersome and time-consuming.

National Research- Development Institute for Chemistry and Petrochemistry  

                Building of ICECHIM, Spl. Independentei nr. 202,
                sector 6, Bucuresti, O.P. 35, CP 174 cod postal 060021

Coordinator:

Institute of Automation and Control Processes of Far Eastern Branch of Russian Academy of Sciences having  headquarters at  5, Radio Str., Vladivostok, 690041, Russia, project dirctor and coordinating director; prof. Oleg Vitrik

 Partner 1 - National Research- Development Institute for Chemistry and Petrochemistry ICECHIM, having  headquarters in Bucuresti Splaiul Independentei nr. 202, sector 6, tel.0213153299, fax 0213123493 Project director: Dr.ing. Andrei Sarbu- Main Scientific Researcher I degree

 Partner 2 -  University of Toulon,  Acting in the name of and behalf of Laboratory MAPIEM having  headquarters at Avenue de l’université – 83130, La Garde - France,  Project director, prof. Hugues Brisset

 Partner 3- S.C. Caloris Group S.A. having  headquartersat8 A, Soseaua Berceni Street, 041914, Bucharest, Romania, Project director Dr.ing. Nicolae Maruntelu, Main Scientific Researcher I degree

EXECUTIVE UNIT FOR FINANCING HIGHER  EDUCATION , RESEARCH  DEVELOPMENT AND INNOVATION

 Program 4 – Partnerships in  priority areas

Conducere Generala CNMP

Director General
Adrian Curaj
Tel: 0213071910
Fax: 0213071919

Address: UEFISCDI  Str. Mendeleev, nr. 21-25, Etaj 3, cam. 321, Sector 1, Bucuresti

Cofunded by European Commission

• January 2016 -  June 2018 (30 month)

Phase list

1. Sarbu Andrei- CS1- project director
2. Bacalum Fanica- CS1- team member
3. Ianchis Raluca- CS 1- team member
4. Purcar Violeta- CS 1- team member
5. Iancu Stela- CS 2- team member
6. Duldner Monica- CS 2- team member
7. Radu Anita- Laura- CS2- team member
8. Nistor Cristina –Lavinia- CS2- team member
9. Iordache Tanta Verona- CS3- team member
10. Zaharia Anamaria- CS3- team member
11. Sandu Teodor- CS3- team member
12. Apostol Steluta- CS3- team member
13. Florea Ana- Mihaela- CS- team member
14. Cursaru Bogdan- ACS- team member
15. Georgescu Bianca Elena- ACS- team member
16. Spatarelu Catalina Paula- ACS- team member
17. Iordachescu Antoaneta- Sing- team member
18. Dominteanu Eugen- Tehn. Pr.- team member
19. Berbec Marioara- Tehn. Pr.- team member

Annex 2 - Public Report Stage 2

Drug abuse is a global problem that directly or indirectly affects the health and well-being of the population. Illicit drugs are those drugs for which use outside medical purposes is prohibited by national or international law. Therefore, it is very important to develop methods for detecting the presence of these unlawful compounds. There are several detection methods, but lately, the use of chemical sensors, characterized by rapid response and portability, is increasingly preferred. In this area, it should be noted that studies and the number of articles on the use of SPR sensors are on the increase.

The design of an optical sensor is made primarily by the application for which it is developed. Sensors can be used for a large number of applications. Chemical sensors are simple, low-cost devices and allow applications in vast areas. A sensor must exhibit a good selectivity, sensitivity, stability for a more efficient operation. The characteristics that a sensor should have are: relatively high signal-to-noise ratio, short response time, high sensitivity, low cost. Biomimetic sensors can be used as an on-site method and can provide sufficient information for routine testing and transport screening.

Due to excellent properties such as low cost, high stability, easy preparation, applicability in many areas, molecularly imprinted polymers (MIPs) have attracted attention in recent years. Molecular imprinting is a technique that gives molecular recognition properties to a polymeric matrix, the principle being also called the "key in the lock".

MIPs can be synthesized by several methods, which are chosen depending on the application, the amount to be detected, the thickness of the film, the desired porosity, the nature of the templates and their functional groups.

The researches carried out in Stage 2 of the project focused on getting MIP sensitive layers for an SPR sensor to detect illicit drug trafficking. Since research on the phase inversion method has yielded less appropriate results, research has focused on getting the so-called sol-gel layers.

At this stage of the project, depositions were made (obtained by the sol-gel method) on the three supports (glass support, gold sensor and optical fibers), in order to develop the sensor, based on SPR detection, for the detection of ephedrine and LSD. In the next step, methamphetamine will also be used as the target analyte.

In the first two experimental chapters are described the methods of synthesis and characterization of ephedrine and LSD imprinted films (using the recipe proposed in the first stage of the project).

 After the filming, the films were analyzed to determine the properties. The FTIR structural analysis does not provide too much information: it was possible to observe the peaks of both the polymer-containing groups and the groups contained in the template (ephedrine and LSD).

Acording to the re-adsorption tests of ephedrine films, MIP obtained by dilution (MIP dil) shows better characteristics. It presented a very high imprinting factor equal to 6, which attests to the specificity and good properties of recognition. The thermo-gravimetric analysis confirms the thermal stability of the films obtained by this method.

The morphological analysis shows the differences between the films deposited on the three different supports. Dilution led to films with better behavior. The films deposited on the glass support were homogeneous compared to those deposited on the glass fibers and on the gold sensor, the latter presenting air bubbles and cracks in the structure.

In the next step optimization of the ephedrine film synthesis technology will be aimed and the methods for improving the compatibility with the gold support of the optical sensor will be studied. Subsequently, the ability of films to recognize both ephedrine and methamphetamine from alcoholic solutions will be tested. LSD films will also be optimized for better compatibility with the support and tested for selective LSD retention in acetonitrile solutions.

Further, in Chapter 3 of the experimental part it was presented the technology of preparation of ephedrine imprinted films according to MIP dil recipe, for which important results were obtained, proving also a good reproducibility with the results obtained in the previous stage, in order to construct the final optical sensor.

In terms of dissemination activity, 1 ISI article was published in the Journal of Lightwave Technology with impact factor 3,671 and an article revision is accepted in an ISI magazine with 3.531 impact factor (European Polymer Journal). Another article is already accepted in Revista de chimie (impact factor 1,232). Four scientific communications were presented at international symposia. A participation in the 2017 Romanian research exhibition took place, with a poster on a patent application in the field of the project. Two patent applications have been filed.

Rezumatul etapei 2

Abuzul de droguri este o problema globala, care afecteaza in mod direct sau indirect sanatatea si bunastarea populatiei. Drogurile ilicite sunt acele droguri pentru care utilizarea in afara scopurilor medicale este interzisa prin legi nationale sau internationale. De aceea este foarte importanta dezvoltarea de metode de detectie a prezentei acestor compusi ilegali. Exista mai multe metode de detectie, dar in ultima perioada se prefera tot mai mult utilizarea senzorilor chimici, caracterizati prin raspuns rapid si portabilitate. In cadrul acestui domeniu trebuie remarcat ca studiile si numarul articolelor privind utilizarea senzorilor SPR sunt in crestere continua.

Proiectarea unui senzor optic este, realizata in primul rand, functie de aplicatia pentru care este dezvoltat. Senzorii pot fi utilizati la un numar mare de aplictii. Senzorii chimici sunt dispozitive simple, realizate cu costuri scazute si permit aplicatii in vaste domenii. Un senzor trebuie sa prezinte o buna selectivitate, senzitivitate, stabilitate pentru o functionare cat mai eficienta. Caracteristicile pe care trebuie sa le aiba un senzor sunt: raportul semnal-zgomot relativ ridicat, timp scurt de raspuns, senzitivitate ridicata, cost redus. Senzorii biomimetici se pot utiliza ca metoda „la fata locului” si pot furniza informatii suficiente pentru testarea de rutina si screeningul transporturilor.

           Datorita proprietatilor excelente, cum ar fi costul scazut, stabilitate mare, preparare usoara, aplicabilitate in multe domenii, MIP au atras atentia in ultimii ani. Imprentarea moleculara este o tehnica prin care se confera proprietati de recunoastere moleculara unei matrici polimerice, modelul fiind numit si „cheie in broasca”.

           MIP  se pot sintetiza prin mai multe metode, acestea fiind alese functie de aplicatie, de cantitatea care trebuie determinata, de grosimea filmului, de porozitatea dorita, de natura templatului si de gruparile functionale.

           Cercetarile efectuate in etapa 2 a proiectului s-au axat pe obtinerea straturilor senzitive de MIP pentru un senzor SPR de detectie a transportului ilicit de droguri. Intrucat cercetarile privind metoda de inversie de faza au dat rezultate mai putin adecvate, cercetarile s-au axat pe obtinerea straturilor senzitive prin metoda sol-gel.

           In aceasta etapa de derulare a proiectului s-au realizat depuneri de filme (obtinute prin metoda sol-gel) pe cele trei suporturi (suport sticla, senzor aur si fibre optice), in vederea dezvoltarii senzorului, bazat pe detectia SPR, pentru detectia efedrinei si LSD-ului. In etapa urmatoare va a fi utilizata si metamfetamina ca analit tinta.

           In primele doua capitole experimentale sunt descrise metodele de sinteza si de caracterizare a filmelor imprentate cu efedrina si cu LSD (dupa reteta propusa in prima etapa).

           Dupa depunere, filmele au fost analizate in vederea determinarii proprietatilor. Analiza structurala FTIR nu ofera prea multe informatii: au putut fi observate peak-uri, atat ale gruparilor continute de polimer, cat si ale gruparilor continute in templat (efedrina si LSD).

           In urma testelor de re-adsorbtie ale filmelor obtinute cu efedrina, MIP obtinut prin diluare prezinta caracteristici mai bune. Acesta a prezentat un factor de imprentare foarte ridicat, egal cu 6, ceea ce atesta specificitatea si proprietatile bune de recunoastere. Analiza termo-gravimetrica atesta stabilitatea termica a filmelor obtinute prin aceasta metoda.

           Analiza morfologica arata diferentele dintre filmele depuse pe cele trei suporturi diferite. Dilutia a condus la filme cu un comportament mai bun. Filmele depuse pe suportul de sticla au fost omogene in comparatie cu cele depuse pe fibrele de sticla si pe senzorul de aur, ultimele prezentand bule de aer si crapaturi in structura.

           In etapa urmatoare se va optimiza tehnologia de sinteza a filmelor cu efedrina in care se va studia intens si metoda de compatibilizare cu suportul din aur al senzorului optic. Se va testa ulterior abilitatea filmelor de a recunoaste atat efedrina cat si metamfetamina din solutii alcoolice. Filmele cu LSD vor fi si ele optimizate pentru compatibilizarea cu suportul si testate pentru retentia selectiva de LSD din solutii de acetonitril.

           In continuare, in capitolul 3 al partii experimentale, a fost prezentata tehnologia de preparare a filmelor imprentate cu efedrina conform retetei MIP dil pentru care au fost obtinute rezultate importante in vederea construirii senzorului optic final dar si o buna reproductibilitate fata de rezultatele obtinute in etapa anterioara.

In ceea ce priveste activitatea de diseminare a fost publicat 1 articol ISI in Journal of Lightwave Technology cu factor de impact 3,671, este acceptat spre publicare pentru anul 2018 un alt articol ISI (FI 1,232) si este acceptat cu revizie majora un articol intr-o revista ISI cu factor de impact 3,531. Au fost prezentate 4 comunicari stiintifice, la simpozioane internationale. S-a participat la expozitia cercetarii 2017, cu un poster privind o cerere de brevet in domeniul proiectului. Au fost depuse 2 cereri de brevet.

Annex 3 - Public Report Stage 3

• http://uefiscdi.gov.ro/
• http://www.icechim.ro/
• http://www.icechim-pd.ro/ro/pol_hitech/polimeri_hitech.html

Dr.ing. Andrei SARBU,  

Tel: 0213128501/127

Fax: 0213123493

e-mail: andr.sarbu@gmail.com

INCDCP-ICECHIM Bucuresti
Departamentul polimeri

Spl. Independentei 202, sector 6, Bucuresti
ROMANIA